JP2009088553A - Group-iii nitride semiconductor layer, light emitting layer, and iii-group nitride semiconductor light emitting element - Google Patents

Group-iii nitride semiconductor layer, light emitting layer, and iii-group nitride semiconductor light emitting element Download PDF

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JP2009088553A
JP2009088553A JP2008308203A JP2008308203A JP2009088553A JP 2009088553 A JP2009088553 A JP 2009088553A JP 2008308203 A JP2008308203 A JP 2008308203A JP 2008308203 A JP2008308203 A JP 2008308203A JP 2009088553 A JP2009088553 A JP 2009088553A
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nitride semiconductor
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Yu Kikuchi
友 菊池
Takashi Udagawa
隆 宇田川
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Resonac Holdings Corp
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Showa Denko KK
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Abstract

<P>PROBLEM TO BE SOLVED: To provide a group-III nitride semiconductor while-color light emitting element having high light intensity and color rendering property, which is easily formed in a simple structure while eliminating the need for delicate composition adjustment of phosphor. <P>SOLUTION: The group-III nitride semiconductor layer 5b provided on the surface of a substrate 1 forms one or more well layer 5b as part of a light emitting layer 5 in a multiple quantum well structure. It is formed of a n-type gallium indium nitride (a composition formula Ga<SB>x</SB>In<SB>1-x</SB>N: 0<x<1) to which acceptor impurities are added and which shows such multiple wavelength light emission that a plurality of lights numerically independent and different in wavelength are emitted at the same time separately from a band end light emission. The gallium indium nitride has an indium composition of 0.01 to 0.25 and contains magnesium having an atom concentration of 4×10<SP>17</SP>cm<SP>-3</SP>to 1×10<SP>19</SP>cm<SP>-3</SP>, as acceptor impurities. <P>COPYRIGHT: (C)2009,JPO&INPIT

Description

本発明は、基板と、その基板の表面上に設けたガリウムを含むIII族窒化物半導体材料からなる障壁層及び井戸層を備えた多重量子井戸構造の発光層とを具備したIII族窒化物半導体発光素子、その井戸層をなすIII族窒化物半導体層、および発光層に関する。   The present invention relates to a group III nitride semiconductor comprising a substrate, and a light emitting layer having a multiple quantum well structure including a barrier layer and a well layer made of a group III nitride semiconductor material containing gallium provided on the surface of the substrate The present invention relates to a light emitting element, a group III nitride semiconductor layer forming the well layer, and a light emitting layer.

従来から、窒化ガリウム・インジウム(GaInN)等のIII族窒化物半導体材料は、白色又は青色等の短波長の発光ダイオード(英略称:LED)やレーザーダイオード(英略称:LD)の発光層を構成するために利用されている(例えば、特許文献1参照)。また、窒化アルミニウム・ガリウム(AlGaN)は、近紫外LED又は紫外LEDの発光層を構成するための材料として用いられている(例えば特許文献2参照)。   Conventionally, a group III nitride semiconductor material such as gallium nitride / indium (GaInN) constitutes a light emitting layer of a light emitting diode (abbreviation: LED) or laser diode (abbreviation: LD) of a short wavelength such as white or blue. It is used for this purpose (see, for example, Patent Document 1). Aluminum gallium nitride (AlGaN) is used as a material for forming a light emitting layer of a near-ultraviolet LED or an ultraviolet LED (see, for example, Patent Document 2).

従来の白色LEDの一種は、光の3原色(赤(R)、緑(G)及び青(B))の各色光を各々出射する、チップ(chip)状又はランプ状の赤色LED、緑色LED及び青色LEDを、それらの発光強度の相対的比率に相応した個数をもって、同一の基体上に集積して配列させ、総体として、混色により白色光を発するようにしたものである(例えば特許文献3乃至9参照)。言わば、配列型(モジュール)白色LEDである。   A type of conventional white LED is a chip-shaped or lamp-shaped red LED or green LED that emits light of each of the three primary colors of light (red (R), green (G), and blue (B)). And blue LEDs are arranged on the same substrate in a number corresponding to the relative ratio of their emission intensity, and as a whole, white light is emitted by color mixing (for example, Patent Document 3). To 9). In other words, it is an array type (module) white LED.

また、従来の白色LEDの別の一種は、一基板上に別個に形成された、赤色光又は緑色光又は青色光をそれぞれ出射する、例えばIII族窒化物半導体からなる発光層を利用して構成されている(例えば特許文献10及び11参照)。個々の発光層から出射される光の3原色(赤(R)、緑(G)及び青(B))に相応する発光を混色させることにより、白色を呈することとした、言わば、RGB型白色LEDである。   In addition, another type of conventional white LED is configured using a light emitting layer made of, for example, a group III nitride semiconductor, which emits red light, green light, or blue light separately formed on one substrate. (See, for example, Patent Documents 10 and 11). It is assumed that white color is exhibited by mixing light emission corresponding to the three primary colors (red (R), green (G), and blue (B)) of light emitted from each light emitting layer. LED.

また、従来の白色LEDの他の一種は、補色の関係にある色の光を出射する発光層を、単一の基板上に各々設けて構成した白色LEDである。例えば、青色光を出射するIII族窒化物半導体発光層と、黄色光を出射する発光層とを、同一基板上に各々形成し、その各々の発光層から出射される異なる2波長の2色(例えば、青色及び黄色)の光を混色させることによる白色LEDである(例えば特許文献12参照)。補色関係にある2色(2波長)の光を混色させれば、白色と視認されることを利用した、言わば、補色型白色LEDである。   In addition, another type of conventional white LED is a white LED in which a light emitting layer that emits light of a complementary color is provided on each single substrate. For example, a group III nitride semiconductor light emitting layer that emits blue light and a light emitting layer that emits yellow light are formed on the same substrate, and two different wavelengths of two colors emitted from the respective light emitting layers ( For example, a white LED obtained by mixing blue and yellow light (for example, see Patent Document 12). It is a complementary color type white LED that utilizes the fact that light of two colors (two wavelengths) in a complementary color relationship is mixed to be visually recognized as white.

また、上記の3種の型のLEDとは別に、III族窒化物半導体発光層から出射される光を利用して、その発光層から出射される光とは異なる波長の蛍光を発する蛍光体を励起させ、発光の波長を変換させるLEDである(例えば特許文献13参照)。例えば、III族窒化物半導体発光層から出射される青色光又は紫外光を利用して蛍光体を励起し、白色光を発するLEDとした、言わば、蛍光型白色LEDである(例えば特許文献14乃至16参照)。青色光又は紫外光により励起されて白色を呈する蛍光体として、イットリウム・アルミニウム・ガーネット(Y3Al512)などが用いられている(例えば特許文献17乃至19参照)。
特公昭55−3834号公報 特開2001−60719号公報 特開平06−314824号公報 特開平07−7223号公報 特開平07−15044号公報 特開平07−235624号公報 特開平07−288341号公報 特開平07−283438号公報 特開平07−335942号公報 特開平06−53549号公報 特開平07−183576号公報 特開2001−257379号公報 特開平07−99345号公報 特許第2900928号公報 特許第3724490号公報 特許第3724498号公報 特許第2927279号公報 特許第3503139号公報 特許第3700502号公報
In addition to the above three types of LEDs, a phosphor that emits fluorescence having a wavelength different from that of the light emitted from the light emitting layer is obtained using light emitted from the group III nitride semiconductor light emitting layer. It is an LED that excites and converts the wavelength of light emission (see, for example, Patent Document 13). For example, an LED that emits white light by exciting a phosphor using blue light or ultraviolet light emitted from a group III nitride semiconductor light emitting layer is a so-called fluorescent white LED (for example, Patent Documents 14 to 14). 16). Yttrium, aluminum, garnet (Y 3 Al 5 O 12 ) or the like is used as a phosphor that is excited by blue light or ultraviolet light and exhibits white (see, for example, Patent Documents 17 to 19).
Japanese Patent Publication No.55-3834 JP 2001-60719 A Japanese Patent Laid-Open No. 06-314824 Japanese Patent Application Laid-Open No. 07-7223 Japanese Patent Laid-Open No. 07-15044 Japanese Patent Application Laid-Open No. 07-235624 JP 07-288341 A Japanese Patent Laid-Open No. 07-283438 JP 07-335842 A Japanese Patent Laid-Open No. 06-53549 Japanese Patent Laid-Open No. 07-183576 JP 2001-257379 A Japanese Patent Application Laid-Open No. 07-99345 Japanese Patent No. 2900928 Japanese Patent No. 3724490 Japanese Patent No. 3724498 Japanese Patent No. 2927279 Japanese Patent No. 3503139 Japanese Patent No. 3700502

しかしながら、上記の配列型白色LEDにあっては、例えば、赤色又は緑色又は青色LEDのチップ又はランプを集積して配列するに必要な据え付け平面積に比較して、それらの各色を出射する発光層の平面積は格段に小さい(上記の特許文献3,5乃至9参照)。すなわち、ランプを敷設するために必要とされる平面積に対して、発光をもたらす発光層が占有する平面積が極小であるため、高い光度(ルーメン/面積)の発光素子を得るには不利である。   However, in the above-described array type white LED, for example, a light emitting layer that emits each color thereof as compared with the installation plane area necessary for stacking and arranging red, green, or blue LED chips or lamps. The plane area is significantly smaller (see Patent Documents 3, 5 to 9 above). That is, since the plane area occupied by the light emitting layer that emits light is extremely small compared to the plane area required for laying the lamp, it is disadvantageous for obtaining a light emitting element with high luminous intensity (lumen / area). is there.

例えば、一辺を0.3mmとする略正方形のLEDチップを、樹脂で囲繞して、垂直断面を砲弾型とし、水平断面を円形とする一般的な形状のランプとなした場合、そのランプの外径(直径)は、一般的には、3mmから5mmである(上記の特許文献3の段落[0007]参照)。従って、外径を5mmとするランプの場合を例にすれば、そのランプの平面積(約20mm2)に比較して、発光層がチップの平面全体に存在しているとしても、その平面積は0.09mm2と格段に小さい。従って、より高光度の発光素子を得るに決して優位とはならない。 For example, if an approximately square LED chip with a side of 0.3 mm is surrounded by a resin and the lamp has a general shape with a vertical cross section of a round shape and a horizontal cross section of a round shape, The diameter (diameter) is generally 3 mm to 5 mm (see paragraph [0007] of Patent Document 3 above). Accordingly, in the case of a lamp having an outer diameter of 5 mm, even if the light emitting layer is present on the entire plane of the chip as compared with the flat area of the lamp (about 20 mm 2 ), the flat area is the same. Is remarkably small at 0.09 mm 2 . Therefore, there is no advantage in obtaining a light emitting device with higher luminous intensity.

また、上記のRGB型白色LEDにあっては、赤色(R)又は緑色(B)又は青色(B)を各々出射できる発光層を、個別に設ける必要がある。複数の発光層を設ける必要があることに加えて、発光層に担体(carrier;電子及び正孔)を閉じ込めて、また、それらの放射再結合によりもたらされる発光を閉じ込めるために、発光層に付帯してクラッド(clad)層等を上記の各発光層につき設けることも必要となる。従って、単一の基板上に複数の発光層と、更に望ましくは、各々の発光層にヘテロ(異種)接合させてクラッド層等を設ける必要があるなど、RGB型白色LEDを形成するための工程は煩雑であり、また冗長である。その場合、異なる色の光を出射する発光層毎にp形及びn形用の電極を設ける必要があり、対応する電気伝導型のクラッド層等に電極を設けるために発光層が削り取られることとなり、各発光の光度も悪化することになる。   Moreover, in said RGB type white LED, it is necessary to provide the light emitting layer which can each radiate | emit red (R), green (B), or blue (B) separately. In addition to the need to provide a plurality of light emitting layers, in order to confine carriers (electrons and holes) in the light emitting layer and to confine the light emission caused by their radiative recombination, the light emitting layer has an incidental effect. Thus, it is necessary to provide a clad layer or the like for each light emitting layer. Accordingly, a process for forming an RGB type white LED, such as a plurality of light emitting layers on a single substrate, and more preferably, a clad layer or the like that is heterojunction bonded to each light emitting layer is required. Is cumbersome and redundant. In that case, it is necessary to provide an electrode for p-type and n-type for each light-emitting layer that emits light of different colors, and the light-emitting layer is scraped off in order to provide an electrode on the corresponding electrically conductive cladding layer or the like. The luminous intensity of each light emission will also deteriorate.

また、上記の補色型白色LEDにあっては、補色関係にある色の光を出射させるために、やはり2またはそれ以上の複数の発光層が必要とされる。更に、高い強度の発光を得るためには、上記のRGB型白色LEDの場合と同様に、各発光層について、クラッド層を接合させ、単一(single)ヘテロ(英略称:SH)又は二重(double)ヘテロ(英略称:DH)接合構造の発光部を形成する必要がある。従って、補色型白色LEDの形成には、RGB型白色LEDの場合と同じく、煩雑で冗長な工程を要する。   Further, in the above complementary color type white LED, in order to emit light having a complementary color, two or more light emitting layers are also required. Further, in order to obtain high intensity light emission, as in the case of the RGB type white LED, a clad layer is bonded to each light emitting layer, and a single hetero (English abbreviation: SH) or double It is necessary to form a light emitting portion having a (double) hetero (English abbreviation: DH) junction structure. Therefore, the formation of the complementary white LED requires a complicated and redundant process, as in the case of the RGB white LED.

また、補色の関係にある色、例えば、青色と黄色とを個別に発光するLEDを近接させて配置して、白色LEDを構成する場合においても(「ワイドギャップ半導体光・電子デバイス」(2006年3月31日、森北出版(株)発行、第1版第1刷)、173〜174頁参照)、LEDを配置するのに必要な平面積に比較して、青色又は黄色の光を出射する発光層の合計の平面積が小さいため、高い光度の発光素子を得るのに必ずしも優位とは成り得ない。   In addition, even in the case where white LEDs are formed by arranging LEDs that emit complementary colors, such as blue and yellow, close to each other (“Wide Gap Semiconductor Optical / Electronic Device” (2006) March 31, published by Morikita Publishing Co., Ltd., 1st edition, 1st printing), pp. 173-174), emits blue or yellow light compared to the plane area required for LED placement Since the total plane area of the light emitting layer is small, it cannot necessarily be advantageous for obtaining a light emitting element with high luminous intensity.

加えて、補色型白色LEDにあっては、白色光を得るために混色させる補色の関係にある2色の光の波長に依存して、帰結される白色光の色調が微妙に変化してしまう問題がある。すなわち、補色型白色LEDにあって、混色させるのは、通常高々、2波長の光であるため、いずれにしても、高く一定した演色性をもたらす白色LEDを安定して得るには技術上の困難さを伴うものとなっている。   In addition, in the complementary color type white LED, the color tone of the resulting white light slightly changes depending on the wavelengths of the two colors of light that are complementary to each other to obtain white light. There's a problem. That is, in a complementary color type white LED, since it is usually light of two wavelengths at most, it is technically necessary to stably obtain a white LED that provides high and constant color rendering in any case. It is difficult.

また、上記の蛍光型白色LEDにあってもやはり、蛍光体を励起して色調の一定した白色光を安定して得るには、励起光となる発光層からの発光の波長を再現良く一定にしなければならない技術上の困難さが付随する。また、発光層からの発光の波長のばらつきに応じて、蛍光体として用いる希土類(rare−earth)元素を添加したY3Al512などの組成を人為的に細々と調整する必要がある。 In addition, even in the above-described fluorescent white LED, in order to stably obtain white light having a constant color tone by exciting the phosphor, the wavelength of light emitted from the light emitting layer, which becomes excitation light, is made constant with good reproducibility. There are technical difficulties that must be met. In addition, it is necessary to artificially adjust the composition of Y 3 Al 5 O 12 and the like to which a rare-earth element used as a phosphor is added according to variations in the wavelength of light emitted from the light emitting layer.

本発明は上記事情に鑑みてなされたもので、簡単な構造で簡易に形成することができ、光度を高めることができ、また演色性も高く一定に安定させることができ、さらに蛍光体の微妙な組成調整も不要となるIII族窒化物半導体発光素子、III族窒化物半導体層および発光層を提供することを目的としている。   The present invention has been made in view of the above circumstances, and can be easily formed with a simple structure, can increase the luminous intensity, can also have a high color rendering property and can be stably stabilized, and can further subtle the phosphor. An object of the present invention is to provide a group III nitride semiconductor light emitting device, a group III nitride semiconductor layer, and a light emitting layer that do not require any composition adjustment.

上記目的を達成するための本発明は、(a)基板の表面上に設けられた、多重量子井戸構造の発光層を構成する1または複数の井戸層を形成するIII族窒化物半導体層において、アクセプター不純物が添加され、バンド端発光とは別に、数的に単独で、波長を相違する複数の発光を同時に出射する多波長発光を呈するn形の窒化ガリウム・インジウム(組成式GaXIn1-XN:0<X<1)から構成され、上記窒化ガリウム・インジウムは、インジウム組成(1−X)が0.01以上で0.25以下で、アクセプター不純物としてマグネシウム(Mg)を、4×1017cm-3以上で1×1019cm-3以下の原子濃度で含む、ことを特徴とするIII族窒化物半導体層である。
また、上記目的を達成するための本発明は、(b)基板の表面上に設けられた、1または複数の井戸層を備える多重量子井戸構造の発光層において、上記井戸層は、上記(a)項に記載のIII族窒化物半導体層であり、当該発光層は、井戸層に含有されたマグネシウムが形成する準位に因り、波長を相違する複数の発光を出射する、ことを特徴とする発光層である。
また、上記目的を達成するための本発明は、(c)基板の表面上に設けられた、n形のIII族窒化物半導体層を井戸層とする多重量子井戸構造の発光層を具備したIII族窒化物半導体発光素子において、上記井戸層は、アクセプター不純物が添加され、バンド端発光とは別に、数的に単独で、波長を相違する複数の発光を同時に出射する多波長発光を呈するn形の窒化ガリウム・インジウム(組成式GaXIn1-XN:0<X<1)から構成され、上記窒化ガリウム・インジウムは、インジウム組成(1−X)が0.01以上で0.25以下で、アクセプター不純物としてマグネシウム(Mg)を、4×1017cm-3以上で1×1019cm-3以下の原子濃度で含む、ことを特徴とするIII族窒化物半導体発光素子である。
また、(1)第1の発明は、基板と、その基板の表面上に設けたガリウムを含むIII族窒化物半導体材料からなる障壁層及び井戸層を備えた多重量子井戸構造の発光層とを具備したIII族窒化物半導体発光素子において、上記多重量子井戸構造をなす井戸層の各々は、障壁層と同一の伝導形を呈するIII族窒化物半導体層からなり、アクセプター不純物が添加され、互いに層厚を異にしている、ことを特徴としている。
In order to achieve the above object, the present invention provides (a) a group III nitride semiconductor layer which is provided on the surface of a substrate and forms one or a plurality of well layers constituting a light emitting layer having a multiple quantum well structure. In addition to the band edge emission, an n-type gallium indium nitride (compositional formula Ga x In 1− X N: 0 <X <1), the gallium nitride indium has an indium composition (1-X) of 0.01 to 0.25 and magnesium (Mg) as an acceptor impurity is 4 × A group III nitride semiconductor layer comprising an atomic concentration of 10 17 cm −3 or more and 1 × 10 19 cm −3 or less.
In order to achieve the above object, the present invention provides: (b) a light emitting layer having a multiple quantum well structure including one or a plurality of well layers provided on a surface of a substrate, wherein the well layer includes the above (a) The group III nitride semiconductor layer described in the item (1), wherein the light emitting layer emits a plurality of light emissions having different wavelengths depending on a level formed by magnesium contained in the well layer. It is a light emitting layer.
In order to achieve the above object, the present invention provides (c) a light emitting layer having a multiple quantum well structure provided on the surface of a substrate and having an n-type group III nitride semiconductor layer as a well layer. In the group nitride semiconductor light-emitting device, the well layer is doped with an acceptor impurity, and separately from the band-edge light emission, the well layer exhibits n-type light emission that emits a plurality of light emissions having different wavelengths simultaneously. Gallium nitride indium (composition formula Ga x In 1-X N: 0 <X <1), and the gallium nitride indium has an indium composition (1-X) of 0.01 or more and 0.25 or less. The group III nitride semiconductor light-emitting device includes magnesium (Mg) as an acceptor impurity at an atomic concentration of 4 × 10 17 cm −3 or more and 1 × 10 19 cm −3 or less.
(1) In the first invention, there is provided a substrate and a light emitting layer having a multiple quantum well structure including a barrier layer and a well layer made of a group III nitride semiconductor material containing gallium provided on the surface of the substrate. In the group III nitride semiconductor light-emitting device provided, each of the well layers having the multiple quantum well structure is composed of a group III nitride semiconductor layer having the same conductivity type as the barrier layer, and acceptor impurities are added to each other to form a layer. It is characterized by having different thicknesses.

(2)第2の発明は、上記した(1)項に記載の発明の構成において、上記多重量子井戸構造をなす井戸層の各々が、基板の表面側より発光層からの発光を取り出す方向に向けて、層厚が順に薄くなっているものである。   (2) According to a second invention, in the configuration of the invention described in the above item (1), each of the well layers having the multiple quantum well structure is configured to extract light emitted from the light emitting layer from the surface side of the substrate. Towards, the layer thickness is gradually reduced.

(3)第3の発明は、上記した(1)項または(2)項に記載の発明の構成において、上記多重量子井戸構造をなす井戸層の各々は、アクセプター不純物の原子濃度が互いに異なっているものである。   (3) According to a third invention, in the configuration of the invention described in the above item (1) or (2), each of the well layers forming the multiple quantum well structure has different atomic concentrations of acceptor impurities. It is what.

(4)第4の発明は、上記した(1)項乃至(3)項の何れかに1項に記載の発明の構成において、上記基板は珪素単結晶からなり、上記多重量子井戸構造をなす井戸層の各々は、アクセプター不純物としてマグネシウムが故意に添加されているものである。   (4) According to a fourth invention, in the configuration of the invention described in any one of the above items (1) to (3), the substrate is made of a silicon single crystal and forms the multiple quantum well structure. Each of the well layers is intentionally added with magnesium as an acceptor impurity.

本発明によれば、発光層が障壁層と井戸層の多重量子井戸構造となるので、簡単な構造で簡易に白色系発光素子を形成することができ、敷設面積も発光層の平面積と略同一となるので光度も高めることができる。また、数的に単一ながら、多波長の発光をもたらせる多重量子井戸構造の発光層を用いることとしたので、その唯一の発光層についてのみp形及びn形用の電極を設ければよく、従来のRGB型白色LEDの場合に比較して、発光層を削り取らなければならない領域を大幅に低減でき、発光効率を改善することができる。   According to the present invention, since the light emitting layer has a multiple quantum well structure including a barrier layer and a well layer, a white light emitting element can be easily formed with a simple structure, and the laying area is substantially equal to the plane area of the light emitting layer. Since they are the same, the luminous intensity can be increased. In addition, since a light emitting layer having a multi-quantum well structure capable of emitting light of multiple wavelengths although being numerically single is used, if electrodes for p-type and n-type are provided only for that single light-emitting layer. As compared with the case of the conventional RGB type white LED, the area where the light emitting layer has to be scraped can be greatly reduced, and the light emission efficiency can be improved.

特に、井戸層を、層厚を相違する複数の井戸層から構成することとしたので、多色発光を呈する各井戸層がもたらす複数の発光の波長を重畳することができ、白色発光の演色性を高く一定に安定させることができ、また、蛍光材料を利用しなくても白色光を得ることができるので、蛍光体の微妙な組成調整も不要となる。   In particular, since the well layer is composed of a plurality of well layers having different layer thicknesses, it is possible to superimpose a plurality of wavelengths of light emitted by each well layer exhibiting multicolor light emission, and color rendering of white light emission. Since the white light can be obtained without using a fluorescent material, fine composition adjustment of the phosphor becomes unnecessary.

また、井戸層の各々にアクセプター不純物を故意に添加したので、単独でも、波長を相違する多色の発光をもたらす井戸層を構成することができ、数的に単一でありながら多色発光を呈する多重量子井戸構造の発光層をもたらせるので、白色発光の演色性を高く一定に安定させることができ、また、蛍光材料を利用しなくても白色光を得ることができるので、蛍光体の微妙な組成調整も不要となる。   In addition, since the acceptor impurity is intentionally added to each of the well layers, it is possible to construct a well layer that can produce multicolor light emission having different wavelengths, and can emit multicolor light emission while being numerically single. As a light emitting layer having a multi-quantum well structure can be provided, the color rendering property of white light emission can be stabilized stably and white light can be obtained without using a fluorescent material. Subtle composition adjustment is also unnecessary.

さらに、井戸層を、障壁層と同一の伝導形を呈する層から構成することとしたので、障壁層との間でのpn接合の形成を回避でき、従って、導通性に優れる多重量子井戸構造の発光層を構成できる。   Furthermore, since the well layer is composed of a layer having the same conductivity type as that of the barrier layer, the formation of a pn junction with the barrier layer can be avoided, and therefore, the multi-quantum well structure having excellent conductivity can be avoided. A light emitting layer can be comprised.

本発明によれば、基板の表面側より発光層からの発光を取り出す方向に向けて、より層厚の薄いIII族窒化物半導体層からなる井戸層を配置して多重量子井戸構造の発光層を構成することとしたので、多重量子井戸構造を成す各井戸層から出射される発光を効率的に視野方向に取り出すことができる。   According to the present invention, a well layer made of a thin group III nitride semiconductor layer is arranged in a direction from which light emitted from the light emitting layer is extracted from the surface side of the substrate, thereby forming a light emitting layer having a multiple quantum well structure. Since it is configured, light emitted from each well layer forming the multiple quantum well structure can be efficiently extracted in the viewing direction.

短波長の発光は、長波長の発光を行う井戸層に吸収されてしまうが、本発明の構成下では、基板の表面側に井戸層幅が広く形成された、量子準位が低く長波長の発光成分を含む多波長の発光をもたらす井戸層を配置し、発光の取り出し方向に、井戸層幅が狭く形成された、量子準位が高くより短波長の発光成分を含む多波長の発光をもたらす井戸層を配置して多重量子井戸構造の発光層を構成することとした。すなわち、短波長の発光を、より長波長の発光を行う井戸層を通過させない構成とした。このため、本発明の構成下では、基板表面側に配置された井戸層から出射される発光が、発光の取り出し方向に配置された井戸層に吸収されることなく、外部視野方向に発光を取り出すことができ、各井戸層から出射される発光を効率的に視野方向に取り出すことができる。また演色性を優れたものとすることができ、且つ高輝度の白色LEDを実現することができる。   Short-wavelength light is absorbed by the well layer that emits long-wavelength light. However, under the structure of the present invention, the well layer is formed wide on the surface side of the substrate, the quantum level is low, and the long-wavelength light is A well layer that emits multi-wavelength light including a light-emitting component is disposed, and the well layer width is narrowly formed in the light-emission direction. A light emitting layer having a multiple quantum well structure is formed by arranging well layers. That is, a configuration in which light having a short wavelength is not passed through a well layer that emits light having a longer wavelength. For this reason, under the configuration of the present invention, the light emitted from the well layer disposed on the substrate surface side is not absorbed by the well layer disposed in the light extraction direction, and the light is extracted in the external visual field direction. The light emitted from each well layer can be efficiently extracted in the viewing direction. Further, the color rendering properties can be improved, and a high-intensity white LED can be realized.

本発明によれば、添加されたアクセプター不純物の原子濃度を互いに相違する、波長を相違する複数の発光を呈する井戸層を複数用いて多重量子井戸構造の発光層を構成することとしたので、数的に単一ながら多波長の発光を呈する発光層が得られ、例えば、補色関係にある二つの異なる波長の光を混色させて白色光とする、所謂、上記の補色型白色LEDに比較して、より演色性に優れる白色LEDを提供できる。   According to the present invention, the multi-quantum well structure light-emitting layer is configured by using a plurality of well layers exhibiting a plurality of light-emissions having different wavelengths and different atomic concentrations of the added acceptor impurities. As a result, it is possible to obtain a light emitting layer that emits light of multiple wavelengths although it is single, for example, as compared to the so-called complementary white LED described above, in which light of two different wavelengths having a complementary color relationship is mixed into white light. Thus, it is possible to provide a white LED that is more excellent in color rendering.

本発明の実施の形態を図面に基づいて詳細に説明する。   Embodiments of the present invention will be described in detail with reference to the drawings.

図1は本発明のIII族窒化物半導体発光素子の断面構造を概略的に示す模式図である。本発明のIII族窒化物半導体発光素子は、図1に示すように、基板1と、その基板1の表面上に設けたガリウムを含むIII族窒化物半導体材料からなる障壁層5a及び井戸層5bを備えた多重量子井戸構造からなる発光層5とを具備した白色発光素子であり、多重量子井戸構造をなす井戸層5bの各々は、障壁層5aと同一の伝導形を呈するIII族窒化物半導体層からなり、アクセプター不純物が添加され、互いに層厚を異にして構成されている。   FIG. 1 is a schematic view schematically showing a cross-sectional structure of a group III nitride semiconductor light emitting device of the present invention. As shown in FIG. 1, the group III nitride semiconductor light-emitting device of the present invention includes a substrate 1, a barrier layer 5a made of a group III nitride semiconductor material containing gallium provided on the surface of the substrate 1, and a well layer 5b. And a light-emitting layer 5 having a multiple quantum well structure and each of the well layers 5b having the multiple quantum well structure has a group III nitride semiconductor having the same conductivity type as that of the barrier layer 5a. It consists of layers, acceptor impurities are added, and the layers have different thicknesses.

基板1としては、極性又は無極性の結晶面を表面とするサファイア(α−Al23単結晶)や酸化亜鉛(ZnO)等の絶縁性又は導電性酸化物結晶、6H又は4H又は3C型炭化珪素(SiC)等の炭化物結晶、シリコン(Si)の半導体結晶からなる基板を例示できる。特に、n形又はp形の伝導性を呈し、表面を{111}結晶面とするシリコン単結晶は、その表面上に本発明に係る多重量子井戸構造を形成するための基板として好適に使用できる。 As the substrate 1, an insulating or conductive oxide crystal such as sapphire (α-Al 2 O 3 single crystal) or zinc oxide (ZnO) having a polar or nonpolar crystal plane as its surface, 6H, 4H or 3C type Examples thereof include a substrate made of a carbide crystal such as silicon carbide (SiC) or a semiconductor crystal of silicon (Si). In particular, a silicon single crystal exhibiting n-type or p-type conductivity and having a {111} crystal face as the surface can be suitably used as a substrate for forming the multiple quantum well structure according to the present invention on the surface. .

基板1の表面上に形成する多重量子井戸構造をなす井戸層5bは、本発明では、単独で波長を相違する複数の波長の発光を同時に出射できる材料から構成する。LEDからの発光の演色性を勘案すれば、井戸層5bから出射される多数(多波長)の発光は、広い波長範囲に分散していることが望ましい。広い波長範囲にわたり、多波長の発光を得るには、多重量子井戸構造にあって、井戸層5bを禁止帯幅エネルギーの大きな半導体材料から形成するのが望ましく、このようなバンドギャップエネルギーの大きな半導体材料として、ガリウム(Ga)を含むIII族窒化物半導体材料を挙げられる。例えば、窒化ガリウム(GaN)又はそれと窒化インジウム(InN)の混晶であるGaXIn1-XN(0<x<1)等のワイドバンドギャップ半導体材料から好ましく構成できる。 In the present invention, the well layer 5b having a multiple quantum well structure formed on the surface of the substrate 1 is made of a material that can emit light of a plurality of wavelengths having different wavelengths independently. Considering the color rendering properties of light emitted from the LED, it is desirable that a large number (multi-wavelength) of light emitted from the well layer 5b is dispersed in a wide wavelength range. In order to obtain multi-wavelength light emission over a wide wavelength range, it is desirable to form the well layer 5b from a semiconductor material having a large forbidden band energy in a multiple quantum well structure. An example of the material is a group III nitride semiconductor material containing gallium (Ga). For example, it can be preferably composed of a wide band gap semiconductor material such as gallium nitride (GaN) or Ga x In 1-x N (0 <x <1) which is a mixed crystal of gallium nitride (GaN) and indium nitride (InN).

井戸層5bと共に多重量子井戸構造をなす障壁層5aは、井戸層5bよりも禁止帯幅エネルギーが大きな、例えばIII族窒化物半導体材料から構成する。例えば、Ga0.85In0.15N混晶からなる井戸層5bについて、障壁層5aをGaNから形成する。多重量子井戸構造をなす障壁層5aと井戸層5bとは同一の伝導形を呈する層から構成する。例えば、n形の井戸層5bと、同じくn形の障壁層5aとで、全体としてn形の多重量子井戸構造を形成する。これにより、井戸層5bと障壁層5aとの間でのpn接合が形成されるのを回避でき、従って、導通性に優れる多重量子井戸構造の発光層5を構成できる。 The barrier layer 5a having a multiple quantum well structure together with the well layer 5b is made of, for example, a group III nitride semiconductor material having a larger band gap energy than the well layer 5b. For example, for the well layer 5b made of a Ga 0.85 In 0.15 N mixed crystal, the barrier layer 5a is formed of GaN. The barrier layer 5a and the well layer 5b having a multiple quantum well structure are composed of layers having the same conductivity type. For example, the n-type well layer 5b and the n-type barrier layer 5a form an n-type multiple quantum well structure as a whole. Thereby, it is possible to avoid the formation of a pn junction between the well layer 5b and the barrier layer 5a, and thus it is possible to configure the light emitting layer 5 having a multiple quantum well structure having excellent conductivity.

井戸層5bと障壁層5aとを同一の伝導型の層とするために井戸層5bに不純物を添加することは必須ではない。例えば、不純物を故意に添加しない、所謂、アンドープ(undope)の状態で、または井戸層5bを形成するための成長環境から意図せず、過失による不純物の汚染に因り、キャリア濃度が5×1017cm-3以上で5×1019cm-3以下の範囲にあれば、本発明に係る井戸層5bとして利用できる。 In order to make the well layer 5b and the barrier layer 5a have the same conductivity type, it is not essential to add impurities to the well layer 5b. For example, in a so-called undoped state where impurities are not added intentionally, or unintentionally from the growth environment for forming the well layer 5b, the carrier concentration is 5 × 10 17 due to impurity contamination due to negligence. If it is in the range of cm −3 or more and 5 × 10 19 cm −3 or less, it can be used as the well layer 5b according to the present invention.

本発明では多重量子井戸構造をなす井戸層5bを、特に、アクセプター不純物を添加したGaを含むIII族窒化物半導体層から構成する。例えば、障壁層5aと同一のn形の伝導形を保持しつつも、アクセプター不純物が添加されたn形のGa0.75In0.25N混晶から井戸層5bを構成する。障壁層5aと同一の伝導形を有し、且つ、アクセプター不純物を含む井戸層5bは、単独でありながら、混色により、白色光を得るに好都合となる波長を相違する多波長の発光をもたらせる。 In the present invention, the well layer 5b having a multiple quantum well structure is particularly composed of a group III nitride semiconductor layer containing Ga to which an acceptor impurity is added. For example, the well layer 5b is composed of an n-type Ga 0.75 In 0.25 N mixed crystal to which an acceptor impurity is added while maintaining the same n-type conductivity as that of the barrier layer 5a. The well layer 5b having the same conductivity type as that of the barrier layer 5a and containing acceptor impurities, while being single, produces multi-wavelength light emission having different wavelengths that are advantageous for obtaining white light by color mixing. Make it.

アクセプター不純物として亜鉛(Zn)を添加してGaInNからなる発光層5を形成する技術が開示されている(特公昭55−3834号参照)。しかしながら、Znのみをアクセプター不純物として添加した井戸層5bは、抵抗が大きく、充分に導電性のある井戸層5bを安定して形成するに至らない。一方で、本発明に係る井戸層5bの形成には、III族窒化物半導体についてアクセプターとなり得る第II族不純物の中でも、マグネシウム(Mg)を好適に使用できる。   A technique for forming a light emitting layer 5 made of GaInN by adding zinc (Zn) as an acceptor impurity is disclosed (see Japanese Patent Publication No. 55-3834). However, the well layer 5b in which only Zn is added as an acceptor impurity has a high resistance and does not stably form the well layer 5b having sufficient conductivity. On the other hand, for the formation of the well layer 5b according to the present invention, magnesium (Mg) can be suitably used among Group II impurities that can be an acceptor for the Group III nitride semiconductor.

本発明に係る多重量子井戸構造の発光層5は、例えば、有機金属気相堆積(MOCVD又はMOVPEなどと略称される)法、分子線エピタキシャル(MBE)法、ハイドライド(hydride)法、ハライド(halyde)法などの気相成長法により形成できる。特に、MBE法は、上記の他の気相成長法と比較すれば、より低温で障壁層5aや井戸層5bを形成できる。このため、例えば、本発明に係る井戸層5bを形成するために用いたMgの障壁層5aへの熱拡散を抑制するのに優位な成長手段となる。   The light emitting layer 5 having a multiple quantum well structure according to the present invention includes, for example, a metal organic vapor phase deposition (abbreviated as MOCVD or MOVPE) method, a molecular beam epitaxial (MBE) method, a hydride method, a halide (halide). ) Method or the like. In particular, the MBE method can form the barrier layer 5a and the well layer 5b at a lower temperature than the other vapor phase growth methods described above. For this reason, for example, this is an advantageous growth means for suppressing thermal diffusion of Mg used to form the well layer 5b according to the present invention into the barrier layer 5a.

アクセプター不純物としてMgを含む井戸層5bにあって、その層厚は1nm以上で20nm以下とするのが好適である。1nm未満の極端に薄い井戸層5bは、層(膜)の2次元的な連続性に欠けるため、結果として、発光素子への動作電流の通流、特に水平(横)方向への電流拡散に係る電気抵抗が増大する、或いは発光領域が減少することとなり不都合である。一方、20nmを超える厚膜を井戸層5bとして使用しても、エネルギーレベルを相違する多くの量子準位を充分に形成するに至らず、従って、様々な量子準位間の遷移に基く、波長を互いに異にする発光が多く得られない不都合がある。   In the well layer 5b containing Mg as an acceptor impurity, the layer thickness is preferably 1 nm or more and 20 nm or less. The extremely thin well layer 5b of less than 1 nm lacks the two-dimensional continuity of the layer (film), and as a result, the operating current flows to the light emitting element, particularly in the horizontal (lateral) direction. Such an electrical resistance increases or the light emitting region decreases, which is disadvantageous. On the other hand, even if a thick film exceeding 20 nm is used as the well layer 5b, it does not sufficiently form many quantum levels having different energy levels, and therefore the wavelength based on the transition between various quantum levels is not achieved. There is an inconvenience that a large amount of light emission with different values cannot be obtained.

また、MBE法は、一般に水素を含まない真空環境下でIII族窒化物半導体層を成長できるため、例えば、電気的に活性化した(アクセプター化した)Mgを多量に含む低抵抗のp形GaXIn1-XN(0≦X≦1)層等を簡易に形成できる利点がある。例えば、窒素(N2)プラズマを窒素源として用いるMBE法によれば、層内のMg原子の濃度が1.5×1019cm-3であるところ、キャリア濃度を8.0×1018cm-3とする低抵抗のp形GaN層を形成できる。従って、Mgの電気的活性化率(便宜上、キャリア濃度をMgの原子濃度を除した値(百分率値)で表わす。)は、アズグロン(as−grown)状態で53%である。本例の如く、MBE法によれば、MOCVD法で成長させたMgドープGaN層の如く、同層から脱水素処理を必要とせずに、電気的活性率を50%以上とするp形GaXIn1-XN(0≦X≦1)層等を容易に形成できる利点がある。 In addition, since the MBE method can generally grow a group III nitride semiconductor layer in a vacuum environment not containing hydrogen, for example, a low-resistance p-type Ga containing a large amount of electrically activated (acceptor) Mg. There is an advantage that an X In 1-X N (0 ≦ X ≦ 1) layer or the like can be easily formed. For example, according to the MBE method using nitrogen (N 2 ) plasma as a nitrogen source, the Mg concentration in the layer is 1.5 × 10 19 cm −3 and the carrier concentration is 8.0 × 10 18 cm. -3 , a low resistance p-type GaN layer can be formed. Therefore, the electrical activation rate of Mg (for convenience, the carrier concentration is expressed by the value obtained by dividing the atomic concentration of Mg (percentage value)) is 53% in the as-grown state. As in this example, according to the MBE method, unlike the Mg-doped GaN layer grown by the MOCVD method, the p-type Ga X having an electrical activity of 50% or more without requiring dehydrogenation treatment from the same layer. There is an advantage that an In 1-X N (0 ≦ X ≦ 1) layer or the like can be easily formed.

Mgなどのアクセプター不純物を含む一井戸層5bと、井戸層5bと同一の伝導形を呈する一障壁層5aとの接合構造からなる一対(one pair)の構造単位をもって多重量子井戸構造を構成するにあって、その多重量子井戸構造を構成する構造単位の対数は、3対以上で40対以下とするのが好適である。本発明に係る井戸層5bは一層であっても、多波長の発光を放射できるが、より演色性に優れる発光を得るには、対の数を4以上とするのが望ましい。例えば、MBE法で成長させたMgドープn形Ga0.85In0.15N混晶からなる井戸層5bと、同じくMBE法で成長させたGaN障壁層5aとを30対(一つの障壁層5aと一つの井戸層5bとの接合体を一対とする)組み合わせて構成した多重量子井戸構造発光層5のフォトルミネッセンス(英略称:PL)スペクトルの一例を図2に示す。この多重量子井戸構造をなす井戸層5bの層厚は4nmであり、障壁層5aの厚さは10nmである。 To construct a multiple quantum well structure with a pair of structural units composed of a junction structure of one well layer 5b containing an acceptor impurity such as Mg and one barrier layer 5a having the same conductivity type as the well layer 5b. The logarithm of the structural units constituting the multiple quantum well structure is preferably 3 pairs or more and 40 pairs or less. Even if the well layer 5b according to the present invention is a single layer, it is possible to emit multi-wavelength light. However, in order to obtain light emission with more excellent color rendering, the number of pairs is preferably 4 or more. For example, a well layer 5b made of Mg-doped n-type Ga 0.85 In 0.15 N mixed crystal grown by the MBE method and 30 pairs of GaN barrier layers 5a also grown by the MBE method (one barrier layer 5a and one barrier layer 5a) FIG. 2 shows an example of the photoluminescence (abbreviation: PL) spectrum of the light emission layer 5 having a multiple quantum well structure formed by combining the junction with the well layer 5b. The thickness of the well layer 5b forming this multiple quantum well structure is 4 nm, and the thickness of the barrier layer 5a is 10 nm.

図2に例示したフォトルミネッセンススペクトルに示すように、本発明に係るアクセプター不純物を含む井戸層5bを備えた多重量子井戸構造の発光層5からは、400nm(4000オングストローム)以上500nm(5000オングストローム)以下の波長の範囲に波長を相違する3本の発光が出射される(図2に記号λ2〜λ4で表わす。)。バンド(band)端発光に対応する発光(図2に記号λBで表わす)とは別に、そのバンド端の発光の波長(本例では、365nm)以上で650nm以下の波長範囲において、波長を相違する合計6本の発光(図2に記号λ1〜λ6で表わす。)が出射され得る。 As shown in the photoluminescence spectrum illustrated in FIG. 2, from the light emitting layer 5 having a multiple quantum well structure including the well layer 5b containing the acceptor impurity according to the present invention, 400 nm (4000 angstrom) or more and 500 nm (5000 angstrom) or less. The three light emissions having different wavelengths in the wavelength range are emitted (represented by symbols λ 2 to λ 4 in FIG. 2). Apart from the emission corresponding to the band edge emission (indicated by the symbol λ B in FIG. 2), the wavelength is different in the wavelength range of the emission at the band edge (in this example, 365 nm) to 650 nm or less. A total of six emitted lights (represented by symbols λ 1 to λ 6 in FIG. 2) can be emitted.

また、バンド端発光(λB)とは相違する波長の複数の発光(λ1〜λ6)にあって、隣接する発光(例えば、λ1とλ2、λ3とλ4など)の波長の差違は、短波長側での発光間、例えばλ1とλ2の発光間では17.5nmであるが、発光の波長が長波長となるに伴い、発光間の波長の差異は徐々に大となる傾向があり、λ5とλ6との発光間では55.5nmとなっているのが特徴である。この多波長の発光ピークの出現の態様は、例えば、MOCVD法により形成されたSiとMgを共にドーピングした発光層5からの主たる発光スペクトルの「肩」部に生ずる、通称、ショルダー(肩)ピークとは、発光間の波長の間隔においても明らかに出現の態様を異にするものである。井戸層の層厚が一定であっても多波長の発光となるのは、アクセプターの添加に因って、放射再結合をもたらす種々の準位が形成されるためと推察される。 In addition, the wavelengths of adjacent light emission (for example, λ 1 and λ 2 , λ 3 and λ 4, etc.) in a plurality of light emission (λ 1 to λ 6 ) having a wavelength different from the band edge light emission (λ B ). The difference in light emission is 17.5 nm between the light emission on the short wavelength side, for example, between the light emission of λ 1 and λ 2 , but the wavelength difference between the light emission gradually increases as the light emission wavelength becomes longer. The characteristic is that the light emission between λ 5 and λ 6 is 55.5 nm. The mode of appearance of this multi-wavelength emission peak is, for example, the so-called shoulder peak generated in the “shoulder” portion of the main emission spectrum from the light emitting layer 5 doped with both Si and Mg formed by the MOCVD method. Is clearly different in appearance even in the wavelength interval between the emitted light. The reason why light emission with multiple wavelengths occurs even when the thickness of the well layer is constant is presumed to be due to the formation of various levels that cause radiative recombination due to the addition of the acceptor.

単独でありながら多波長の発光を同時に発光できる、本発明に係る井戸層5bを用いて多重量子井戸構造の発光層5を構成するに際し、基板1の表面側より発光層5からの発光を外部へ取り出す方向に向けて、より層厚の薄いアクセプター不純物を含む井戸層5bを配置すると、外部への発光の取り出し効率に優れる白色LEDを得るに好都合となる。層厚が薄い井戸層5bからは、短波長の発光成分を多く含む多波長発光がもたらされる。他方、層厚が厚い井戸層5bからは、長波長の発光成分を多く含む多波長発光がもたらされる。短波長の発光は、長波長の発光を帰結する井戸層5bに吸収されてしまう。このため、基板1の表面側より発光層5からの発光を外部へ取り出す方向に向けて、より層厚の薄い井戸層5bを配置すると、基板1の表面側に位置する井戸層5bからの発光が吸収されるのを抑止でき、外部視野方向に向けて透過させるのに好適となるからである。   When the light emitting layer 5 having the multiple quantum well structure is formed by using the well layer 5b according to the present invention which can emit light of multiple wavelengths at the same time, the light emitted from the light emitting layer 5 is externally transmitted from the surface side of the substrate 1. When the well layer 5b containing the acceptor impurity having a thinner layer thickness is arranged in the direction of taking out the light, it is convenient to obtain a white LED having excellent light emission extraction efficiency to the outside. The well layer 5b having a small layer thickness provides multi-wavelength light emission containing a large amount of short-wavelength light-emitting components. On the other hand, the well layer 5b having a large layer thickness provides multi-wavelength light emission containing a large amount of long-wavelength light-emitting components. The short wavelength light emission is absorbed by the well layer 5b resulting in the long wavelength light emission. For this reason, when the well layer 5b having a smaller thickness is disposed in the direction in which light emitted from the light emitting layer 5 is extracted to the outside from the surface side of the substrate 1, light emission from the well layer 5b located on the surface side of the substrate 1 This is because it is possible to suppress the absorption of water and is suitable for transmitting in the direction of the external visual field.

全て層厚を異にする井戸層5bを用いて多重量子井戸構造を作製した場合は、層厚に相応して各井戸層5bからは互いに波長を相違する発光が出射され、それらの発光を重畳して外部へ取り出せるため、演色性に優れる白色LEDを提供できる。例えば、赤色又は緑色又は青色の何れかの帯域の光を主にもたらすのに好適な層厚の多波長発光を呈する井戸層5bを配置しても演色性に優れる白色LEDを構成できる。視感度の低い帯域の光を出射する同一の層厚の井戸層5bを複数、配置し、その上方の発光の外部取り出し方向に層厚を順次、薄くした井戸層5bを配置して、発光層5をなす多重量子井戸構造を構成する例を挙げられる。   When a multi-quantum well structure is formed using well layers 5b having different thicknesses, light emission having different wavelengths is emitted from each well layer 5b in accordance with the layer thickness, and the light emission is superimposed. Thus, a white LED having excellent color rendering properties can be provided. For example, a white LED having excellent color rendering can be formed even when the well layer 5b exhibiting multi-wavelength emission having a layer thickness suitable for mainly providing light in a red, green, or blue band is provided. A plurality of well layers 5b having the same layer thickness for emitting light in a band with low visibility are arranged, and a well layer 5b having a reduced thickness is sequentially arranged in the direction of external extraction of light emission above the well layer 5b. An example of forming a multiple quantum well structure of 5 is given.

赤色又は緑色又は青色の何れかの帯域の発光を主成分としてもたらす各井戸層5bは、例えば、GaXIn1-XN(0<x<1)混晶からなる井戸層5bにあって、インジウムの組成(1−X)を相違させて形成することができる。しかし、MBE法やMOCVD等の成長方法により、In組成を相違する井戸層5bを形成するには、成長温度やGaとInとの原料供給比率を変化させる必要がある。このため、同一の成長温度及び原料供給比率の条件下で、成長時間を単純に調整して井戸層5bの層厚を制御する技術手段と比較すれば煩雑な操作を余儀なくされる。 Each well layer 5b that mainly emits light in a band of red, green, or blue is, for example, in the well layer 5b made of Ga x In 1-x N (0 <x <1) mixed crystal, It can be formed with different indium compositions (1-X). However, in order to form the well layer 5b having a different In composition by a growth method such as MBE or MOCVD, it is necessary to change the growth temperature and the raw material supply ratio of Ga and In. For this reason, if compared with the technical means which controls the layer thickness of the well layer 5b simply by adjusting the growth time under the conditions of the same growth temperature and raw material supply ratio, a complicated operation is unavoidable.

また、アクセプター不純物の原子濃度を互いに相違する各井戸層5bから出射される光の波長は、アクセプター不純物の原子濃度に対応して異なったものとなる。これにより、井戸層5bの層厚が一定である場合でも、井戸層5bの内部に含まれるアクセプター不純物の原子濃度を変化させることで、多波長の光を出現させる波長範囲を制御するのにより好都合となる。例えば、Mgドープn形Ga0.75In0.25N井戸層5bの場合で、その井戸層5bの内部のMg原子の濃度を1×1019原子/cm3、8×1018原子/cm3、及び2×1018原子/cm3と相違する井戸層5bを用いて多重(3重)の量子井戸構造発光層5を形成したときは、波長400nm以上で600nm以下の範囲に多波長発光を出現させることができる。 In addition, the wavelengths of light emitted from the well layers 5b having different acceptor impurity atomic concentrations are different in accordance with the acceptor impurity atomic concentrations. Thereby, even when the thickness of the well layer 5b is constant, it is more convenient to control the wavelength range in which multi-wavelength light appears by changing the atomic concentration of the acceptor impurity contained in the well layer 5b. It becomes. For example, in the case of the Mg-doped n-type Ga 0.75 In 0.25 N well layer 5b, the concentration of Mg atoms inside the well layer 5b is 1 × 10 19 atoms / cm 3 , 8 × 10 18 atoms / cm 3 , and 2 When the multiple (triple) quantum well structure light emitting layer 5 is formed using the well layer 5b different from × 10 18 atoms / cm 3 , multi-wavelength light emission should appear in the wavelength range of 400 nm to 600 nm. Can do.

以上述べたように、本発明では、発光層5が障壁層5aと井戸層5bの多重量子井戸構造となるので、多波長を呈する発光層を、簡単な構造で簡易に形成することができ、敷設面積も発光層5の平面積と略同一となるので光度も高めることができる。また、発光層5が単一であるので、その発光層5のみに対応してp形及びn形の電極を設ければよく、RGB型白色LEDや補色型白色LEDの場合に比較して、発光層5を削り取る領域を大幅に低減でき、発光効率を改善することができる。   As described above, in the present invention, since the light emitting layer 5 has a multiple quantum well structure of the barrier layer 5a and the well layer 5b, a light emitting layer exhibiting multiple wavelengths can be easily formed with a simple structure, Since the laying area is substantially the same as the plane area of the light emitting layer 5, the luminous intensity can be increased. Moreover, since the light emitting layer 5 is single, it suffices to provide p-type and n-type electrodes corresponding to only the light emitting layer 5, compared to the case of RGB type white LED or complementary color type white LED, The area where the light emitting layer 5 is scraped off can be greatly reduced, and the light emission efficiency can be improved.

また、井戸層5bを、層厚を相違する複数の井戸層5b,5b,…から構成することとしたので、各井戸層5bがもたらす複数の発光の波長を互いに異にする多色発光とすることができ、白色発光の演色性を高く一定に安定させられ、蛍光材料を利用しなくても白色光を得ることができるので、蛍光体の微妙な組成調整も不要となる。   In addition, since the well layer 5b is composed of a plurality of well layers 5b, 5b,... Having different layer thicknesses, multicolor light emission in which the wavelengths of the plurality of light emissions produced by the well layers 5b are different from each other is obtained. In addition, the color rendering property of white light emission can be stabilized at a high level, and white light can be obtained without using a fluorescent material, so that fine composition adjustment of the phosphor is not necessary.

また、井戸層5bの各々にアクセプター不純物を故意に添加したので、数的に単一でありながら、波長を相違する多色の発光をもたらす発光層5を構成することができ、その多色発光特性により、白色発光の演色性を高く一定に安定させることができ、また、蛍光材料を利用しなくても白色光を得ることができるので、蛍光体の微妙な組成調整も不要となる。   In addition, since the acceptor impurity is intentionally added to each of the well layers 5b, it is possible to construct the light emitting layer 5 that emits multicolor light having different wavelengths while being numerically single. Due to the characteristics, the color rendering property of white light emission can be stabilized to be high and constant, and since white light can be obtained without using a fluorescent material, fine composition adjustment of the phosphor becomes unnecessary.

さらに、井戸層5bを、障壁層5aと同一の伝導形を呈する層から構成することとしたので、障壁層5aとの間でのpn接合の形成を回避でき、従って、導通性に優れる多重量子井戸構造の発光層5を構成できる。   Furthermore, since the well layer 5b is composed of a layer having the same conductivity type as that of the barrier layer 5a, the formation of a pn junction with the barrier layer 5a can be avoided, and therefore, the multi-quantum having excellent conductivity. The light emitting layer 5 having a well structure can be formed.

また、基板1の表面側より発光層5からの発光を取り出す方向に向けて、より層厚の薄いIII族窒化物半導体層からなる井戸層5b,5b,…を配置して多重量子井戸構造の発光層5を構成することとしたので、多重量子井戸構造を成す各井戸層5b,5b,…から出射される発光を効率的に視野方向に取り出すことができる。   Further, the well layers 5b, 5b,... Made of a group III nitride semiconductor layer having a thinner layer thickness are arranged from the surface side of the substrate 1 in the direction in which the light emission from the light emitting layer 5 is extracted. Since the light emitting layer 5 is configured, the light emitted from the well layers 5b, 5b,... Constituting the multiple quantum well structure can be efficiently extracted in the viewing direction.

すなわち、短波長の光が、長波長の光を発する井戸層に吸収されてしまうのを回避するために、基板1の表面側に井戸層幅を広くして形成した、量子準位が低く長波長の発光成分を含む多波長の発光をもたらす井戸層5bを配置し、発光の取り出し方向に、井戸層幅を狭くして形成した、量子準位が高くより短波長の発光成分を含む多波長の発光をもたらす井戸層5bを配置して多重量子井戸構造の発光層5を構成することとした。この構成下では、短波長の発光は、より長波長の発光を行う井戸層5bを通過しない。このため、基板表面側に配置された井戸層5bから出射される発光が、発光の取り出し方向に配置された井戸層5bに吸収されることなく、外部視野方向に発光を取り出すことができ、各井戸層5bから出射される発光を効率的に視野方向に取り出すことができる。また演色性を優れたものとすることができ、且つ高輝度の白色LEDを実現することができる。   In other words, in order to avoid absorption of short-wavelength light into a well layer that emits long-wavelength light, a quantum layer with a low quantum level is formed on the surface side of the substrate 1 with a wide well layer width. A multi-wavelength having a higher quantum level and a shorter wavelength light-emitting component formed by arranging a well layer 5b that emits multi-wavelength light including a light-emitting component at a wavelength and narrowing the well layer width in the light emission extraction direction The light emitting layer 5 having a multi-quantum well structure is formed by arranging the well layer 5b that causes the light emission. Under this configuration, light having a short wavelength does not pass through the well layer 5b that emits light having a longer wavelength. For this reason, light emitted from the well layer 5b disposed on the substrate surface side can be extracted in the external visual field direction without being absorbed by the well layer 5b disposed in the light extraction direction. Light emitted from the well layer 5b can be efficiently extracted in the viewing direction. Further, the color rendering properties can be improved, and a high-intensity white LED can be realized.

また、本発明によれば、添加されたアクセプター不純物の原子濃度を互いに相違する、単独でも波長を相違する複数の発光を呈する井戸層5bを複数用いて多重量子井戸構造の発光層5を構成することとしたので、各井戸層5bからの発光が重畳した多波長の発光を呈する発光層5が得られ、例えば、補色関係にある二つの異なる波長の発光を混色させて白色光とする、所謂、補色型白色LEDに比較して、より演色性に優れる白色LEDを提供できる。   In addition, according to the present invention, the light emitting layer 5 having a multiple quantum well structure is configured by using a plurality of well layers 5b having different atomic concentrations of the added acceptor impurities and exhibiting a plurality of light emission having different wavelengths even independently. Therefore, the light emitting layer 5 exhibiting multi-wavelength light emission in which the light emission from each well layer 5b is superimposed is obtained. For example, the so-called white light is obtained by mixing the light emission of two different wavelengths having a complementary color relationship. Compared with the complementary color type white LED, it is possible to provide a white LED which is more excellent in color rendering.

以下、本発明のIII族窒化物半導体発光素子の実施例を図面を参照して説明する。   Hereinafter, examples of the group III nitride semiconductor light emitting device of the present invention will be described with reference to the drawings.

(第1実施例) 図3は、第1実施例の多重量子井戸構造の発光層を備えたIII族窒化物半導体発光素子の構造を示す断面模式図である。また、図4は、その多重量子井戸構造の発光層から放射されるフォトルミネッセンススペクトルである。   First Example FIG. 3 is a schematic cross-sectional view showing the structure of a group III nitride semiconductor light emitting device including a light emitting layer having a multiple quantum well structure according to a first example. FIG. 4 shows a photoluminescence spectrum emitted from the light emitting layer having the multiple quantum well structure.

III族窒化物半導体発光素子10を作製するための構造体を形成するにあたっては、基板101として、{111}珪素単結晶(シリコン)を用いた。   In forming the structure for producing the group III nitride semiconductor light emitting device 10, {111} silicon single crystal (silicon) was used as the substrate 101.

基板101の表面は、無機酸を使用して洗浄後、分子線エピタキシャル(MBE)成長装置の成長室に搬送し、その成長室の内部を超高真空に排気した。その後、成長室の真空度を維持しながら、基板101の温度を780℃に昇温して、基板101の表面101aが(7×7)構造の再構成を呈する迄、継続して加熱した。   The surface of the substrate 101 was cleaned using an inorganic acid, transferred to a growth chamber of a molecular beam epitaxial (MBE) growth apparatus, and the inside of the growth chamber was evacuated to an ultrahigh vacuum. Thereafter, while maintaining the degree of vacuum in the growth chamber, the temperature of the substrate 101 was raised to 780 ° C., and the substrate 101 was continuously heated until the surface 101a of the substrate 101 exhibited a (7 × 7) structure reconstruction.

(7×7)構造の再構成を呈する様に清浄化された基板101の表面101a上には、プラズマ化させた窒素を窒素源とするMBE成長法(窒素プラズマMBE法)により、アンドープの窒化アルミニウム(AlN)層102(層厚=60nm)を形成した。AlN層102上には、窒素プラズマMBE法により、アンドープ窒化アルミニウム・ガリウム混晶(AlXGa1-XN)層103(層厚=300nm)を堆積した。混晶層103をなすAlXGa1-XN層のアルミニウム(Al)組成比(X)は、下層のAlN層102との接合面から、混晶層103の表面に向けて、0.25から0(零)へと連続的に変化させた。 On the surface 101a of the substrate 101 cleaned so as to exhibit a (7 × 7) structure reconstruction, undoped nitridation is performed by MBE growth method (nitrogen plasma MBE method) using nitrogen that has been converted to plasma as a nitrogen source. An aluminum (AlN) layer 102 (layer thickness = 60 nm) was formed. On the AlN layer 102, an undoped aluminum nitride / gallium mixed crystal (Al x Ga 1-x N) layer 103 (layer thickness = 300 nm) was deposited by nitrogen plasma MBE. The aluminum (Al) composition ratio (X) of the Al x Ga 1-x N layer forming the mixed crystal layer 103 is 0.25 from the bonding surface with the lower AlN layer 102 toward the surface of the mixed crystal layer 103. From 0 to 0 (zero) continuously.

AlXGa1-XN層103上には、窒素プラズマMBE法により、珪素(Si)ドープn形GaN層104(層厚=1200nm)を堆積した。キャリア濃度は8×1018cm-3であった。 A silicon (Si) -doped n-type GaN layer 104 (layer thickness = 1200 nm) was deposited on the Al x Ga 1-x N layer 103 by nitrogen plasma MBE. The carrier concentration was 8 × 10 18 cm −3 .

n形GaN層104上には、窒素プラズマMBE法により、基板101の温度を540℃として、多重量子井戸構造の障壁層とするn形GaN層105a(層厚=10nm)を堆積した。次に、窒素プラズマMBE法により、540℃で、このn形GaN障壁層105aに接合させて、マグネシウム(Mg)を含むn形窒化ガリウム・インジウム混晶(Ga0.99In0.01N)からなる井戸層(層厚=2nm)105bを設けた。このn形障壁層105aとn形井戸層105bとからなる一対の構造単位を4対(4ペア(pair))、積層させて、全体としてn形の伝導を呈する多重量子井戸構造の発光層105を形成した。井戸層に含まれるMgの原子濃度は、一般的な2次イオン質量分析法によれば、4×1017原子/cm3であった。 On the n-type GaN layer 104, an n-type GaN layer 105 a (layer thickness = 10 nm) serving as a barrier layer having a multiple quantum well structure was deposited by nitrogen plasma MBE at a temperature of the substrate 101 of 540 ° C. Next, a well layer made of an n-type gallium nitride / indium mixed crystal (Ga 0.99 In 0.01 N) containing magnesium (Mg) is bonded to the n-type GaN barrier layer 105a at 540 ° C. by a nitrogen plasma MBE method. (Layer thickness = 2 nm) 105b was provided. A light emitting layer 105 having a multi-quantum well structure that exhibits n-type conduction as a whole by stacking four pairs (four pairs) of a pair of structural units including the n-type barrier layer 105a and the n-type well layer 105b. Formed. According to general secondary ion mass spectrometry, the atomic concentration of Mg contained in the well layer was 4 × 10 17 atoms / cm 3 .

水素を実質的に含まない10-6パスカル(Pa)程度の高真空環境下で成長させた上記の障壁層105a及び井戸層105bからなる多重量子井戸構造の発光層105から得られる室温でのフォトルミネッセンススペクトルを図4に示す。数的に単一の発光層であっても、波長を相違する多数の発光が出射されていることを明示するために表1に発光ピーク波長とその波長における強度とを纏める。

Figure 2009088553
Photo at room temperature obtained from the light emitting layer 105 having the multiple quantum well structure comprising the barrier layer 105a and the well layer 105b grown in a high vacuum environment of about 10 −6 Pascal (Pa) substantially free of hydrogen. The luminescence spectrum is shown in FIG. Even in a single light emitting layer, the emission peak wavelengths and the intensities at the wavelengths are summarized in Table 1 in order to clearly show that a large number of light emissions having different wavelengths are emitted.
Figure 2009088553

数的に単一の発光層であっても、バンド(band)端の発光波長(波長=366.5nm)より長波長であり、波長550nmのより短波長の範囲に、合計7つの発光が出射されている。隣接する発光ピーク間の波長の差異は、6nm以上で90nm以下であった。発光の波長が長波長である程、隣接する発光ピーク間の間隔(波長差)は広がる傾向を示した。また、井戸層の層厚が一定で、アクセプターの原子濃度が一定であっても多波長の発光がもたらされるのは、水素を全くと云って良い程、含まない高真空環境下で井戸層を形成したため、電気的に活性なMgを井戸層内に多量に存在させることができ、この電気的に活性なMgにより。多くの放射再結合に寄与できる準位が多く形成できたためと推察された。   Even in a single light emitting layer, a total of seven light emissions are emitted in the wavelength range longer than the emission wavelength at the band edge (wavelength = 366.5 nm) and shorter than the wavelength of 550 nm. Has been. The difference in wavelength between adjacent emission peaks was 6 nm or more and 90 nm or less. The longer the emission wavelength, the wider the interval (wavelength difference) between adjacent emission peaks. In addition, even if the thickness of the well layer is constant and the atomic concentration of the acceptor is constant, multi-wavelength light emission is caused by the well layer in a high vacuum environment that does not contain hydrogen at all. Due to the formation, a large amount of electrically active Mg can be present in the well layer, and this electrically active Mg. This is probably because many levels that can contribute to many radiative recombination were formed.

多重量子井戸構造の発光層105の最終端(最表層)をなすGa0.80In0.20N井戸層105b上には、窒素プラズマMBE法により、Mgドープp形GaN層106(層厚=100nm)を設けて、構造体の形成を終了した。p形GaN層106の内部のMgの原子濃度は1×1019cm-3であり、同層106のキャリア濃度は8×1018cm-3であった。すなわち、電気的活性化率は80%であった。 An Mg-doped p-type GaN layer 106 (layer thickness = 100 nm) is provided on the Ga 0.80 In 0.20 N well layer 105b which forms the final end (outermost layer) of the light emitting layer 105 having a multiple quantum well structure by nitrogen plasma MBE. This completes the formation of the structure. The atomic concentration of Mg inside the p-type GaN layer 106 was 1 × 10 19 cm −3 , and the carrier concentration of the layer 106 was 8 × 10 18 cm −3 . That is, the electrical activation rate was 80%.

n形オーミック電極を形成する領域を、一般的なドライエッチング法により除去し、n形オーミック電極107を形成した。また、p形GaN層106の表面にはp形オーミック電極108を形成し、一辺の長さを350μmとする正方形状の発光素子(LED)10を作製した。   A region for forming the n-type ohmic electrode was removed by a general dry etching method to form an n-type ohmic electrode 107. A p-type ohmic electrode 108 was formed on the surface of the p-type GaN layer 106, and a square light-emitting element (LED) 10 having a side length of 350 μm was produced.

発光素子(LED)10の順方向電流を20mAとした際の順方向電圧(Vf)は3.5Vであった。また、順方向に50mAの電流を通流した際には、チップ(chip)状態のLED10の発光層の全面から目視で緑色を帯びた白色の発光が出射された。50mAの順方向電流を通流した際の発光の演色性を色度図上の座標値で表わすと、x座標値で0.26、y座標値で0.38であり、従って、z座標値で0.36であった。   The forward voltage (Vf) when the forward current of the light emitting element (LED) 10 was 20 mA was 3.5V. Further, when a current of 50 mA was passed in the forward direction, white light emission with a green color was emitted from the entire surface of the light emitting layer of the LED 10 in a chip state. When the color rendering property of light emission when a forward current of 50 mA is passed is expressed by the coordinate values on the chromaticity diagram, the x coordinate value is 0.26 and the y coordinate value is 0.38. It was 0.36.

(第2実施例) 図5は、第2実施例のIII族窒化物半導体発光素子(LED)の多重量子井戸構造の発光層の構成を模式的に示す断面図である。   Second Example FIG. 5 is a cross-sectional view schematically showing a configuration of a light emitting layer having a multiple quantum well structure of a group III nitride semiconductor light emitting device (LED) of a second example.

上記の第1実施例に記載したSi基板上に設けたAlN層、AlGaN混晶層及びn形GaN層(図5では符号を「204」とする)からなる積層構造体上に、窒素プラズマMBE法により、図5に示す多重量子井戸構造の発光層205を以下に記載の如く形成した。   Nitrogen plasma MBE is formed on a laminated structure comprising an AlN layer, an AlGaN mixed crystal layer, and an n-type GaN layer (reference numeral “204” in FIG. 5) provided on the Si substrate described in the first embodiment. By the method, the light emitting layer 205 having the multiple quantum well structure shown in FIG. 5 was formed as described below.

多重量子井戸構造の発光層205を形成するにあって、n形GaN層204には、先ず、窒素プラズマMBE法により、層厚を16nmとするn形GaN障壁層205aを設けた。次に、この障壁層205aに接合させて、多重量子井戸構造をなすn形井戸層205bとしてMgドープGa0.80In0.20N井戸層を設けた。このn形障壁層205aとn形井戸層205bとからなる一対の構造単位を10対(10ペア)、積層させて、全体としてn形の伝導を呈する多重量子井戸構造の発光層305を形成した。 In forming the light emitting layer 205 having a multiple quantum well structure, the n-type GaN layer 204 was first provided with an n-type GaN barrier layer 205a having a layer thickness of 16 nm by nitrogen plasma MBE. Next, an Mg-doped Ga 0.80 In 0.20 N well layer was provided as an n-type well layer 205b having a multiple quantum well structure bonded to the barrier layer 205a. A pair of structural units composed of the n-type barrier layer 205a and the n-type well layer 205b (10 pairs) are stacked to form a light emitting layer 305 having a multiple quantum well structure that exhibits n-type conduction as a whole. .

10対の構造単位を積層して形成した多重量子井戸構造をなす10の井戸層205bの層厚は、n形GaN層204側から多重量子井戸構造の表面に向けて積層方向に減少させた。なお、本実施例では積層方向と発光素子(LED)の発光の取り出し方向とは同一方向である。井戸層205bの層厚は、多重量子井戸構造の最下の井戸層で12nmとし、その次の井戸層の層厚は11nmとし、またその次の井戸層の層厚は10nmとし、すなわち、多重量子井戸構造の最表層側に向けて1nmずつ減少させ、最表層の井戸層の層厚は3nmとした(図5参照)。各井戸層205bの層厚は変化させたものの、各井戸層205b内には、原子濃度にして6×1017原子/cm3と略一定となる様にMgをドーピングした。 The layer thickness of ten well layers 205b forming a multiple quantum well structure formed by stacking 10 pairs of structural units was decreased in the stacking direction from the n-type GaN layer 204 side toward the surface of the multiple quantum well structure. In this embodiment, the stacking direction and the light emission direction of the light emitting element (LED) are the same direction. The thickness of the well layer 205b is 12 nm at the bottom well layer of the multiple quantum well structure, the layer thickness of the next well layer is 11 nm, and the layer thickness of the next well layer is 10 nm. The thickness was decreased by 1 nm toward the outermost layer side of the quantum well structure, and the thickness of the outermost well layer was 3 nm (see FIG. 5). Although the thickness of each well layer 205b was changed, Mg was doped in each well layer 205b so that the atomic concentration was substantially constant at 6 × 10 17 atoms / cm 3 .

多重量子井戸構造の発光層205の最表層をなすMgドープGa0.80In0.20N井戸層205b(層厚=3nm)上には、窒素プラズマMBE法により、層厚を10nmとするMgドープp形Al0.03Ga0.97N層を堆積して、発光素子(LED)用途の積層構造体の形成を終了した。 On the Mg-doped Ga 0.80 In 0.20 N well layer 205b (layer thickness = 3 nm) which is the outermost layer of the light emitting layer 205 having a multiple quantum well structure, a Mg-doped p-type Al film having a layer thickness of 10 nm is formed by nitrogen plasma MBE method. A 0.03 Ga 0.97 N layer was deposited to complete the formation of the laminated structure for light emitting device (LED) use.

上記の多重量子井戸構造の発光層205を含む積層構造体から得られる室温でのフォトルミネッセンススペクトルを図6に示す。図6に示すのは、上記の層厚を相違する各井戸層205bからの多波長発光成分が重畳した結果としてのスペクトルである。波長400nmより800nmの広い波長範囲に亘り、合計10の発光が放射された。隣接する発光間の波長の差異は17.5nmから78.0nmであり、その波長の間隔は、発光波長が長波長となる程、広がっていた。また、ヘリウム−カドミウム(He−Cd)レーザー光(波長=325nm)を励起光として照射した際に視認される積層構造体からの発光色は白色であった。   FIG. 6 shows a photoluminescence spectrum at room temperature obtained from the stacked structure including the light emitting layer 205 having the multiple quantum well structure. FIG. 6 shows a spectrum as a result of superimposing the multi-wavelength light emitting components from the respective well layers 205b having different layer thicknesses. A total of 10 emissions were emitted over a wide wavelength range from 400 nm to 800 nm. The difference in wavelength between adjacent light emissions was 17.5 nm to 78.0 nm, and the interval between the wavelengths increased as the emission wavelength became longer. In addition, the color of light emitted from the laminated structure that was visually recognized when irradiated with helium-cadmium (He—Cd) laser light (wavelength = 325 nm) as excitation light was white.

第1実施例に記載をしたのと同様に、n形オーミック電極を形成する領域を、一般的なドライエッチング法により除去し、n形オーミック電極を形成した。また、上記のp形Al0.03Ga0.97N層の表面にはp形オーミック電極を形成し、発光素子(LED)を作製した。 In the same manner as described in the first example, the region for forming the n-type ohmic electrode was removed by a general dry etching method to form the n-type ohmic electrode. A p-type ohmic electrode was formed on the surface of the p-type Al 0.03 Ga 0.97 N layer to produce a light-emitting element (LED).

発光素子(LED)の順方向電流を20mAとした際の順方向電圧(Vf)は3.4Vであった。また、順方向に20mAの電流を通流した際には、チップ(chip)状態のLEDから目視で白色の発光が出射された。   The forward voltage (Vf) when the forward current of the light emitting element (LED) was 20 mA was 3.4V. Further, when a current of 20 mA was passed in the forward direction, white light emission was emitted visually from the LED in the chip state.

(第3実施例) 図7は、第3実施例の多重量子井戸構造の発光層を備えたIII族窒化物半導体発光素子の構造を示す断面模式図である。図8は、第3実施例の多重量子井戸構造の発光層を備えたIII族窒化物半導体発光素子(LED)用途の積層構造体についてのフォトルミネッセンススペクトルである。   Third Example FIG. 7 is a schematic cross-sectional view showing the structure of a group III nitride semiconductor light emitting device including a light emitting layer having a multiple quantum well structure according to a third example. FIG. 8 is a photoluminescence spectrum of a laminated structure for a group III nitride semiconductor light emitting device (LED) provided with a light emitting layer having a multiple quantum well structure according to the third embodiment.

上記の第1及び第2実施例に記載したSi基板上に設けたAlN層及びAlGaN混晶層(図7では符号を「303」とする)からなる積層構造体上に、窒素プラズマMBE法により、多重量子井戸構造の発光層を以下に記載の如く形成した。   On the laminated structure comprising the AlN layer and the AlGaN mixed crystal layer (reference numeral “303” in FIG. 7) provided on the Si substrate described in the first and second embodiments, a nitrogen plasma MBE method is used. A light emitting layer having a multiple quantum well structure was formed as described below.

多重量子井戸構造の発光層を形成するにあって、第1及び第2実施例に記載したAlGaN混晶層303には、先ず、窒素プラズマMBE法により、層厚を10nmとするn形GaN障壁層305aを設けた。次に、この障壁層305aに接合させて、層厚を3nmとするMgドープn形Ga0.75In0.25N井戸層305bを設けた。このn形障壁層305aとn形井戸層305bとからなる一対の構造単位を5対(5ペア)、積層させて、全体としてn形の電気伝導を呈する多重量子井戸構造の発光層305を形成した。 In forming a light emitting layer having a multiple quantum well structure, an AlGaN mixed crystal layer 303 described in the first and second embodiments is first formed into an n-type GaN barrier having a layer thickness of 10 nm by nitrogen plasma MBE. Layer 305a was provided. Next, an Mg-doped n-type Ga 0.75 In 0.25 N well layer 305b having a layer thickness of 3 nm was provided to be joined to the barrier layer 305a. A pair of structural units composed of the n-type barrier layer 305a and the n-type well layer 305b is stacked to form a light emitting layer 305 having a multiple quantum well structure that exhibits n-type electrical conduction as a whole. did.

5対の構造単位を積層して形成した多重量子井戸構造をなす5つの井戸層305b,305b,…の内部のMgの原子濃度は、AlGaN混晶層303側から積層方向(発光の取り出し方向と同一方向)に向けて減少させた。井戸層305bの内部のMgの原子濃度は、多重量子井戸構造の最下の井戸層で1×1019原子/cm3とし、それより上方の井戸層については、8×1018原子/cm3、6×1018原子/cm3、4×1018原子/cm3、及び2×1018原子/cm3と順次、Mgの原子濃度を減少させた。これより、層厚を一定としつつも、Mgの原子濃度を相違する5つの井戸層305bを備えた多重量子井戸構造の発光層305を形成した。 The atomic concentration of Mg inside the five well layers 305b, 305b,... Formed of a multi-quantum well structure formed by stacking five pairs of structural units is determined from the AlGaN mixed crystal layer 303 side in the stacking direction (the emission extraction direction and Decreased in the same direction). The atomic concentration of Mg inside the well layer 305b is 1 × 10 19 atoms / cm 3 in the bottom well layer of the multiple quantum well structure, and 8 × 10 18 atoms / cm 3 in the well layer above it. The atomic concentration of Mg was sequentially decreased to 6 × 10 18 atoms / cm 3 , 4 × 10 18 atoms / cm 3 , and 2 × 10 18 atoms / cm 3 . Thus, the light emitting layer 305 having a multiple quantum well structure including five well layers 305b having different Mg atomic concentrations while maintaining a constant layer thickness was formed.

多重量子井戸構造の発光層305の最表層をなすMgドープGaN井戸層(Mg原子濃度=2×1018原子/cm3)上には、窒素プラズマMBE法により、層厚を10nmとするMgドープp形GaN層306を堆積して、発光素子(LED)用途の積層構造体の形成を終了した。 On the Mg-doped GaN well layer (Mg atom concentration = 2 × 10 18 atoms / cm 3 ), which is the outermost layer of the light-emitting layer 305 having a multiple quantum well structure, Mg-doped to a layer thickness of 10 nm by nitrogen plasma MBE method A p-type GaN layer 306 was deposited to complete the formation of a laminated structure for a light emitting device (LED).

上記の多重量子井戸構造の発光層305を含む積層構造体から得られる室温でのフォトルミネッセンススペクトルを図8に示す。図8に示すのは、上記の層厚一定でMg原子濃度を相違する各井戸層305bからの多波長発光成分が重畳してなるスペクトルである。波長400nmより600nmの波長範囲において、発光ピーク波長を402.5nm、429.0nm、458.0nm、493.0nm、538.0nm、及び593.0nmとする計6の発光が確認された。波長400nmより600nmの波長範囲に出現した上記の発光にあって、隣接する発光間の波長の差異は26.5nmから55.0nmであり、その波長の間隔は、発光波長が長波長となる程、広がっていた。また、ヘリウム−カドミウム(He−Cd)レーザー光(波長=325nm)を励起光として照射した際に視認される積層構造体からの発光色は青白色であった。   A photoluminescence spectrum at room temperature obtained from the stacked structure including the light emitting layer 305 having the multiple quantum well structure is shown in FIG. FIG. 8 shows a spectrum formed by superimposing multi-wavelength light emitting components from the well layers 305b having different layer thicknesses and different Mg atom concentrations. In the wavelength range from 400 nm to 600 nm, a total of 6 luminescences with emission peak wavelengths of 402.5 nm, 429.0 nm, 458.0 nm, 493.0 nm, 538.0 nm, and 593.0 nm were confirmed. In the above-described light emission that appeared in the wavelength range from 400 nm to 600 nm, the wavelength difference between adjacent light emissions is 26.5 nm to 55.0 nm, and the wavelength interval increases as the emission wavelength becomes longer. It was spreading. Moreover, the emission color from the laminated structure visually recognized when helium-cadmium (He—Cd) laser light (wavelength = 325 nm) was irradiated as excitation light was bluish white.

図9は図7の積層構造体を用いて作製した発光素子(LED)の平面断面図である。上記の積層構造体の、n形オーミック電極307を形成する領域307aに在るp形GaN層306及び多重量子井戸構造の発光層305を一般的なドライエッチング法により除去し、発光層305の下方のn形AlGaN混晶層303の表面を露出させた。然る後、その領域307aに露出させたn形AlGaN混晶層303の表面上に、図9に示す如く、n形オーミック電極307を形成した。上記のp形GaN層306の表面には、一般的なフォトリソグラフ技術を利用してパターニングした平面格子状のp形オーミック電極308を形成した。格子状に配置した幅4μmのp形オーミック電極308は、p形GaN層306にオーミック接触をなす白金(Pt)系金属から構成した。また、p形GaN層306の表面上の一端には、この格子状p形オーミック電極308に電気的に導通させて結線(ボンデング)用の台座(パッド)電極309を設けて、発光素子(LED)30を作製した。   FIG. 9 is a cross-sectional plan view of a light emitting device (LED) manufactured using the laminated structure of FIG. The p-type GaN layer 306 and the light emitting layer 305 having a multiple quantum well structure in the region 307a for forming the n-type ohmic electrode 307 are removed by a general dry etching method, The surface of the n-type AlGaN mixed crystal layer 303 was exposed. Thereafter, an n-type ohmic electrode 307 was formed on the surface of the n-type AlGaN mixed crystal layer 303 exposed in the region 307a, as shown in FIG. On the surface of the p-type GaN layer 306, a p-type ohmic electrode 308 having a planar lattice shape patterned using a general photolithography technique was formed. The p-type ohmic electrode 308 having a width of 4 μm arranged in a lattice shape is made of a platinum (Pt) -based metal that makes ohmic contact with the p-type GaN layer 306. Further, a pedestal (pad) electrode 309 for connection (bonding) is provided at one end on the surface of the p-type GaN layer 306 so as to be electrically connected to the lattice-shaped p-type ohmic electrode 308, and a light-emitting element (LED ) 30 was produced.

発光素子(LED)の順方向電流を20mAとした際の順方向電圧(Vf)は3.4Vであった。また、順方向に20mAの電流を通流した際には、一辺の長さを350μmとする正方形状のLEDチップ(chip)から目視で白色の発光が出射された。   The forward voltage (Vf) when the forward current of the light emitting element (LED) was 20 mA was 3.4V. Further, when a current of 20 mA was passed in the forward direction, white light emission was emitted visually from a square LED chip having a side length of 350 μm.

本発明のIII族窒化物半導体発光素子の断面構造を概略的に示す模式図である。It is a schematic diagram which shows roughly the cross-sectional structure of the group III nitride semiconductor light-emitting device of this invention. 本発明に係る多重量子井戸構造発光層からの多波長発光スペクトル例である。It is an example of the multiwavelength emission spectrum from the multiple quantum well structure light emitting layer which concerns on this invention. 第1実施例に係るLEDの断面模式図である。It is a cross-sectional schematic diagram of LED which concerns on 1st Example. 第1実施例に記載の積層構造体からの多波長発光のスペクトルである。It is the spectrum of the multiwavelength emission from the laminated structure as described in 1st Example. 第2実施例に記載の多重量子井戸構造発光層の断面模式図である。It is a cross-sectional schematic diagram of the multiple quantum well structure light emitting layer as described in 2nd Example. 第2実施例に記載の積層構造体からの多波長発光のスペクトルである。It is the spectrum of the multiwavelength emission from the laminated structure as described in 2nd Example. 第3実施例に記載の多重量子井戸構造発光層の断面模式図である。It is a cross-sectional schematic diagram of the multiple quantum well structure light emitting layer as described in 3rd Example. 第3実施例に記載の積層構造体からの多波長発光のスペクトルである。It is the spectrum of the multiwavelength emission from the laminated structure as described in 3rd Example. 第3実施例に係るLEDの平面模式図である。It is a plane schematic diagram of LED which concerns on 3rd Example.

符号の説明Explanation of symbols

1 基板
5 多重量子井戸構造の発光層
5a 障壁層
5b 井戸層
10 III族窒化物半導体発光素子
101 基板
101a 基板の表面
102 窒化アルミニウム層
103 窒化アルミニウム・ガリウム混晶層
104 n形GaN層
105 発光層
105a 障壁層
105b 井戸層
106 p形GaN層
107 n形オーミック電極
108 p形オーミック電極
204 n形GaN層
205 発光層
205a 障壁層
205b 井戸層
303 窒化アルミニウム・ガリウム混晶層
305 発光層
305a 障壁層
305b 井戸層
306 p形GaN層
307 n形オーミック電極
307a n形オーミック電極を形成する領域
308 p形オーミック電極
309 台座電極
DESCRIPTION OF SYMBOLS 1 Substrate 5 Light emitting layer of multiple quantum well structure 5a Barrier layer 5b Well layer 10 Group III nitride semiconductor light emitting device 101 Substrate 101a Surface 102 of substrate Aluminum nitride layer 103 Aluminum nitride / gallium mixed crystal layer 104 n-type GaN layer 105 Light emitting layer 105a barrier layer 105b well layer 106 p-type GaN layer 107 n-type ohmic electrode 108 p-type ohmic electrode 204 n-type GaN layer 205 light-emitting layer 205a barrier layer 205b well layer 303 aluminum nitride / gallium mixed crystal layer 305 light-emitting layer 305a barrier layer 305b Well layer 306 p-type GaN layer 307 n-type ohmic electrode 307a Region for forming n-type ohmic electrode 308 p-type ohmic electrode 309 Base electrode

Claims (35)

基板の表面上に設けられた、多重量子井戸構造の発光層を構成する1または複数の井戸層を形成するIII族窒化物半導体層において、
アクセプター不純物が添加され、バンド端発光とは別に、数的に単独で、波長を相違する複数の発光を同時に出射する多波長発光を呈するn形の窒化ガリウム・インジウム(組成式GaXIn1-XN:0<X<1)から構成され、
上記窒化ガリウム・インジウムは、インジウム組成(1−X)が0.01以上で0.25以下で、アクセプター不純物としてマグネシウム(Mg)を、4×1017cm-3以上で1×1019cm-3以下の原子濃度で含む、
ことを特徴とするIII族窒化物半導体層。
In a group III nitride semiconductor layer forming one or a plurality of well layers constituting a light emitting layer having a multiple quantum well structure provided on a surface of a substrate,
In addition to the band edge emission, an n-type gallium indium nitride (compositional formula Ga x In 1− X N: 0 <X <1),
The gallium nitride indium has an indium composition (1-X) of 0.01 or more and 0.25 or less, and magnesium (Mg) as an acceptor impurity is 4 × 10 17 cm −3 or more and 1 × 10 19 cm −. Including at an atomic concentration of 3 or less,
A group III nitride semiconductor layer characterized by the above.
基板の表面上に設けられた、1または複数の井戸層を備える多重量子井戸構造の発光層において、
上記井戸層は、請求項1に記載のIII族窒化物半導体層であり、
当該発光層は、井戸層に含有されたマグネシウムが形成する準位に因り、波長を相違する複数の発光を出射する、
ことを特徴とする発光層。
In a light emitting layer having a multiple quantum well structure including one or a plurality of well layers provided on a surface of a substrate,
The well layer is a group III nitride semiconductor layer according to claim 1,
The light emitting layer emits a plurality of light emission having different wavelengths depending on the level formed by magnesium contained in the well layer.
A light emitting layer characterized by that.
当該発光層は、400nm以上で800nm以下の範囲の、波長を相違する複数の発光を出射する、請求項2に記載の発光層。   The said light emitting layer is a light emitting layer of Claim 2 which radiate | emits several light emission from which a wavelength differs in the range of 400 nm or more and 800 nm or less. 当該発光層は、合計10の異なる波長の発光を出射する、請求項3に記載の発光層。   The light emitting layer according to claim 3, wherein the light emitting layer emits light having a total of 10 different wavelengths. 当該発光層は、365nm以上で650nm以下の範囲の、波長を相違する複数の発光を出射する、請求項2に記載の発光層。   The said light emitting layer is a light emitting layer of Claim 2 which radiate | emits several light emission from which a wavelength differs in the range of 365 nm or more and 650 nm or less. 当該発光層は、合計6の異なる波長の発光を出射する、請求項5に記載の発光層。   The light emitting layer according to claim 5, wherein the light emitting layer emits light having a total of six different wavelengths. 当該発光層は、400nm以上で600nm以下の範囲の、波長を相違する複数の発光を出射する、請求項2に記載の発光層。   The said light emitting layer is a light emitting layer of Claim 2 which radiate | emits several light emission from which a wavelength differs in the range of 400 nm or more and 600 nm or less. 当該発光層は、366.5nm以上で550nm以下の範囲の、波長を相違する複数の発光を出射する、請求項2に記載の発光層。   The said light emitting layer is a light emitting layer of Claim 2 which radiate | emits the some light emission from which a wavelength differs in the range of 366.5 nm or more and 550 nm or less. 当該発光層は、合計7の異なる波長の発光を出射する、請求項8に記載の発光層。   The light emitting layer according to claim 8, wherein the light emitting layer emits light having a total of seven different wavelengths. 当該発光層は、400nm以上で500nm以下の範囲の、波長を相違する複数の発光を出射する、請求項2に記載の発光層。   The said light emitting layer is a light emitting layer of Claim 2 which radiate | emits several light emission from which a wavelength differs in the range of 400 nm or more and 500 nm or less. 当該発光層は、合計3の異なる波長の発光を出射する、請求項10に記載の発光層。   The light emitting layer according to claim 10, wherein the light emitting layer emits light having a total of three different wavelengths. 当該発光層が出射する発光は、最も隣接する発光との波長の差異が、発光波長が長い程、より大きい、請求項2乃至11の何れか1項に記載の発光層。   The light emitting layer according to any one of claims 2 to 11, wherein the light emitted from the light emitting layer has a larger wavelength difference from the nearest light emission as the light emission wavelength is longer. 最も隣接する発光との波長の差異を、6nm以上で90nm以下とする、請求項12に記載の発光層。   The light emitting layer according to claim 12, wherein the wavelength difference between the adjacent light emission is 6 nm or more and 90 nm or less. 発光の波長が長波長である程、発光の強度が小さい、請求項13に記載の発光層。   The light emitting layer according to claim 13, wherein the longer the wavelength of light emission, the lower the intensity of light emission. 最も隣接する発光との波長の差異を、17.5nm以上で78.0nm以下とする、請求項12に記載の発光層。   The light emitting layer according to claim 12, wherein the wavelength difference between the adjacent light emission is 17.5 nm or more and 78.0 nm or less. 最も隣接する発光との波長の差異を、26.5nm以上で55.0nm以下とする、請求項12に記載の発光層。   The light emitting layer according to claim 12, wherein a difference in wavelength from the most adjacent light emission is 26.5 nm or more and 55.0 nm or less. 基板の表面上に設けられた、1または複数の井戸層を備える多重量子井戸構造の発光層を具備したIII族窒化物半導体発光素子において、
上記井戸層は、請求項1に記載のIII族窒化物半導体層であり、
上記発光層は、井戸層に含有されたマグネシウムが形成する準位に因り、波長を相違する複数の発光を出射する、
ことを特徴とするIII族窒化物半導体発光素子。
In a group III nitride semiconductor light-emitting device provided with a light-emitting layer having a multiple quantum well structure including one or a plurality of well layers provided on the surface of a substrate,
The well layer is a group III nitride semiconductor layer according to claim 1,
The light emitting layer emits a plurality of light emissions having different wavelengths, depending on the level formed by magnesium contained in the well layer.
A group III nitride semiconductor light emitting device characterized by the above.
上記井戸層の数が、3以上で40以下である、請求項17に記載のIII族窒化物半導体発光素子。   The group III nitride semiconductor light-emitting device according to claim 17, wherein the number of the well layers is 3 or more and 40 or less. 上記発光層は、400nm以上で800nm以下の範囲の、波長を相違する複数の発光を出射する、請求項17または18に記載のIII族窒化物半導体発光素子。   The group III nitride semiconductor light-emitting element according to claim 17 or 18, wherein the light-emitting layer emits a plurality of lights having different wavelengths in a range of 400 nm to 800 nm. 上記発光層は、合計10の異なる波長の発光を出射する、請求項19に記載のIII族窒化物半導体発光素子。   The group III nitride semiconductor light-emitting device according to claim 19, wherein the light-emitting layer emits light having a total of 10 different wavelengths. 上記発光層は、365nm以上で650nm以下の範囲の、波長を相違する複数の発光を出射する、請求項17または18に記載のIII族窒化物半導体発光素子。   19. The group III nitride semiconductor light-emitting element according to claim 17, wherein the light-emitting layer emits a plurality of lights having different wavelengths in a range of 365 nm to 650 nm. 上記発光層は、合計6の異なる波長の発光を出射する、請求項21に記載のIII族窒化物半導体発光素子。   The group III nitride semiconductor light-emitting device according to claim 21, wherein the light-emitting layer emits light having a total of six different wavelengths. 上記発光層は、400nm以上で600nm以下の範囲の、波長を相違する複数の発光を出射する、請求項17または18に記載のIII族窒化物半導体発光素子。   The group III nitride semiconductor light-emitting element according to claim 17 or 18, wherein the light-emitting layer emits a plurality of lights having different wavelengths in a range of 400 nm to 600 nm. 上記発光層は、366.5nm以上で550nm以下の範囲の、波長を相違する複数の発光を出射する、請求項17または18に記載のIII族窒化物半導体発光素子。   19. The group III nitride semiconductor light-emitting element according to claim 17, wherein the light-emitting layer emits a plurality of lights having different wavelengths in a range of 366.5 nm to 550 nm. 上記発光層は、合計7の異なる波長の発光を出射する、請求項24に記載のIII族窒化物半導体発光素子。   The group III nitride semiconductor light emitting device according to claim 24, wherein the light emitting layer emits light having a total of seven different wavelengths. 上記発光層は、400nm以上で500nm以下の範囲の、波長を相違する複数の発光を出射する、請求項17または18に記載のIII族窒化物半導体発光素子。   The group III nitride semiconductor light-emitting element according to claim 17 or 18, wherein the light-emitting layer emits a plurality of lights having different wavelengths in a range of 400 nm to 500 nm. 上記発光層は、合計3の異なる波長の発光を出射する、請求項26に記載のIII族窒化物半導体発光素子。   27. The group III nitride semiconductor light emitting device according to claim 26, wherein the light emitting layer emits light having a total of three different wavelengths. 上記発光層が出射する発光は、最も隣接する発光との波長の差異が、発光波長が長い程、より大きい、請求項17乃至27の何れか1項に記載のIII族窒化物半導体発光素子。   28. The group III nitride semiconductor light-emitting element according to any one of claims 17 to 27, wherein the light emitted from the light-emitting layer has a larger wavelength difference from the nearest light emission as the emission wavelength is longer. 最も隣接する発光との波長の差異を、6nm以上で90nm以下とする、請求項28に記載のIII族窒化物半導体発光素子。   29. The group III nitride semiconductor light-emitting device according to claim 28, wherein a wavelength difference between the adjacent light emission is 6 nm or more and 90 nm or less. 発光の波長が長波長である程、発光の強度が小さい、請求項29に記載のIII族窒化物半導体発光素子。   30. The group III nitride semiconductor light-emitting device according to claim 29, wherein the longer the wavelength of light emission, the lower the intensity of light emission. 最も隣接する発光との波長の差異を、17.5nm以上で78.0nm以下とする、請求項28に記載のIII族窒化物半導体発光素子。   29. The group III nitride semiconductor light-emitting device according to claim 28, wherein a wavelength difference between the adjacent light emission is 17.5 nm or more and 78.0 nm or less. 最も隣接する発光との波長の差異を、26.5nm以上で55.0nm以下とする、請求項28に記載のIII族窒化物半導体発光素子。   29. The group III nitride semiconductor light-emitting device according to claim 28, wherein a wavelength difference between the adjacent light emission is 26.5 nm or more and 55.0 nm or less. 上記井戸層の上方に、アズ−グローン(as−grown)で電気的活性化率を50%以上とするマグネシウムを添加したp形窒化ガリウム・インジウム(組成式GaXIn1-XN:0≦X≦1)層が設けられている、請求項17乃至32の何れか1項に記載のIII族窒化物半導体発光素子。 Above the well layer, p-type gallium nitride indium added with as-grown as-grown electrical activation rate of 50% or more (composition formula Ga x In 1 -x N: 0 ≦ The group III nitride semiconductor light-emitting device according to any one of claims 17 to 32, wherein a layer X ≦ 1) is provided. アズ−グローン(as−grown)で電気的活性化率を80%とするマグネシウムを添加した窒化ガリウム(GaN)層が設けられている、ことを特徴とする請求項33に記載のIII族窒化物半導体発光素子。   34. Group III nitride according to claim 33, characterized in that it is provided with a gallium nitride (GaN) layer to which magnesium is added with an as-grown electrical activation rate of 80%. Semiconductor light emitting device. 緑色を帯びた白色の発光を出射する、ことを特徴とする請求項34に記載のIII族窒化物半導体発光素子。   35. The group III nitride semiconductor light-emitting device according to claim 34, which emits greenish white light.
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JP2014045015A (en) * 2012-08-24 2014-03-13 Meijo University Nitride semiconductor element having multiple active layers, nitride semiconductor light emitting element, nitride semiconductor light receiving element, and method for manufacturing nitride semiconductor element

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