JPWO2009072365A1 - Amorphous transparent conductive film for gallium nitride compound semiconductor light emitting device - Google Patents
Amorphous transparent conductive film for gallium nitride compound semiconductor light emitting device Download PDFInfo
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- JPWO2009072365A1 JPWO2009072365A1 JP2009544615A JP2009544615A JPWO2009072365A1 JP WO2009072365 A1 JPWO2009072365 A1 JP WO2009072365A1 JP 2009544615 A JP2009544615 A JP 2009544615A JP 2009544615 A JP2009544615 A JP 2009544615A JP WO2009072365 A1 JPWO2009072365 A1 JP WO2009072365A1
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- Prior art keywords
- oxide
- transparent conductive
- conductive film
- gallium nitride
- compound semiconductor
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- 239000004065 semiconductor Substances 0.000 title claims abstract description 137
- 229910002601 GaN Inorganic materials 0.000 title claims abstract description 130
- -1 gallium nitride compound Chemical class 0.000 title claims description 46
- JMASRVWKEDWRBT-UHFFFAOYSA-N Gallium nitride Chemical compound [Ga]#N JMASRVWKEDWRBT-UHFFFAOYSA-N 0.000 claims abstract description 89
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- 150000001875 compounds Chemical class 0.000 claims abstract description 45
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- APFVFJFRJDLVQX-UHFFFAOYSA-N indium atom Chemical compound [In] APFVFJFRJDLVQX-UHFFFAOYSA-N 0.000 claims abstract description 30
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- JCXGWMGPZLAOME-UHFFFAOYSA-N bismuth atom Chemical compound [Bi] JCXGWMGPZLAOME-UHFFFAOYSA-N 0.000 claims abstract description 19
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- OTRPZROOJRIMKW-UHFFFAOYSA-N triethylindigane Chemical compound CC[In](CC)CC OTRPZROOJRIMKW-UHFFFAOYSA-N 0.000 description 2
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- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L33/00—Semiconductor devices having potential barriers specially adapted for light emission; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof
- H01L33/36—Semiconductor devices having potential barriers specially adapted for light emission; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof characterised by the electrodes
- H01L33/40—Materials therefor
- H01L33/42—Transparent materials
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L2224/00—Indexing scheme for arrangements for connecting or disconnecting semiconductor or solid-state bodies and methods related thereto as covered by H01L24/00
- H01L2224/01—Means for bonding being attached to, or being formed on, the surface to be connected, e.g. chip-to-package, die-attach, "first-level" interconnects; Manufacturing methods related thereto
- H01L2224/42—Wire connectors; Manufacturing methods related thereto
- H01L2224/47—Structure, shape, material or disposition of the wire connectors after the connecting process
- H01L2224/48—Structure, shape, material or disposition of the wire connectors after the connecting process of an individual wire connector
- H01L2224/4805—Shape
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L2224/00—Indexing scheme for arrangements for connecting or disconnecting semiconductor or solid-state bodies and methods related thereto as covered by H01L24/00
- H01L2224/01—Means for bonding being attached to, or being formed on, the surface to be connected, e.g. chip-to-package, die-attach, "first-level" interconnects; Manufacturing methods related thereto
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- H01L2224/47—Structure, shape, material or disposition of the wire connectors after the connecting process
- H01L2224/48—Structure, shape, material or disposition of the wire connectors after the connecting process of an individual wire connector
- H01L2224/481—Disposition
- H01L2224/48151—Connecting between a semiconductor or solid-state body and an item not being a semiconductor or solid-state body, e.g. chip-to-substrate, chip-to-passive
- H01L2224/48221—Connecting between a semiconductor or solid-state body and an item not being a semiconductor or solid-state body, e.g. chip-to-substrate, chip-to-passive the body and the item being stacked
- H01L2224/48245—Connecting between a semiconductor or solid-state body and an item not being a semiconductor or solid-state body, e.g. chip-to-substrate, chip-to-passive the body and the item being stacked the item being metallic
- H01L2224/48247—Connecting between a semiconductor or solid-state body and an item not being a semiconductor or solid-state body, e.g. chip-to-substrate, chip-to-passive the body and the item being stacked the item being metallic connecting the wire to a bond pad of the item
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- H—ELECTRICITY
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- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
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- H01L2224/47—Structure, shape, material or disposition of the wire connectors after the connecting process
- H01L2224/48—Structure, shape, material or disposition of the wire connectors after the connecting process of an individual wire connector
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- H—ELECTRICITY
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- H01L2224/47—Structure, shape, material or disposition of the wire connectors after the connecting process
- H01L2224/49—Structure, shape, material or disposition of the wire connectors after the connecting process of a plurality of wire connectors
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L33/00—Semiconductor devices having potential barriers specially adapted for light emission; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof
- H01L33/02—Semiconductor devices having potential barriers specially adapted for light emission; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof characterised by the semiconductor bodies
- H01L33/26—Materials of the light emitting region
- H01L33/30—Materials of the light emitting region containing only elements of Group III and Group V of the Periodic Table
- H01L33/32—Materials of the light emitting region containing only elements of Group III and Group V of the Periodic Table containing nitrogen
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- Engineering & Computer Science (AREA)
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- Led Devices (AREA)
Abstract
インジウム、亜鉛及びスズからなる群から選ばれる１以上の金属の酸化物と、ハフニウム、タンタル、タングステン、ビスマス及びランタノイド系元素からなる群から選ばれる１以上の元素を含む酸化物を含み、バンドギャップが３．０ｅＶ以上であり、波長４６０ｎｍにおける屈折率が２．１以上であり、仕事関数が５．５ｅＶ以上である窒化ガリウム系化合物半導体発光素子用非晶質透明導電膜。A band gap including an oxide of at least one metal selected from the group consisting of indium, zinc and tin and an oxide including at least one element selected from the group consisting of hafnium, tantalum, tungsten, bismuth and lanthanoid elements Is an amorphous transparent conductive film for a gallium nitride-based compound semiconductor light emitting device, having a refractive index at a wavelength of 460 nm of 2.1 or more and a work function of 5.5 eV or more.
Description
本発明は、窒化ガリウム系化合物半導体発光素子用非晶質透明導電膜に関する。特に、窒化ガリウム系化合物半導体発光素子の駆動電圧を低下させることができる非晶質透明導電膜に関する。 The present invention relates to an amorphous transparent conductive film for a gallium nitride-based compound semiconductor light emitting device. In particular, the present invention relates to an amorphous transparent conductive film that can reduce the driving voltage of a gallium nitride-based compound semiconductor light emitting device.
近年、短波長光発光素子用半導体材料として、窒化物系半導体である窒化ガリウム系化合物半導体材料が注目を集めている。窒化ガリウム系化合物半導体は、サファイア単結晶等の酸化物又はＩＩＩ−Ｖ族化合物を基板として、この基板上に有機金属気相化学反応法（ＭＯＣＶＤ法）、分子線エピタキシー法（ＭＢＥ法）等を用いることにより形成できる。 In recent years, gallium nitride-based compound semiconductor materials, which are nitride-based semiconductors, have attracted attention as semiconductor materials for short-wavelength light-emitting elements. Gallium nitride-based compound semiconductors use an oxide such as sapphire single crystal or a group III-V compound as a substrate, and a metal organic vapor phase chemical reaction method (MOCVD method), a molecular beam epitaxy method (MBE method), etc. are formed on this substrate. It can be formed by using.
窒化ガリウム系化合物半導体発光素子は、横方向への電流拡散が小さいという特徴を有する。従って、窒化ガリウム系化合物半導体発光素子に電圧を印加した場合、電極直下の半導体にのみ電流が注入され、電極直下の発光層で発光した光は電極に遮られてしまい、外部に取り出すのが困難であった。そこで、窒化ガリウム系化合物半導体発光素子では、通常、正極として透明電極が用いられ、発光層から発せられる光を正極を透過して取り出す。 The gallium nitride compound semiconductor light emitting device has a feature that current diffusion in the lateral direction is small. Therefore, when a voltage is applied to the gallium nitride-based compound semiconductor light emitting device, current is injected only into the semiconductor directly under the electrode, and light emitted from the light emitting layer directly under the electrode is blocked by the electrode, making it difficult to extract to the outside. Met. Therefore, in a gallium nitride-based compound semiconductor light emitting device, a transparent electrode is usually used as a positive electrode, and light emitted from the light emitting layer is extracted through the positive electrode.
上記透明電極としては、Ｎｉ／Ａｕ、ＩＴＯ（Ｉｎ２Ｏ３−ＳｎＯ２）、ＩＺＯ（Ｉｎ２Ｏ３−ＺｎＯ）等の周知の導電材料が用いられる。これら導電材料のうち、Ｎｉ／Ａｕ等の金属は、ｐ型半導体層との接触抵抗は小さいものの、光の透過率が低い。一方、ＩＴＯ等の酸化物は、光の透過率は高いものの、接触抵抗が大きいという問題があった。As the transparent electrode, a well-known conductive material such as Ni / Au, ITO (In 2 O 3 —SnO 2 ), or IZO (In 2 O 3 —ZnO) is used. Among these conductive materials, a metal such as Ni / Au has a low contact resistance with the p-type semiconductor layer, but has a low light transmittance. On the other hand, oxides such as ITO have a problem that contact resistance is large although light transmittance is high.
例えば特許文献１は、窒化ガリウム系化合物半導体発光素子に用いる正極として、ＩＴＯ等の導電性に優れた金属酸化物層とコンタクト金属層とを組み合わせた構成を開示している。しかし、特許文献１に記載の窒化ガリウム系化合物半導体発光素子は、正極に用いられているコンタクト金属層によってｐ型半導体層との接触抵抗を下げることは可能であるものの、コンタクト金属層自体の光透過率が低いため、十分な光取出し効率を得ることができず、発光出力が低くなるという問題があった。
For example,
窒化ガリウム系化合物半導体発光素子の正極としてＩＴＯ等の導電酸化物膜を用いる場合において、導電酸化物膜を３００℃以上で熱アニール処理を行うことにより、導電酸化物膜の比抵抗を減少させることができる。これは、熱アニール処理によって導電酸化物膜中のＳｎドーパントが活性化し、導電酸化物膜のキャリア濃度が増加するためである。 When a conductive oxide film such as ITO is used as the positive electrode of a gallium nitride compound semiconductor light emitting device, the specific resistance of the conductive oxide film is reduced by performing a thermal annealing process on the conductive oxide film at 300 ° C. or higher. Can do. This is because the Sn dopant in the conductive oxide film is activated by the thermal annealing treatment, and the carrier concentration of the conductive oxide film increases.
しかしながら、上記熱アニール処理を行った場合、導電酸化物膜とｐ型半導体層との界面付近で元素の相互拡散が生じ、導電酸化物膜の比抵抗の低減の妨げになるだけでなく、ｐ型半導体層の比抵抗の増大や、導電酸化物膜とｐ型半導体層との接触抵抗の増大が生じてしまうといった問題があった。特に、ｐ型半導体層中のガリウム元素の導電酸化物膜中への拡散は、導電性酸化物膜の比抵抗及び接触抵抗の低減の妨げとなるという問題があった。 However, when the thermal annealing treatment is performed, mutual diffusion of elements occurs near the interface between the conductive oxide film and the p-type semiconductor layer, which not only hinders the reduction of the specific resistance of the conductive oxide film, but also p There is a problem that the specific resistance of the p-type semiconductor layer increases and the contact resistance between the conductive oxide film and the p-type semiconductor layer increases. In particular, the diffusion of the gallium element in the p-type semiconductor layer into the conductive oxide film has a problem that it hinders the reduction of the specific resistance and contact resistance of the conductive oxide film.
上記問題を解決するため、特許文献２はｐ型半導体層上に透光性導電酸化物膜を成膜後、該透光性導電酸化膜にレーザーアニール処理を行う方法を開示している。この方法は、熱アニール処理のみを行った場合に比べ、ｐ型半導体層と透光性導電酸化膜との界面のＧａ元素の拡散を抑えることができるため、透光性導電酸化膜の比抵抗を減少させることができ、透光性導電酸化膜とｐ型半導体層との接触抵抗を低減することができる。しかし、当該方法によってもガリウム元素の拡散を防ぐことはできなかった。 In order to solve the above problem, Patent Document 2 discloses a method of forming a light-transmitting conductive oxide film on a p-type semiconductor layer and then performing laser annealing on the light-transmitting conductive oxide film. Since this method can suppress the diffusion of Ga element at the interface between the p-type semiconductor layer and the translucent conductive oxide film, compared with the case where only the thermal annealing treatment is performed, the specific resistance of the translucent conductive oxide film And the contact resistance between the translucent conductive oxide film and the p-type semiconductor layer can be reduced. However, the diffusion of the gallium element could not be prevented even by this method.
例えば、特許文献２が開示する透明導電膜は、ＩＴＯ又はＩＺＯであり、これらの屈折率は、ＩｎＧａＮが発する４６０ｎｍの波長において、それぞれ、１．９２及び２．０７であり、ＩｎＧａＮが有する屈折率約２．５より小さく、光取出し効率が小さかった。また、ＧａＮ（Ｉｎ）が発する波長３８０ｎｍにおいては、ＩＴＯ、ＩＺＯのバンドギャップがそれぞれ、３．２ｅＶ及び２．９ｅＶであるため、３８０ｎｍの光を吸収してしまい、光取出し効率が非常に小さなものであった。また、ＩＴＯ、ＩＺＯの仕事関数は、それぞれ約５．０ｅＶ及び５．２ｅＶであり、ｐＧａＮのＨＯＭＯレベルの準位と大きく離れており、正孔を注入するための障壁が大きく、駆動電圧も大きいままであった。 For example, the transparent conductive film disclosed in Patent Document 2 is ITO or IZO, and the refractive indexes thereof are 1.92 and 2.07, respectively, at a wavelength of 460 nm emitted from InGaN. It was smaller than about 2.5, and the light extraction efficiency was small. In addition, at the wavelength of 380 nm emitted by GaN (In), the band gaps of ITO and IZO are 3.2 eV and 2.9 eV, respectively, so that light of 380 nm is absorbed and the light extraction efficiency is very small. Met. The work functions of ITO and IZO are about 5.0 eV and 5.2 eV, respectively, which are far from the HOMO level of pGaN, have a large barrier for injecting holes, and have a large driving voltage. It remained.
また、特許文献２において、ＴｉＴａＯ２又はＴｉＮｂＯ２からなる透光性導電酸化膜は、ＴｉＯ２の屈折率２．６はＧａＮの屈折率とほぼ等しいため、ＧａＮ上での光取出し効率に優れた透光性導電酸化膜として使用可能であることが提案されているが、ＴｉＴａＯ２及びＴｉＮｂＯ２は導電性が低く、実際に透明導電酸化膜として使用するには困難である。加えて、これら酸化物は結晶質にしなければ導電率が向上しないことから、高温での熱処理を必要とし、実用的ではなかった。
本発明の目的は、駆動電圧を低減し、光取出し効率を高めることのできる窒化ガリウム系化合物半導体発光素子用非晶質透明導電膜を提供することである。 An object of the present invention is to provide an amorphous transparent conductive film for a gallium nitride-based compound semiconductor light-emitting element that can reduce drive voltage and increase light extraction efficiency.
本発明によれば、以下の窒化ガリウム系化合物半導体発光素子用非晶質透明導電膜等が提供される。
１．インジウム、亜鉛及びスズからなる群から選ばれる１以上の金属の酸化物と、
ハフニウム、タンタル、タングステン、ビスマス及びランタノイド系元素からなる群から選ばれる１以上の元素を含む酸化物を含み、
バンドギャップが３．０ｅＶ以上であり、
波長４６０ｎｍにおける屈折率が２．１以上であり、
仕事関数が５．５ｅＶ以上である窒化ガリウム系化合物半導体発光素子用非晶質透明導電膜。
２．前記インジウム、亜鉛及びスズからなる群から選ばれる１以上の金属の酸化物が、酸化インジウム−酸化亜鉛、酸化インジウム−酸化スズ、酸化亜鉛−酸化スズ又は酸化インジウム−酸化スズ−酸化亜鉛である１に記載の窒化ガリウム系化合物半導体発光素子用非晶質透明導電膜。
３．前記インジウム、亜鉛及びスズからなる群から選ばれる１以上の金属の酸化物が、酸化インジウム−酸化亜鉛であって、インジウム及び亜鉛の原子比がＩｎ／（Ｉｎ＋Ｚｎ）＝０．５〜０．９５である１又は２に記載の窒化ガリウム系化合物半導体発光素子用非晶質透明導電膜。
４．前記インジウム、亜鉛及びスズからなる群から選ばれる１以上の金属の酸化物が、酸化インジウム−酸化スズであって、インジウム及びスズの原子比がＩｎ／（Ｉｎ＋Ｓｎ）＝０．７〜０．９５である１又は２に記載の窒化ガリウム系化合物半導体発光素子用非晶質透明導電膜。
５．酸化亜鉛を主成分とする金属酸化物と、
ハフニウム、タンタル、タングステン、ビスマス及びランタノイド系元素からなる群から選ばれる１以上の元素を含む酸化物を含み、
バンドギャップが３．２ｅＶ以上であり、
波長４６０ｎｍにおける屈折率が２．２以上であり、
仕事関数が５．５ｅＶ以上である窒化ガリウム系化合物半導体発光素子用非晶質透明導電膜。
６．酸化スズを主成分とする金属酸化物と、
ハフニウム、タンタル、タングステン、ビスマス及びランタノイド系元素からなる群から選ばれる１以上の元素を含む酸化物を含み、
バンドギャップが３．５ｅＶ以上であり、
波長３８０ｎｍにおける屈折率が２．３以上であり、
仕事関数が５．５ｅＶ以上である窒化ガリウム系化合物半導体発光素子用非晶質透明導電膜。
７．さらに添加物として酸化ガリウムを含み、
前記非晶質透明導電膜中の全金属元素に対する前記添加物のガリウム原子の原子比が１〜１０ａｔ％である６に記載の窒化ガリウム系化合物半導体発光素子用非晶質透明導電膜。
８．１〜７のいずれかに記載の窒化ガリウム系化合物半導体発光素子用非晶質透明導電膜が、ｐ型窒化ガリウム半導体に直接接合した窒化ガリウム系化合物半導体発光素子。
９．前記窒化ガリウム系化合物半導体発光素子用非晶質透明導電膜上にさらに透明導電膜を積層してなる８に記載の窒化ガリウム系化合物半導体発光素子。
１０．前記窒化ガリウム系化合物半導体発光素子用非晶質透明導電膜が、その成膜時に酸化インジウム−酸化スズ又は酸化インジウム−酸化亜鉛を同時に成膜することにより、ｐ型窒化ガリウム半導体側から徐々に屈折率が低下する屈折率分布を有する８又は９に記載の窒化ガリウム系化合物半導体発光素子。The present invention provides the following amorphous transparent conductive film for gallium nitride-based compound semiconductor light-emitting elements.
1. One or more metal oxides selected from the group consisting of indium, zinc and tin;
An oxide containing one or more elements selected from the group consisting of hafnium, tantalum, tungsten, bismuth and lanthanoid elements,
The band gap is 3.0 eV or more,
The refractive index at a wavelength of 460 nm is 2.1 or more,
An amorphous transparent conductive film for a gallium nitride-based compound semiconductor light-emitting device having a work function of 5.5 eV or more.
2. The oxide of one or more metals selected from the group consisting of indium, zinc and tin is indium oxide-zinc oxide, indium oxide-tin oxide, zinc oxide-tin oxide or indium oxide-tin oxide-
3. The oxide of one or more metals selected from the group consisting of indium, zinc and tin is indium oxide-zinc oxide, and the atomic ratio of indium and zinc is In / (In + Zn) = 0.5 to 0.95. The amorphous transparent conductive film for gallium nitride-based compound semiconductor light-emitting elements according to 1 or 2, wherein
4). The oxide of one or more metals selected from the group consisting of indium, zinc and tin is indium oxide-tin oxide, and the atomic ratio of indium and tin is In / (In + Sn) = 0.7 to 0.95. The amorphous transparent conductive film for gallium nitride-based compound semiconductor light-emitting elements according to 1 or 2, wherein
5. A metal oxide based on zinc oxide,
An oxide containing one or more elements selected from the group consisting of hafnium, tantalum, tungsten, bismuth and lanthanoid elements,
The band gap is 3.2 eV or more,
The refractive index at a wavelength of 460 nm is 2.2 or more,
An amorphous transparent conductive film for a gallium nitride-based compound semiconductor light-emitting device having a work function of 5.5 eV or more.
6). A metal oxide mainly composed of tin oxide;
An oxide containing one or more elements selected from the group consisting of hafnium, tantalum, tungsten, bismuth and lanthanoid elements,
The band gap is 3.5 eV or more,
The refractive index at a wavelength of 380 nm is 2.3 or more,
An amorphous transparent conductive film for a gallium nitride-based compound semiconductor light-emitting device having a work function of 5.5 eV or more.
7). Furthermore, it contains gallium oxide as an additive,
7. The amorphous transparent conductive film for a gallium nitride-based compound semiconductor light-emitting element according to 6, wherein an atomic ratio of gallium atoms of the additive to all metal elements in the amorphous transparent conductive film is 1 to 10 at%.
A gallium nitride-based compound semiconductor light-emitting device in which the amorphous transparent conductive film for a gallium nitride-based compound semiconductor light-emitting device according to any one of 8.1 to 7 is directly bonded to a p-type gallium nitride semiconductor.
9. 9. The gallium nitride compound semiconductor light emitting device according to 8, wherein a transparent conductive film is further laminated on the amorphous transparent conductive film for the gallium nitride compound semiconductor light emitting device.
10. The amorphous transparent conductive film for a gallium nitride compound semiconductor light-emitting element is gradually refracted from the p-type gallium nitride semiconductor side by simultaneously forming indium oxide-tin oxide or indium oxide-zinc oxide at the time of film formation. 10. The gallium nitride-based compound semiconductor light-emitting device according to 8 or 9, having a refractive index distribution in which the rate decreases.
本発明によれば、駆動電圧を低減し、光取出し効率を高めることのできる窒化ガリウム系化合物半導体発光素子用非晶質透明導電膜を提供することができる。 ADVANTAGE OF THE INVENTION According to this invention, the amorphous transparent conductive film for gallium nitride compound semiconductor light-emitting devices which can reduce a drive voltage and can improve light extraction efficiency can be provided.
本発明の第１の窒化ガリウム系化合物半導体発光素子用非晶質透明導電膜（以下、単に本発明の第１の非晶質透明導電膜という場合がある）は、インジウム、亜鉛及びスズからなる群から選ばれる１以上の金属の酸化物と、ハフニウム、タンタル、タングステン、ビスマス及びランタノイド系元素からなる群から選ばれる１以上の元素を含む酸化物を含み、バンドギャップが３．０ｅＶ以上であり、波長４６０ｎｍにおける屈折率が２．１以上であり、仕事関数が５．５ｅＶ以上である。 The first amorphous transparent conductive film for a gallium nitride-based compound semiconductor light emitting device of the present invention (hereinafter sometimes simply referred to as the first amorphous transparent conductive film of the present invention) is made of indium, zinc, and tin. One or more metal oxides selected from the group and an oxide containing one or more elements selected from the group consisting of hafnium, tantalum, tungsten, bismuth and lanthanoid elements, and the band gap is 3.0 eV or more The refractive index at a wavelength of 460 nm is 2.1 or more, and the work function is 5.5 eV or more.
本発明の第１の非晶質透明導電膜が含むインジウム、亜鉛及びスズからなる群から選ばれる１以上の金属の酸化物（以下、単に金属酸化物と略す場合がある）は、好ましくは酸化インジウム−酸化亜鉛（ＩＺＯ）、酸化インジウム−酸化スズ（ＩＴＯ）、酸化亜鉛−酸化スズ（ＺＴＯ）又は酸化インジウム−酸化スズ−酸化亜鉛（ＩＴＺＯ）である。これらの中でも、低温で成膜しても得られる導電膜の比抵抗が小さく、成膜に用いるターゲットの異物発生が少なく、且つ安定して成膜できることから、より好ましくはインジウム及び亜鉛の原子比（Ｉｎ／（Ｉｎ＋Ｚｎ））が０．５〜０．９５である酸化インジウム−酸化亜鉛、又はインジウム及びスズの原子比（Ｉｎ／（Ｉｎ＋Ｓｎ））が０．７〜０．９５である酸化インジウム−酸化スズである。 The oxide of one or more metals selected from the group consisting of indium, zinc and tin contained in the first amorphous transparent conductive film of the present invention (hereinafter sometimes simply referred to as metal oxide) is preferably oxidized. Indium-zinc oxide (IZO), indium oxide-tin oxide (ITO), zinc oxide-tin oxide (ZTO) or indium oxide-tin oxide-zinc oxide (ITZO). Among these, the atomic ratio of indium and zinc is more preferable because the specific resistance of the conductive film obtained even when the film is formed at a low temperature is small, the generation of foreign matter on the target used for film formation is small, and the film can be formed stably. Indium oxide-zinc oxide in which (In / (In + Zn)) is 0.5 to 0.95, or indium oxide in which the atomic ratio of indium and tin (In / (In + Sn)) is 0.7 to 0.95— It is tin oxide.
上記金属酸化物として、ＩＺＯを用いる場合、ＩＺＯ中のＺｎＯ濃度は、好ましくは３〜３８重量％であり、非晶質透明導電膜の熱安定を高める観点から、より好ましくは５〜２０重量％である。 When IZO is used as the metal oxide, the ZnO concentration in IZO is preferably 3 to 38% by weight, and more preferably 5 to 20% by weight from the viewpoint of enhancing the thermal stability of the amorphous transparent conductive film. It is.
上記金属酸化物として、ＩＴＯを用いる場合、ＩＴＯ中のＳｎＯ２濃度は、好ましくは５〜１５重量％であり、非晶質透明導電膜の比抵抗をさらに低減する観点から、より好ましくは７.５〜１２．５重量％である。When ITO is used as the metal oxide, the SnO 2 concentration in the ITO is preferably 5 to 15% by weight, more preferably from the viewpoint of further reducing the specific resistance of the amorphous transparent conductive film. 5 to 12.5% by weight.
上記金属酸化物として、ＺＴＯを用いる場合、好ましくはＺＴＯ中のＺｎＯ濃度が５〜８０重量％であり、ＺＴＯ中のＳｎＯ２濃度が２０〜９５重量％である。非晶質透明導電膜の熱安定性を高める観点から、より好ましくはＺＴＯ中のＺｎＯ濃度が５０〜７５重量％であり、ＳｎＯ２濃度が２５〜５０重量％である。When ZTO is used as the metal oxide, the ZnO concentration in ZTO is preferably 5 to 80% by weight, and the SnO 2 concentration in ZTO is 20 to 95% by weight. From the viewpoint of enhancing the thermal stability of the amorphous transparent conductive film, the ZnO concentration in ZTO is more preferably 50 to 75% by weight and the SnO 2 concentration is 25 to 50% by weight.
上記金属酸化物として、ＩＴＺＯを用いる場合、好ましくはＩＴＺＯ中のＩｎ２Ｏ３濃度が２〜９５重量％であり、ＺｎＯ濃度が３〜９５重量％であり、ＳｎＯ２濃度が２〜９５重量％である。非晶質透明導電膜の熱安定性を高める観点から、より好ましくはＩＴＺＯ中のＩｎ２Ｏ３濃度が１０〜８０重量％であり、ＺｎＯ濃度が1０〜７５重量％であり、ＳｎＯ２濃度が１０〜５０重量％である。When ITZO is used as the metal oxide, the In 2 O 3 concentration in ITZO is preferably 2 to 95% by weight, the ZnO concentration is 3 to 95% by weight, and the SnO 2 concentration is 2 to 95% by weight. It is. From the viewpoint of increasing the thermal stability of the amorphous transparent conductive film, the In 2 O 3 concentration in ITZO is more preferably 10 to 80 wt%, the ZnO concentration is 10 to 75 wt%, and the SnO 2 concentration is 10 to 50% by weight.
本発明の第１の非晶質透明導電膜が含むハフニウム、タンタル、タングステン、ビスマス及びランタノイド系元素からなる群から選ばれる１以上の元素を含む酸化物において、ランタノイド元素とは、ランタン、セリウム、ネオジム、サマリウム、ユウロピウム、ガドリニウム、ジスプロニウム、ホルミウム、エルビウム、ツリウム、イッテリビウム、ルテニウムであり、好ましくはランタン、セリウム、サマリウム、イッテリビウムである。 In the oxide containing one or more elements selected from the group consisting of hafnium, tantalum, tungsten, bismuth, and lanthanoid elements included in the first amorphous transparent conductive film of the present invention, the lanthanoid element is lanthanum, cerium, Neodymium, samarium, europium, gadolinium, dyspronium, holmium, erbium, thulium, ytterbium and ruthenium, preferably lanthanum, cerium, samarium and ytterbium.
本発明の第１の非晶質透明導電膜は、ハフニウム、タンタル、タングステン、ビスマス及びランタノイド系元素を含むことにより、透明導電膜を非晶質にでき、また、屈折率及び仕事関数を大きくすることができる。加えて、これら元素は、ガリウム元素と複合酸化物を形成し、非晶質透明導電膜内にガリウムが拡散することを防ぐことができる。同様に、複合酸化物を形成することから、例えば非晶質透明導電膜と窒化ガリウム層との密着性が向上し、窒化ガリウム系化合物半導体発光素子の安定性を向上させることができる。 The first amorphous transparent conductive film of the present invention contains hafnium, tantalum, tungsten, bismuth, and a lanthanoid element, so that the transparent conductive film can be made amorphous and the refractive index and work function are increased. be able to. In addition, these elements can form a complex oxide with the gallium element and prevent gallium from diffusing into the amorphous transparent conductive film. Similarly, since the composite oxide is formed, for example, the adhesion between the amorphous transparent conductive film and the gallium nitride layer is improved, and the stability of the gallium nitride-based compound semiconductor light emitting device can be improved.
ハフニウム、タンタル、タングステン、ビスマス及びランタノイド系元素の含有量は、好ましくは非晶質透明導電膜中の全金属元素に対して原子比で１〜３０ａｔ％である。これら元素の含有量が３０ａｔ％超の場合、非晶質透明導電膜の抵抗値が大きくなり過ぎ、透明導電膜として機能しないおそれがある。一方、これら元素の含有量が１ａｔ％未満の場合、仕事関数が５．５ｅＶ未満となる、及び屈折率が４６０ｎｍにおいて２．１未満になるおそれがある。 The content of hafnium, tantalum, tungsten, bismuth and lanthanoid elements is preferably 1 to 30 at% in terms of atomic ratio with respect to all metal elements in the amorphous transparent conductive film. When the content of these elements exceeds 30 at%, the resistance value of the amorphous transparent conductive film becomes too large, and there is a possibility that the element does not function as a transparent conductive film. On the other hand, when the content of these elements is less than 1 at%, the work function may be less than 5.5 eV, and the refractive index may be less than 2.1 at 460 nm.
本発明の第１の非晶質透明導電膜は、バンドギャップが３．０ｅＶ以上である。窒化インジウムガリウム（ＩｎＧａＮ）半導体のバンドギャップは２．７ｅＶ程度であり、窒化ガリウム系化合物半導体発光素子の発光波長は、用いる窒化ガリウム系化合物のバンドギャップに由来する光を発光するので、窒化インジウムガリウムのバンドギャップより大きいバンドギャップを有する本発明の第１の非晶質透明導電膜は、窒化インジウムガリウムを用いた半導体発光素子に対して十分な透明性を有する。
尚、本発明の第１の非晶質透明導電膜のバンドギャップの上限は特に限定されないが、例えば３．８ｅＶである。The first amorphous transparent conductive film of the present invention has a band gap of 3.0 eV or more. The band gap of indium gallium nitride (InGaN) semiconductor is about 2.7 eV, and the emission wavelength of the gallium nitride compound semiconductor light emitting device emits light derived from the band gap of the gallium nitride compound used. The first amorphous transparent conductive film of the present invention having a band gap larger than the band gap of the present invention is sufficiently transparent to a semiconductor light emitting device using indium gallium nitride.
The upper limit of the band gap of the first amorphous transparent conductive film of the present invention is not particularly limited, but is, for example, 3.8 eV.
本発明の第１の非晶質透明導電膜は、ハフニウム、タンタル、タングステン、ビスマス又はランタノイド系元素を１以上含むので、波長４６０ｎｍにおける屈折率が２．１以上となる。窒化ガリウムの波長４６０ｎｍにおける屈折率も２．１以上であるので、本発明の第１の非晶質透明導電膜を窒化ガリウム系化合物半導体発光素子に用いることにより、当該発光素子の光取出し効率を向上させることができる。
尚、本発明の第１の非晶質透明導電膜の波長４６０ｎｍにおける屈折率の上限は特に限定されないが、例えば２．４である。Since the first amorphous transparent conductive film of the present invention contains one or more hafnium, tantalum, tungsten, bismuth or lanthanoid elements, the refractive index at a wavelength of 460 nm is 2.1 or more. Since the refractive index of gallium nitride at a wavelength of 460 nm is 2.1 or more, the light extraction efficiency of the light emitting device can be improved by using the first amorphous transparent conductive film of the present invention for the gallium nitride compound semiconductor light emitting device. Can be improved.
In addition, although the upper limit of the refractive index in the wavelength of 460 nm of the 1st amorphous transparent conductive film of this invention is not specifically limited, For example, it is 2.4.
本発明の第１の非晶質透明導電膜は、仕事関数が５．５ｅＶ以上であり、後述するｐＧａＮコンタクト層の仕事関数と同じ又は近くなることから、非晶質透明導電膜及びｐＧａＮコンタクト層間のエネルギー障壁が緩和され、窒化ガリウム系化合物半導体発光素子の駆動電圧（Ｖｆ）を低減することができる。
尚、本発明の第１の非晶質透明導電膜の仕事関数の上限は特に限定されないが、例えば６．２ｅＶである。The first amorphous transparent conductive film of the present invention has a work function of 5.5 eV or more and is the same as or close to the work function of the pGaN contact layer described later. The energy barrier is reduced, and the driving voltage (Vf) of the gallium nitride compound semiconductor light emitting device can be reduced.
The upper limit of the work function of the first amorphous transparent conductive film of the present invention is not particularly limited, but is, for example, 6.2 eV.
本発明の第２の窒化ガリウム系化合物半導体発光素子用非晶質透明導電膜（以下、単に本発明の第２の非晶質透明導電膜という場合がある）は、酸化亜鉛を主成分とする金属酸化物と、ハフニウム、タンタル、タングステン、ビスマス及びランタノイド系元素からなる群から選ばれる１以上の元素を含む酸化物を含み、バンドギャップが３．２ｅＶ以上であり、波長４６０ｎｍにおける屈折率が２．２以上であり、仕事関数が５．５ｅＶ以上である。 The second amorphous transparent conductive film for a gallium nitride compound semiconductor light emitting device of the present invention (hereinafter sometimes simply referred to as the second amorphous transparent conductive film of the present invention) contains zinc oxide as a main component. A metal oxide and an oxide containing one or more elements selected from the group consisting of hafnium, tantalum, tungsten, bismuth, and lanthanoid elements, a band gap of 3.2 eV or more, and a refractive index of 2 at a wavelength of 460 nm. .2 or more and the work function is 5.5 eV or more.
上記において、酸化亜鉛を主成分とする金属酸化物とは、金属酸化物中の全金属元素に対する亜鉛原子の原子比（Ｚｎ／金属酸化物中の全金属元素）が、０．５以上であることを意味する。上記酸化亜鉛を主成分とする金属酸化物は他に、インジウム、ガリウム、アルミニウム、スズ等を含むことができる。 In the above, the metal oxide whose main component is zinc oxide is that the atomic ratio of zinc atoms to all metal elements in the metal oxide (Zn / all metal elements in the metal oxide) is 0.5 or more. Means that. In addition, the metal oxide containing zinc oxide as a main component can contain indium, gallium, aluminum, tin, and the like.
酸化亜鉛を主成分とする金属酸化物が酸化亜鉛−酸化インジウムの場合、金属酸化物中のインジウムと亜鉛の原子比Ｉｎ／（Ｚｎ＋Ｉｎ）は、好ましくは０．００５〜０．０５であり、より好ましくは０．０１〜０．０３である。Ｉｎ／（Ｚｎ＋Ｉｎ）が０．００５未満の場合、酸化インジウムの添加効果が小さく、比抵抗が低下しないおそれがある。一方、Ｉｎ／（Ｚｎ＋Ｉｎ）が０．０５超の場合、酸化インジウムのキャリヤー散乱効果により、比抵抗が下がらないおそれがある。 When the metal oxide whose main component is zinc oxide is zinc oxide-indium oxide, the atomic ratio In / (Zn + In) of indium to zinc in the metal oxide is preferably 0.005 to 0.05, and more Preferably it is 0.01-0.03. When In / (Zn + In) is less than 0.005, the effect of adding indium oxide is small, and the specific resistance may not decrease. On the other hand, when In / (Zn + In) is more than 0.05, the specific resistance may not decrease due to the carrier scattering effect of indium oxide.
酸化亜鉛を主成分とする金属酸化物が酸化亜鉛−酸化ガリウムの場合、金属酸化物中のガリウムと亜鉛の原子比Ｇａ／（Ｚｎ＋Ｇａ）は、好ましくは０．００５〜０．０５であり、より好ましくは０．０１〜０．０３である。Ｇａ／（Ｚｎ＋Ｇａ）が０．００５未満の場合、酸化ガリウムの添加効果が小さく、比抵抗が低下しないおそれがある。一方、Ｇａ／（Ｚｎ＋Ｇａ）が０．０５超の場合、酸化ガリウムのキャリヤー散乱効果により、比抵抗が下がらないおそれがある。 When the metal oxide mainly composed of zinc oxide is zinc oxide-gallium oxide, the atomic ratio Ga / (Zn + Ga) of gallium to zinc in the metal oxide is preferably 0.005 to 0.05, and more Preferably it is 0.01-0.03. When Ga / (Zn + Ga) is less than 0.005, the effect of adding gallium oxide is small, and the specific resistance may not decrease. On the other hand, when Ga / (Zn + Ga) exceeds 0.05, the specific resistance may not decrease due to the carrier scattering effect of gallium oxide.
酸化亜鉛を主成分とする金属酸化物が酸化亜鉛―酸化アルミニウムの場合、金属酸化物中のアルミニウムと亜鉛の原子比Ａｌ／（Ｚｎ＋Ａｌ）は、好ましくは０．００５〜０．０５であり、より好ましくは０．０１〜０．０３である。Ａｌ／（Ｚｎ＋Ａｌ）が０．００５未満の場合、酸化アルミニウムの添加効果が小さく、比抵抗が低下しないおそれがある。一方、Ａｌ／（Ｚｎ＋Ａｌ）が０．０５超の場合、酸化アルミニウムのキャリヤー散乱効果により、比抵抗が下がらないおそれがある。 When the metal oxide mainly composed of zinc oxide is zinc oxide-aluminum oxide, the atomic ratio Al / (Zn + Al) of aluminum to zinc in the metal oxide is preferably 0.005 to 0.05, and more Preferably it is 0.01-0.03. When Al / (Zn + Al) is less than 0.005, the effect of adding aluminum oxide is small, and the specific resistance may not decrease. On the other hand, when Al / (Zn + Al) is more than 0.05, the specific resistance may not decrease due to the carrier scattering effect of aluminum oxide.
酸化亜鉛を主成分とする金属酸化物が酸化亜鉛―酸化スズの場合、金属酸化物中のスズと亜鉛の原子比Ｓｎ／（Ｚｎ＋Ｓｎ）は、好ましくは０．０５〜０．５であり、より好ましくは０．２〜０．４である。原子比Ｓｎ／（Ｚｎ＋Ｓｎ）が、上記領域にあるときに、得られる膜が非晶質となり、均一な膜としやすくなる。
尚、Ｓｎ／（Ｚｎ＋Ｓｎ）が０．０５未満の場合、酸化スズの添加効果が小さく、比抵抗が低下しないおそれがある。When the metal oxide mainly composed of zinc oxide is zinc oxide-tin oxide, the atomic ratio Sn / (Zn + Sn) of tin and zinc in the metal oxide is preferably 0.05 to 0.5, and more Preferably it is 0.2-0.4. When the atomic ratio Sn / (Zn + Sn) is in the above region, the obtained film becomes amorphous, and a uniform film is easily obtained.
When Sn / (Zn + Sn) is less than 0.05, the effect of adding tin oxide is small, and the specific resistance may not decrease.
本発明の第２の非晶質透明導電膜は、バンドギャップが３．２ｅＶ以上である。上述したとおり、窒化インジウムガリウム（ＩｎＧａＮ）半導体のバンドギャップは２．７ｅＶ程度であるので、この非晶質透明導電膜は、窒化インジウムガリウムを用いた半導体発光素子に対して十分な透明性を有する。
尚、本発明の第２の非晶質透明導電膜のバンドギャップの上限は特に限定されないが、例えば４．５ｅＶである。The second amorphous transparent conductive film of the present invention has a band gap of 3.2 eV or more. As described above, since the band gap of indium gallium nitride (InGaN) semiconductor is about 2.7 eV, this amorphous transparent conductive film has sufficient transparency with respect to a semiconductor light emitting device using indium gallium nitride. .
The upper limit of the band gap of the second amorphous transparent conductive film of the present invention is not particularly limited, but is, for example, 4.5 eV.
本発明の第２の非晶質透明導電膜は、ハフニウム、タンタル、タングステン、ビスマス又はランタノイド系元素を１以上含むので、波長４６０ｎｍにおける屈折率が２．２以上となる。窒化ガリウムの波長４６０ｎｍにおける屈折率も２．１以上であるので、本発明の第２の非晶質透明導電膜を窒化ガリウム系化合物半導体発光素子に用いることにより、当該発光素子の光取出し効率を向上させることができる。
尚、本発明の第２の非晶質透明導電膜の波長４６０ｎｍにおける屈折率の上限は特に限定されないが、例えば２．５である。Since the second amorphous transparent conductive film of the present invention contains one or more hafnium, tantalum, tungsten, bismuth or lanthanoid elements, the refractive index at a wavelength of 460 nm is 2.2 or more. Since the refractive index of gallium nitride at a wavelength of 460 nm is 2.1 or more, the light extraction efficiency of the light emitting device can be improved by using the second amorphous transparent conductive film of the present invention for the gallium nitride compound semiconductor light emitting device. Can be improved.
The upper limit of the refractive index of the second amorphous transparent conductive film of the present invention at a wavelength of 460 nm is not particularly limited, but is, for example, 2.5.
本発明の第２の非晶質透明導電膜の上記以外の構成要件は、第１の非晶質透明導電膜と同様である。 Other structural requirements of the second amorphous transparent conductive film of the present invention are the same as those of the first amorphous transparent conductive film.
本発明の第３の窒化ガリウム系化合物半導体発光素子用非晶質透明導電膜（以下、単に本発明の第３の非晶質透明導電膜という場合がある）は、酸化スズを主成分とする金属酸化物と、ハフニウム、タンタル、タングステン、ビスマス及びランタノイド系元素からなる群から選ばれる１以上の元素を含む酸化物を含み、バンドギャップが３．５ｅＶ以上、波長３８０ｎｍにおける屈折率が２．３以上、及び仕事関数が５．５ｅＶ以上である。 The third amorphous transparent conductive film for a gallium nitride compound semiconductor light emitting device of the present invention (hereinafter sometimes simply referred to as the third amorphous transparent conductive film of the present invention) contains tin oxide as a main component. A metal oxide and an oxide containing one or more elements selected from the group consisting of hafnium, tantalum, tungsten, bismuth, and lanthanoid elements, a band gap of 3.5 eV or more, and a refractive index of 2.3 at a wavelength of 380 nm. The work function is 5.5 eV or more.
上記において、酸化スズを主成分とする金属酸化物とは、金属酸化物中の全金属元素に対するスズ原子の原子比（Ｓｎ／金属酸化物中の全金属元素）が、０．５以上であることを意味する。上記酸化スズを主成分とする金属酸化物は他に、インジウム、亜鉛等を含むことができる。 In the above, the metal oxide whose main component is tin oxide is that the atomic ratio of tin atoms to all metal elements in the metal oxide (Sn / all metal elements in the metal oxide) is 0.5 or more. Means that. In addition, the metal oxide containing tin oxide as a main component can contain indium, zinc, and the like.
酸化スズを主成分とする金属酸化物が酸化スズ―酸化インジウムの場合、金属酸化物中のインジウムとスズの原子比Ｉｎ／（Ｉｎ＋Ｓｎ）は、好ましくは０．０５〜０．５であり、より好ましくは０．２〜０．４である。原子比Ｉｎ／（Ｉｎ＋Ｓｎ）が上記領域にあるときに、得られる膜が非晶質となり、均一な膜としやすくなる。
尚、Ｉｎ／（Ｉｎ＋Ｓｎ）が０．０５未満の場合、酸化インジウムの添加効果が小さく、比抵抗が低下しないおそれがある。When the metal oxide mainly composed of tin oxide is tin oxide-indium oxide, the atomic ratio In / (In + Sn) of indium to tin in the metal oxide is preferably 0.05 to 0.5, and more Preferably it is 0.2-0.4. When the atomic ratio In / (In + Sn) is in the above-described region, the obtained film becomes amorphous and is easily formed as a uniform film.
When In / (In + Sn) is less than 0.05, the effect of adding indium oxide is small, and the specific resistance may not decrease.
酸化スズを主成分とする金属酸化物が酸化スズ―酸化亜鉛の場合、金属酸化物中の亜鉛とスズの原子比Ｚｎ／（Ｚｎ＋Ｓｎ）は、好ましくは０．０１〜０．３であり、より好ましくは０．０５〜０．２５である。原子比Ｚｎ／（Ｚｎ＋Ｓｎ）が上記領域にあるときに、得られる膜が非晶質となり、均一な膜としやすくなる。
尚、Ｚｎ／（Ｚｎ＋Ｓｎ）が０．０１未満の場合、酸化亜鉛の添加効果が小さく、比抵抗が低下しないおそれがある。一方、Ｚｎ／（Ｚｎ＋Ｓｎ）が０．３超の場合、酸化亜鉛のキャリヤー散乱効果が大きくなり、比抵抗が増大するおそれがある。When the metal oxide mainly composed of tin oxide is tin oxide-zinc oxide, the atomic ratio Zn / (Zn + Sn) of zinc to tin in the metal oxide is preferably 0.01 to 0.3, and more Preferably it is 0.05-0.25. When the atomic ratio Zn / (Zn + Sn) is in the above-described region, the obtained film becomes amorphous and is easily formed as a uniform film.
In addition, when Zn / (Zn + Sn) is less than 0.01, there is a possibility that the effect of adding zinc oxide is small and the specific resistance does not decrease. On the other hand, when Zn / (Zn + Sn) is more than 0.3, the carrier scattering effect of zinc oxide is increased, and the specific resistance may be increased.
本発明の第３の非晶質透明導電膜は、バンドギャップが３．５ｅＶ以上である。例えば窒化ガリウム（ＧａＮ）半導体のバンドギャップは３．４ｅＶ程度であり窒化ガリウム系化合物半導体発光素子の発光波長は、用いる窒化ガリウム系化合物のバンドギャップに由来する光を発光するので、窒化ガリウムのバンドギャップより大きいバンドギャップを有する本発明の第３の非晶質透明導電膜は、窒化ガリウムを用いた半導体発光素子に対して十分な透明性を有する。
尚、本発明の第３の非晶質透明導電膜のバンドギャップの上限は特に限定されないが、例えば３．８ｅＶである。The third amorphous transparent conductive film of the present invention has a band gap of 3.5 eV or more. For example, the band gap of a gallium nitride (GaN) semiconductor is about 3.4 eV, and the emission wavelength of the gallium nitride compound semiconductor light emitting device emits light derived from the band gap of the gallium nitride compound used. The third amorphous transparent conductive film of the present invention having a band gap larger than the gap has sufficient transparency for a semiconductor light emitting element using gallium nitride.
The upper limit of the band gap of the third amorphous transparent conductive film of the present invention is not particularly limited, but is, for example, 3.8 eV.
本発明の第３の非晶質透明導電膜は、ハフニウム、タンタル、タングステン、ビスマス又はランタノイド系元素を１以上含むので、波長３８０ｎｍにおける屈折率が２．３以上となり、窒化ガリウム系化合物半導体発光素子の光取出し効率を向上させることができる。
尚、本発明の第３の非晶質透明導電膜の波長３８０ｎｍにおける屈折率の上限は特に限定されないが、例えば２．６である。Since the third amorphous transparent conductive film of the present invention contains one or more hafnium, tantalum, tungsten, bismuth or lanthanoid elements, the refractive index at a wavelength of 380 nm is 2.3 or more, and the gallium nitride compound semiconductor light emitting device The light extraction efficiency can be improved.
The upper limit of the refractive index of the third amorphous transparent conductive film of the present invention at a wavelength of 380 nm is not particularly limited, but is 2.6, for example.
本発明の第３の非晶質透明導電膜の上記以外の構成要件は、第１の非晶質透明導電膜と同様である。 The other structural requirements of the third amorphous transparent conductive film of the present invention are the same as those of the first amorphous transparent conductive film.
本発明の第３の非晶質透明導電膜は、好ましくはさらに添加物として酸化ガリウムを含む。この酸化ガリウムの添加量は、好ましくは非晶質透明導電膜中の全金属元素に対してガリウム原子の原子比が１〜１０ａｔ％となる量である。添加量が１ａｔ％未満の場合、非晶質透明導電膜のバンドギャップを広げる効果が小さくなるおそれがある。一方、添加量が１０ａｔ％超の場合、非晶質透明導電膜の比抵抗が上昇するおそれがある。 The third amorphous transparent conductive film of the present invention preferably further contains gallium oxide as an additive. The amount of gallium oxide added is preferably such that the atomic ratio of gallium atoms is 1 to 10 at% with respect to all metal elements in the amorphous transparent conductive film. When the addition amount is less than 1 at%, the effect of widening the band gap of the amorphous transparent conductive film may be reduced. On the other hand, when the addition amount exceeds 10 at%, the specific resistance of the amorphous transparent conductive film may increase.
尚、本発明の第３の非晶質透明導電膜が酸化ガリウムを含む場合において、ガリウム元素が非晶質透明導電膜に拡散しても、非晶質透明導電膜の性能への影響は少なく、問題なく窒化ガリウム系化合物半導体発光素子を駆動することができる。 In the case where the third amorphous transparent conductive film of the present invention contains gallium oxide, even if gallium element diffuses into the amorphous transparent conductive film, there is little influence on the performance of the amorphous transparent conductive film. The gallium nitride compound semiconductor light emitting device can be driven without any problem.
本発明の第１の非晶質透明導電膜は、インジウム、亜鉛及びスズからなる群から選ばれる１以上の金属の酸化物と、ハフニウム、タンタル、タングステン、ビスマス及びランタノイド系元素からなる群から選ばれる１以上の元素を含む酸化物から実質的になる、又はこれら成分のみからなる。「実質的になる」とは、上記成分に加えて後述するその他の成分を含みうることである。 The first amorphous transparent conductive film of the present invention is selected from the group consisting of one or more metal oxides selected from the group consisting of indium, zinc and tin, and the group consisting of hafnium, tantalum, tungsten, bismuth and lanthanoid elements. Consisting essentially of an oxide containing one or more elements or consisting solely of these components. “Substantially” means that in addition to the above components, other components described later may be included.
本発明の第２の非晶質透明導電膜は、酸化亜鉛を主成分とする金属酸化物と、ハフニウム、タンタル、タングステン、ビスマス及びランタノイド系元素からなる群から選ばれる１以上の元素を含む酸化物から実質的になる、又はこれら成分のみからなる。「実質的になる」とは、上記成分に加えて後述するその他の成分を含むうることである。 The second amorphous transparent conductive film of the present invention is an oxide containing one or more elements selected from the group consisting of metal oxides mainly composed of zinc oxide and hafnium, tantalum, tungsten, bismuth and lanthanoid elements. Consists essentially of the product, or consists solely of these components. “Substantially” means that in addition to the above components, other components described later may be included.
本発明の第３の非晶質透明導電膜は、酸化スズを主成分とする金属酸化物と、ハフニウム、タンタル、タングステン、ビスマス及びランタノイド系元素からなる群から選ばれる１以上の元素を含む酸化物に、任意に酸化ガリウムを含んで実質的になる、又はこれら成分のみからなる。「実質的になる」とは、上記成分に加えて後述するその他の成分を含みうることである。 The third amorphous transparent conductive film of the present invention is an oxide containing at least one element selected from the group consisting of metal oxides mainly composed of tin oxide and hafnium, tantalum, tungsten, bismuth and lanthanoid elements. The product optionally comprises gallium oxide or consists solely of these components. “Substantially” means that in addition to the above components, other components described later may be included.
本発明の第１〜第３の非晶質透明導電膜（以下、これらをまとめて本発明の非晶質透明導電膜という場合がある）は、本発明の効果を損なわない範囲で、Ｔｉ、Ｚｒ、Ｎｂ、Ｍｏ等を含む金属酸化物をさらに含んでもよい。 The first to third amorphous transparent conductive films of the present invention (hereinafter sometimes collectively referred to as the amorphous transparent conductive film of the present invention) are Ti, A metal oxide containing Zr, Nb, Mo, or the like may be further included.
本発明の透明導電膜は非晶質である。透明導電膜が結晶質である場合、結晶化の際に透明導電膜中の原子の再配置が起こり、接触する窒化ガリウムとの界面に応力を発生する。その結果、透明導電膜が剥離したり、接触抵抗が大きくなるおそれがある。本発明の透明導電膜は非晶質であるので、上記再配置や再配列がなく、発光素子の安定した駆動が可能である。 The transparent conductive film of the present invention is amorphous. When the transparent conductive film is crystalline, rearrangement of atoms in the transparent conductive film occurs during crystallization, and stress is generated at the interface with the contacting gallium nitride. As a result, the transparent conductive film may be peeled off or the contact resistance may be increased. Since the transparent conductive film of the present invention is amorphous, there is no rearrangement or rearrangement described above, and the light emitting element can be driven stably.
本発明の非晶質透明導電膜は、スパッタリング法により成膜することができる。用いるターゲットは、所望する非晶質透明導電膜の組成を有するターゲットを用いればよい。用いるスパッタリング法としては、ＤＣスパッタリング法又はＲＦスパッタリング法を適用でき、生産性の観点から好ましくは成膜速度が速く、装置も安価であるＤＣスパッタリング法を用いる。 The amorphous transparent conductive film of the present invention can be formed by a sputtering method. The target to be used may be a target having a desired amorphous transparent conductive film composition. As a sputtering method to be used, a DC sputtering method or an RF sputtering method can be applied. From the viewpoint of productivity, the DC sputtering method is preferably used because the film formation rate is high and the apparatus is inexpensive.
本発明の非晶質透明導電膜は、室温で成膜することができる。これにより成膜後に通常行うレーザーアニール処理を省略することができる。尚、レーザーアニール処理を行ってもよく、この処理を行う場合、例えばｐ型半導体層が含む元素の拡散が起こりにくい２００〜３００℃の温度域で行うとよい。レーザーアニール処理を行うことにより、非晶質透明導電膜の透過率を高めることができ、駆動電圧が低く、発光出力の高い窒化ガリウム系化合物半導体発光素子を得ることができる。 The amorphous transparent conductive film of the present invention can be formed at room temperature. Thereby, the laser annealing process normally performed after film-forming can be skipped. Laser annealing treatment may be performed, and in this case, for example, it may be performed in a temperature range of 200 to 300 ° C. where diffusion of elements included in the p-type semiconductor layer hardly occurs. By performing the laser annealing treatment, the transmittance of the amorphous transparent conductive film can be increased, and a gallium nitride compound semiconductor light emitting device with a low driving voltage and a high light emission output can be obtained.
インジウム、亜鉛及びスズからなる群から選ばれる１以上の金属の酸化物を含む本発明の非晶質透明導電膜は、酸素を混入したアルゴンを供給しながらスパッタリングすることにより、バンドギャップを３．０ｅＶ以上（本発明の第２の非晶質透明導電膜では３．２ｅＶ以上、第３の非晶質透明導電膜では３．５ｅＶ以上）にすることができる。酸素を含まないアルゴンを供給した場合は、バンドギャップが３．０ｅＶ未満となるおそれがある。 The amorphous transparent conductive film of the present invention containing one or more metal oxides selected from the group consisting of indium, zinc and tin has a band gap of 3. by sputtering while supplying argon mixed with oxygen. 0 eV or more (3.2 eV or more for the second amorphous transparent conductive film of the present invention, 3.5 eV or more for the third amorphous transparent conductive film). When argon containing no oxygen is supplied, the band gap may be less than 3.0 eV.
上記酸素の供給量は最適酸素量よりも多くするとよい。最適酸素量より多くの酸素を供給することにより、非晶質透明導電膜の屈折率、仕事関数の大きくすることができる。
尚、最適酸素量とは非晶質透明導電膜の抵抗値が最も低くなる酸素量であり、酸素の供給量を変化させて、導電膜の比抵抗を計測することにより求めることができる。The oxygen supply amount may be larger than the optimum oxygen amount. By supplying more oxygen than the optimum oxygen amount, the refractive index and work function of the amorphous transparent conductive film can be increased.
The optimal oxygen amount is the oxygen amount at which the resistance value of the amorphous transparent conductive film is the lowest, and can be obtained by measuring the specific resistance of the conductive film while changing the oxygen supply amount.
酸素の供給量は、最適酸素量より多ければ特に限定されないが、最適酸素量の１．０１倍〜２．０倍の範囲であるとよく、好ましくは１．０５倍〜１．５倍、より好ましくは１．１倍〜１．５倍である。酸素の供給量が、最適酸素量の１．０１倍未満の場合、非晶質透明導電膜の屈折率及び仕事関数が大きくならないおそれがある。一方、酸素の供給量が最適酸素量の２．０倍超の場合、非晶質透明導電膜の比抵抗が大きくなりすぎるおそれがある。 The supply amount of oxygen is not particularly limited as long as it is larger than the optimum oxygen amount, but it may be in the range of 1.01 to 2.0 times the optimum oxygen amount, preferably 1.05 to 1.5 times. Preferably they are 1.1 times-1.5 times. When the supply amount of oxygen is less than 1.01 times the optimum oxygen amount, the refractive index and work function of the amorphous transparent conductive film may not increase. On the other hand, when the supply amount of oxygen is more than 2.0 times the optimum oxygen amount, the specific resistance of the amorphous transparent conductive film may be too large.
尚、ターゲットが多量の酸素を包含している、装置のチャンバー内部に酸素や水が吸着している等が原因で、アルゴン１００％が最適酸素量となる場合がある。その場合には、スパッタ圧力の０．００５〜０．１倍の分圧となる酸素量を供給して成膜すればよい。 Note that 100% argon may be the optimum oxygen amount because the target contains a large amount of oxygen or oxygen or water is adsorbed inside the chamber of the apparatus. In that case, the film may be formed by supplying an oxygen amount which is 0.005 to 0.1 times the sputtering pressure.
以下、本発明の窒化ガリウム系化合物半導体発光素子を図面を参照して説明する。
図１は上記非晶質透明導電膜を含む本発明の窒化ガリウム系化合物半導体発光素子の一実施形態を示す概略断面図であり、図２は図１に示す窒化ガリウム系化合物半導体発光素子の上面図である。
窒化ガリウム系化合物半導体発光素子１は、基板１０上に凸形状を有するｎ型半導体層１２が積層しており、ｎ型半導体層１２の凸部上には発光層１４、ｐ型半導体層１６、非晶質透明導電膜１８及び正極ボンディングパッド２０がこの順に積層しており、ｎ型半導体層１２の凹部上には、発光層１４等と並列に負極２２が積層している。The gallium nitride compound semiconductor light emitting device of the present invention will be described below with reference to the drawings.
FIG. 1 is a schematic sectional view showing an embodiment of the gallium nitride compound semiconductor light emitting device of the present invention including the above amorphous transparent conductive film, and FIG. 2 is a top view of the gallium nitride compound semiconductor light emitting device shown in FIG. FIG.
In the gallium nitride compound semiconductor
本発明の窒化ガリウム系化合物半導体発光素子１は、本発明の非晶質透明導電膜１８がｐ型半導体層１６上に直接積層している。尚、本発明の非晶質透明導電膜１８は、低温で成膜可能であるので、ｐ型半導体層１６にダメージを与えることなく積層することができる。
In the gallium nitride compound semiconductor
本発明の非晶質透明導電膜は仕事関数が５．５ｅＶ以上であるので、ｐ型窒化ガリウム半導体と直接接合することにより、これら接合面におけるエネルギー障壁を小さくすることができる。結果、窒化ガリウム系化合物半導体発光素子は低電圧で駆動可能となる。 Since the amorphous transparent conductive film of the present invention has a work function of 5.5 eV or more, the energy barrier at these junction surfaces can be reduced by directly joining the p-type gallium nitride semiconductor. As a result, the gallium nitride compound semiconductor light emitting device can be driven at a low voltage.
ｐ型窒化ガリウム半導体が、例えばｐ型窒化インジウムガリウム（ＩｎＧａＮ）半導体である場合において、非晶質透明導電膜として本発明の第１の非晶質透明導電膜を用いると、当該非晶質透明導電膜は波長４６０ｎｍにおける屈折率が２．１以上であり、ｐ型窒化インジウムガリウム半導体の屈折率に近く、窒化ガリウム系化合物半導体発光素子の光取出し効率を向上させることができる。 When the p-type gallium nitride semiconductor is, for example, a p-type indium gallium nitride (InGaN) semiconductor, when the first amorphous transparent conductive film of the present invention is used as the amorphous transparent conductive film, the amorphous transparent The conductive film has a refractive index of 2.1 or more at a wavelength of 460 nm, is close to the refractive index of the p-type indium gallium nitride semiconductor, and can improve the light extraction efficiency of the gallium nitride-based compound semiconductor light emitting device.
また、本発明の第１の非晶質透明導電膜は、バンドギャップが３．０ｅＶ以上である。窒化インジウムガリウム半導体のバンドギャップは２．７ｅＶ程度であり、窒化ガリウム系化合物半導体発光素子の発光波長は、用いる窒化ガリウム系化合物のバンドギャップに由来する光を発光するので、窒化インジウムガリウムのバンドギャップより大きいバンドギャップを有する本発明の第１の非晶質透明導電膜は十分な透明性を有し、発光素子の光取出し効率をさらに向上させることができる。 The first amorphous transparent conductive film of the present invention has a band gap of 3.0 eV or more. The band gap of indium gallium nitride semiconductor is about 2.7 eV, and the emission wavelength of the gallium nitride compound semiconductor light emitting device emits light derived from the band gap of the gallium nitride compound used. The first amorphous transparent conductive film of the present invention having a larger band gap has sufficient transparency, and can further improve the light extraction efficiency of the light emitting element.
ｐ型窒化ガリウム半導体が、例えばｐ型インジウムドープ窒化ガリウム半導体である場合は、ｐ型インジウムドープ窒化ガリウム半導体のバンドギャップは３．４ｅＶ程度であり、窒化ガリウム系化合物半導体発光素子の発光は波長が３８０ｎｍ程度まで短波長化する。この場合において、非晶質透明導電膜として本発明の第２の非晶質透明導電膜を用いると、当該非晶質透明導電膜はバンドギャップが３．５ｅＶ以上、仕事関数が５．５ｅＶ以上、及び波長３８０ｎｍにおける屈折率が２．３以上であるので、上記と同様の理由で発光素子の光取出し効率を向上させることができる。 When the p-type gallium nitride semiconductor is, for example, a p-type indium-doped gallium nitride semiconductor, the band gap of the p-type indium-doped gallium nitride semiconductor is about 3.4 eV, and the light emission of the gallium nitride-based compound semiconductor light-emitting element has a wavelength. The wavelength is shortened to about 380 nm. In this case, when the second amorphous transparent conductive film of the present invention is used as the amorphous transparent conductive film, the amorphous transparent conductive film has a band gap of 3.5 eV or more and a work function of 5.5 eV or more. Since the refractive index at a wavelength of 380 nm is 2.3 or more, the light extraction efficiency of the light emitting element can be improved for the same reason as described above.
非晶質透明導電膜１８の膜厚は、比抵抗及び透過率の観点から、好ましくは３５ｎｍ〜１０００００ｎｍであり、生産コストの観点から、より好ましくは３５ｎｍ〜１０００ｎｍである。具体的には非晶質透明導電膜１８の膜厚は、透過率が極大になるように設定するとよい。透過率が極大となる膜厚は、下記式により求めることができる。
λ／ｎ×（１／４＋ｍ／２）
［式中、λは発光素子が発する光の波長を表し、
ｎは非晶質透明導電膜の屈折率を表し、及び
ｍは０以上の整数を表す。］The film thickness of the amorphous transparent
λ / n × (1/4 + m / 2)
[In the formula, λ represents the wavelength of light emitted from the light emitting element,
n represents the refractive index of the amorphous transparent conductive film, and m represents an integer of 0 or more. ]
例えば窒化ガリウム系化合物半導体発光素子の発する光の波長が４６０ｎｍであり、非晶質透明導電膜の屈折率が２．１である場合、透過率が極大となる非晶質透明導電膜の膜厚は、５５ｎｍ（ｍ＝０）、１６５ｎｍ（ｍ＝１）、２７５ｎｍ（ｍ＝３）となる。 For example, when the wavelength of light emitted from a gallium nitride-based compound semiconductor light-emitting element is 460 nm and the refractive index of the amorphous transparent conductive film is 2.1, the film thickness of the amorphous transparent conductive film that maximizes the transmittance Are 55 nm (m = 0), 165 nm (m = 1), and 275 nm (m = 3).
ちなみに非晶質透明導電膜の透過率が極小となる膜厚は、下記式により求めることができる。
λ／ｎ×（ｍ／２）
［式中、λは発光素子が発する光の波長を表し、
ｎは非晶質透明導電膜の屈折率を表し、及び
ｍは０以上の整数を表す。］Incidentally, the film thickness at which the transmittance of the amorphous transparent conductive film is minimized can be obtained by the following formula.
λ / n × (m / 2)
[In the formula, λ represents the wavelength of light emitted from the light emitting element,
n represents the refractive index of the amorphous transparent conductive film, and m represents an integer of 0 or more. ]
例えば窒化ガリウム系化合物半導体発光素子の発する光の波長が４６０ｎｍであり、非晶質透明導電膜の屈折率が２．１である場合には、透過率が極小となる非晶質透明導電膜の膜厚は、１１０ｎｍ（ｍ＝１）となる。 For example, when the wavelength of light emitted from a gallium nitride-based compound semiconductor light-emitting element is 460 nm and the refractive index of the amorphous transparent conductive film is 2.1, the transmittance of the amorphous transparent conductive film with the minimum transmittance is obtained. The film thickness is 110 nm (m = 1).
本発明の窒化ガリウム系化合物半導体発光素子１において、好ましくは直接接合した非晶質透明導電膜１８及びｐ型半導体層１６の積層体の非晶質透明導電膜１８上にさらに透明導電膜を積層する。特に本発明の非晶質透明導電膜１８の比抵抗が大きく、電極として用いる場合には、さらに透明導電膜を積層することにより、非晶質透明導電膜１８が有する光取出し効率向上効果及びエネルギー障壁低減効果はそのままに、電極の抵抗を下げることができる。
In the gallium nitride compound semiconductor
さらに積層する透明導電膜としては、例えばＩＴＯ、ＩＺＯを用いることができ、その膜厚は、上述の透過率が極大となる膜厚にするとよい。 Further, as the transparent conductive film to be laminated, for example, ITO or IZO can be used, and the film thickness is preferably set to a film thickness that maximizes the above-described transmittance.
また、非晶質透明導電膜１８は、好ましくはその成膜時に酸化インジウム−酸化スズ又は酸化インジウム−酸化亜鉛を同時に成膜することにより、ｐ型半導体層１６側から徐々に屈折率が低下する屈折率分布を有する。このようにして成膜して得られる非晶質透明導電膜は、その内部に屈折率及び仕事関数の傾斜を有し、内部における発光の損失を低減できる。その結果、窒化ガリウム系化合物半導体発光素子の光取出し効率を向上させることができる。
Further, the refractive index of the amorphous transparent
上記屈折率及び仕事関数の傾斜を有する非晶質透明導電膜は、共スパッタ法を用いることにより成膜することができる。具体的には、本発明の第１の非晶質透明導電膜又は第２の非晶質透明導電膜を成膜するための第１のターゲット、及びＩＴＯ又はＩＺＯからなる第２のターゲットを調製し、それぞれスパッタ装置に装着する。ターゲット装着後、成膜開始時には電力を第１のターゲットのみに印加し、その後、第２のターゲットにも電力を徐々に印加していき、それと同時に第１のターゲットへの印加電力を下げていく。最終的には第２のターゲットのみに電力を印加することで、屈折率及び仕事関数の傾斜を有する非晶質透明導電膜を成膜することができる。 The amorphous transparent conductive film having the refractive index and the work function gradient can be formed by using a co-sputtering method. Specifically, a first target for forming the first amorphous transparent conductive film or the second amorphous transparent conductive film of the present invention and a second target made of ITO or IZO are prepared. Each is mounted on a sputtering device. After the target is mounted, power is applied only to the first target at the start of film formation, and then the power is gradually applied to the second target, and at the same time, the power applied to the first target is decreased. . Finally, an amorphous transparent conductive film having a refractive index and a work function gradient can be formed by applying power only to the second target.
基板１０は周知の基板を用いることができ、例えばサファイア単結晶（Ａｌ２Ｏ３；Ａ面、Ｃ面、Ｍ面、Ｒ面）、スピネル単結晶（ＭｇＡｌ２Ｏ４）、ＺｎＯ単結晶、ＬｉＡｌＯ２単結晶、ＬｉＧａＯ２単結晶、ＭｇＯ単結晶等の酸化物単結晶、Ｓｉ単結晶、ＳｉＣ単結晶、ＧａＡｓ単結晶、ＡｌＮ単結晶、ＧａＮ単結晶、ＺｒＢ２等のホウ化物単結晶等の材料からなる基板を用いることができ、好ましくはサファイア単結晶又はＳｉＣ単結晶を用いた基板である。
尚、基板１０の面方位は特に限定されない。また、基板１０はジャスト基板であってもよく、オフ角を付与した基板であってもよい。A known substrate can be used as the
The plane orientation of the
基板１０上のｎ型半導体層１２、発光層１４及びｐ型半導体層１６からなる積層体は、周知の各種構造を有する積層体を用いることができる。例えばｐ型半導体層は、キャリア濃度が一般的な濃度であればよく、１×１０１７ｃｍ−３程度と比較的キャリア濃度が低いｐ型半導体層であっても、本発明の非晶質透明導電膜を積層することができる。As the laminate composed of the n-
これらｎ型半導体層１２、発光層１４及びｐ型半導体層１６を構成する窒化ガリウム系化合物半導体としては、例えば一般式ＡｌＸＧａＹＩｎＺＮ１−ＡＭＡ（０≦Ｘ≦１、０≦Ｙ≦１、０≦Ｚ≦１で且つ、Ｘ＋Ｙ＋Ｚ＝１。記号Ｍは窒素（Ｎ）とは別の第Ｖ族元素を表し、０≦Ａ＜１である。）で表わされる窒化物系化合物半導体を用いることができる。Examples of the gallium nitride compound semiconductor constituting the n-
上記窒化ガリウム系化合物半導体の成長方法は特に限定されず、ＭＯＣＶＤ（有機金属化学気相成長法）、ＨＶＰＥ（ハイドライド気相成長法）、ＭＢＥ（分子線エピタキシー法）等の周知の方法を適用できる。これらの成長方法のうち、膜厚制御性、量産性の観点からＭＯＣＶＤ法を用いると好ましい。 The growth method of the gallium nitride compound semiconductor is not particularly limited, and well-known methods such as MOCVD (metal organic chemical vapor deposition), HVPE (hydride vapor deposition), MBE (molecular beam epitaxy) can be applied. . Of these growth methods, the MOCVD method is preferably used from the viewpoints of film thickness controllability and mass productivity.
ＭＯＣＶＤ法において、キャリアガスとして水素（Ｈ２）又は窒素（Ｎ２）を、ＩＩＩ族原料であるＧａ源としてトリメチルガリウム（ＴＭＧ）又はトリエチルガリウム（ＴＥＧ）を、Ａｌ源としてトリメチルアルミニウム（ＴＭＡ）又はトリエチルアルミニウム（ＴＥＡ）を、Ｉｎ源としてトリメチルインジウム（ＴＭＩ）又はトリエチルインジウム（ＴＥＩ）を、Ｖ族原料であるＮ源としてアンモニア（ＮＨ３）、ヒドラジン（Ｎ２Ｈ４）等を用いることができる。また、ドーパントとしては、ｎ型半導体層にはＳｉ原料としてモノシラン（ＳｉＨ４）又はジシラン（Ｓｉ２Ｈ６）を、Ｇｅ原料としてゲルマンガス（ＧｅＨ４）、テトラメチルゲルマニウム（（ＣＨ３）４Ｇｅ）、テトラエチルゲルマニウム（（Ｃ２Ｈ５）４Ｇｅ）等の有機ゲルマニウム化合物を用いることができる。In the MOCVD method, hydrogen (H 2 ) or nitrogen (N 2 ) is used as a carrier gas, trimethyl gallium (TMG) or triethyl gallium (TEG) is used as a Ga source which is a group III material, and trimethyl aluminum (TMA) or Al is used as an Al source. Triethylaluminum (TEA) can be used, trimethylindium (TMI) or triethylindium (TEI) can be used as an In source, and ammonia (NH 3 ), hydrazine (N 2 H 4 ), or the like can be used as an N source that is a group V raw material. . Moreover, as a dopant, monosilane (SiH 4 ) or disilane (Si 2 H 6 ) is used as an Si raw material for the n-type semiconductor layer, germane gas (GeH 4 ), and tetramethyl germanium ((CH 3 ) 4 Ge are used as the Ge raw material. ), And organic germanium compounds such as tetraethylgermanium ((C 2 H 5 ) 4 Ge) can be used.
ＭＢＥ法では、元素状のゲルマニウムもドーピング源として用いることができる。ｐ型半導体層には、Ｍｇ原料として、例えばビスシクロペンタジエニルマグネシウム（Ｃｐ２Ｍｇ）又はビスエチルシクロペンタジエニルマグネシウム（ＥｔＣｐ２Ｍｇ）を用いる。In the MBE method, elemental germanium can also be used as a doping source. For the p-type semiconductor layer, for example, biscyclopentadienyl magnesium (Cp 2 Mg) or bisethylcyclopentadienyl magnesium (EtCp 2 Mg) is used as the Mg raw material.
図３は、窒化ガリウム系化合物半導体発光素子１に用いることができる窒化ガリウム系化合物半導体の一実施形態を示す概略断面図である。
窒化ガリウム系化合物半導体２は、サファイア基板３０上に、ＧａＮ下地層３２、ｎ型ＧａＮコンタクト層３４、ｎ型ＡｌＧａＮクラッド層３６、ＩｎＧａＮ発光層３８、ｐ型ＡｌＧａＮクラッド層４０及びｐ型ＧａＮコンタクト層４２がこの順に積層した構造を有する。FIG. 3 is a schematic cross-sectional view showing an embodiment of a gallium nitride compound semiconductor that can be used in the gallium nitride compound semiconductor
The gallium nitride compound semiconductor 2 includes a
窒化ガリウム系化合物半導体発光素子１は、例えば図３に示す窒化ガリウム系化合物半導体２のｎ型ＡｌＧａＮクラッド層３６、ＩｎＧａＮ発光層３８、ｐ型ＡｌＧａＮクラッド層４０及びｐ型ＧａＮコンタクト層４２の一部をエッチングによって除去することによってｎ型ＧａＮコンタクト層３４を露出させ、当該ｎ型ＧａＮコンタクト層３４の露出部に負極を設け、及びｐ型ＧａＮコンタクト層４２上に正極を設けることにより作製できる。
The gallium nitride compound semiconductor
正極ボンディングパッド２０は、回路基板又はリードフレームと電気接続することができ、Ａｕ、Ａｌ、Ｎｉ、Ｃｕ等からなる。
正極ボンディングパッド２０の厚さは、好ましくは１００〜１０００ｎｍであり、膜厚が大きいほどボンダビリティーが高くなることから、より好ましくは３００〜１０００ｎｍであり、製造コストの観点からさらに好ましくは３００〜５００ｎｍである。The positive
The thickness of the positive
負極２２としては、公知材料を用いることができ、例えばＴｉ／Ａｕを負極として用いる。
As the
本発明の窒化ガリウム系化合物半導体発光素子は駆動電圧（Ｖｆ）が低く、優れた光取出し効率を有するので、例えばＬＥＤランプに用いることができる。本発明の窒化ガリウム系化合物半導体発光素子を用いたＬＥＤランプの形状は特に限定されず、例えば汎用用途の砲弾型、パソコン又は携帯電話のバックライト用途のサイドビュー型、表示器用途のトップビュー型のいずれでもよい。 The gallium nitride-based compound semiconductor light-emitting device of the present invention has a low driving voltage (Vf) and excellent light extraction efficiency, so that it can be used for, for example, an LED lamp. The shape of the LED lamp using the gallium nitride compound semiconductor light emitting device of the present invention is not particularly limited. For example, a shell type for general use, a side view type for backlighting a personal computer or a mobile phone, and a top view type for display use. Either of these may be used.
図４は、本発明の窒化ガリウム系化合物半導体発光素子を用いたＬＥＤランプ（砲弾型）の一実施形態を示す概略断面図である。ＬＥＤランプ３は凹形状の台座部を有するフレームと棒状フレームの２つフレーム５０が対向しており、上記台座部と窒化ガリウム系化合物半導体発光素子１が樹脂等を介して結合している。この発光素子１と２つのフレーム５０は、２つのワイヤー５２を介して電気的に結合しており、これらワイヤー５２を含む発光素子１周辺を透明樹脂５４が覆うようにて保護している。
［実施例］FIG. 4 is a schematic cross-sectional view showing an embodiment of an LED lamp (bullet type) using the gallium nitride-based compound semiconductor light emitting element of the present invention. In the LED lamp 3, a frame having a concave pedestal portion and two
[Example]
実施例１
以下のようにして、図１の構造を有する窒化ガリウム系化合物半導体発光素子を作製した。
まず、ＭＯＣＶＤ法を用いて、基板であるサファイアのｃ面（（０００１）結晶面）上に、ＡｌＮからなるバッファ層を介して、順次、アンドープＧａＮ下地層（層厚＝２μｍ）、Ｓｉドープｎ型ＧａＮコンタクト層（層厚＝２μｍ、キャリア濃度＝１×１０１９ｃｍ−３）、Ｓｉドープｎ型Ａｌ０．０７Ｇａ０．９３Ｎクラッド層（層厚＝１２．５ｎｍ、キャリア濃度＝１×１０１８ｃｍ−３）、６層のＳｉドープＧａＮ障壁層（層厚＝１４．０ｎｍ、キャリア濃度＝１×１０１８ｃｍ−３）と５層のアンドープＩｎ０．２０Ｇａ０．８０Ｎの井戸層（層厚＝２．５ｎｍ）とからなる多重量子構造の発光層、Ｍｇドープｐ型Ａｌ０．０７Ｇａ０．９３Ｎクラッド層（層厚１０ｎｍ）、及びＭｇドープｐ型ＧａＮコンタクト層（層厚＝１００ｎｍ）を積層し、エピタキシャル構造を有する積層体を作製した。Example 1
A gallium nitride compound semiconductor light emitting device having the structure of FIG. 1 was produced as follows.
First, an undoped GaN underlayer (layer thickness = 2 μm) and Si-doped n are sequentially formed on the c-plane ((0001) crystal plane) of sapphire, which is a substrate, through a buffer layer made of AlN, using MOCVD. Type GaN contact layer (layer thickness = 2 μm, carrier concentration = 1 × 10 19 cm −3 ), Si-doped n-type Al 0.07 Ga 0.93 N cladding layer (layer thickness = 12.5 nm, carrier concentration = 1 ×) 10 18 cm −3 ), six Si-doped GaN barrier layers (layer thickness = 14.0 nm, carrier concentration = 1 × 10 18 cm −3 ), and five undoped In 0.20 Ga 0.80 N wells A light emitting layer having a multi-quantum structure comprising a layer (layer thickness = 2.5 nm), an Mg-doped p-type Al 0.07 Ga 0.93 N clad layer (
ＨＦ及びＨＣｌを用いて、上記積層体のｐ型ＧａＮコンタクト層表面を洗浄した後、ｐ型ＧａＮコンタクト層上に、酸化イッテリビウム（全金属元素に対するＹｂの原子比：Ｙｂ／全金属元素＝８ａｔ％）、酸化インジウム（全金属元素に対するＩｎの原子比：Ｉｎ／全金属元素＝８０ａｔ％）及び酸化スズ（全金属元素に対するＳｎの原子比：Ｓｎ／全金属元素＝１２ａｔ％）からなる非晶質透明導電膜を形成した。この非晶質透明導電膜はＤＣマグネトロンスパッタを用いて成膜し、膜厚は約２５０ｎｍであった。 After cleaning the surface of the p-type GaN contact layer of the laminate using HF and HCl, ytterbium oxide (atomic ratio of Yb to all metal elements: Yb / all metal elements = 8 at%) is formed on the p-type GaN contact layer. ), Indium oxide (atomic ratio of In to all metal elements: In / total metal element = 80 at%), and tin oxide (atomic ratio of Sn to all metal elements: Sn / total metal element = 12 at%) A transparent conductive film was formed. This amorphous transparent conductive film was formed using DC magnetron sputtering, and the film thickness was about 250 nm.
得られた非晶質透明導電膜について、以下の評価を行った。結果を表１に示す。
（１）比抵抗
得られた非晶質透明導電膜について、ロレスタ（三菱化学株式会社製）を用いて表面抵抗を計測し、及び触針式膜厚測定器を用いて膜厚を測定し、これら測定結果を基に比抵抗を算出した。
（２）バンドギャップ
得られた非晶質透明導電膜について、分光光度計を用いて透過率を測定して吸収係数を求め、吸収系数の２乗を波長に対しプロットし、その吸収切片をバンドギャップとした。
（３）屈折率
反射・透過システム（Ｆｉｌｍ Ｔｅｋ３０００、ヤーマン株式会社製）を用いて、得られた非晶質透明導電膜の透過率、反射率を測定し、屈折率をフィティングにより求めた。
（４）仕事関数
ＡＣ１（理研計器社製）を用いて、非晶質透明導電膜の照射する光エネルギーと放出される電子の量をプロットし、電子放出の立ち上がり切片を仕事関数として求めた。The following evaluation was performed about the obtained amorphous transparent conductive film. The results are shown in Table 1.
(1) Specific resistance About the obtained amorphous transparent conductive film, surface resistance was measured using Loresta (made by Mitsubishi Chemical Corporation), and film thickness was measured using a stylus type film thickness meter, The specific resistance was calculated based on these measurement results.
(2) Band gap About the obtained amorphous transparent conductive film, the transmittance | permeability is measured using a spectrophotometer, an absorption coefficient is calculated | required, the square of the absorption system number is plotted with respect to a wavelength, The absorption intercept is banded. It was a gap.
(3) Refractive index Using a reflection / transmission system (Film Tek3000, manufactured by Yarman Co., Ltd.), the transmittance and reflectance of the obtained amorphous transparent conductive film were measured, and the refractive index was determined by fitting.
(4) Work function Using AC1 (manufactured by Riken Keiki Co., Ltd.), the light energy irradiated by the amorphous transparent conductive film and the amount of emitted electrons were plotted, and the rising intercept of electron emission was obtained as a work function.
成膜した非晶質透明導電膜は正極として機能し、４６０ｎｍの波長領域で９０％以上の高い透過率を有していた。尚、透過率は、同じ厚さの非晶質透明導電膜をガラス板上に積層して透過率測定用のサンプル調製し、調製したサンプルについて分光光度計を用いて測定することにより求めた。また、調製したサンプルの透過率は、ガラス板のみで測定した光透過ブランク値を考慮して測定した。 The formed amorphous transparent conductive film functioned as a positive electrode, and had a high transmittance of 90% or more in a wavelength region of 460 nm. In addition, the transmittance | permeability was calculated | required by laminating | stacking the amorphous transparent conductive film of the same thickness on a glass plate, preparing the sample for a transmittance | permeability measurement, and measuring the prepared sample using a spectrophotometer. Moreover, the transmittance | permeability of the prepared sample was measured in consideration of the light transmission blank value measured only with the glass plate.
非晶質透明導電膜成膜後、エピタキシャル構造を有する積層体に一般的なドライエッチングを施し、Ｓｉドープｎ型ＧａＮコンタクト層の一部を露出させた。その後、真空蒸着法を用いて非晶質透明導電膜（正極）上の一部及びＳｉドープｎ型ＧａＮコンタクト層上に、Ｔｉからなる第１の層（層厚＝１００ｎｍ）、Ａｕからなる第２の層（層厚＝４００ｎｍ）を順次積層した積層体を形成し、それぞれ正極ボンディングパッド及び負極とし、窒化ガリウム系化合物半導体発光素子を作製した。 After the amorphous transparent conductive film was formed, general dry etching was performed on the laminated body having an epitaxial structure to expose a part of the Si-doped n-type GaN contact layer. Thereafter, a first layer made of Ti (layer thickness = 100 nm) and a first layer made of Au are formed on a part of the amorphous transparent conductive film (positive electrode) and the Si-doped n-type GaN contact layer by using a vacuum deposition method. A stacked body in which two layers (layer thickness = 400 nm) were sequentially stacked was formed, and a gallium nitride-based compound semiconductor light-emitting device was fabricated using a positive electrode bonding pad and a negative electrode, respectively.
正極ボンディングパッド及び負極を形成した後、サファイアからなる基板の裏面をダイヤモンド微粒等の砥粒を使用して研磨し、最終的に鏡面に仕上げた。その後、作製した窒化ガリウム系化合物半導体発光素子を裁断し、３５０μｍ角の正方形チップとした。得られたチップをリードフレーム状に載置した後、金（Ａｕ）線でリードフレームと結線した。 After forming the positive electrode bonding pad and the negative electrode, the back surface of the substrate made of sapphire was polished using abrasive grains such as diamond fine grains, and finally finished to a mirror surface. Thereafter, the produced gallium nitride compound semiconductor light emitting device was cut into a 350 μm square chip. After the obtained chip was placed in a lead frame shape, it was connected to the lead frame with a gold (Au) wire.
得られたチップを、プローブ針を用いて通電し、電流印加値２０ｍＡにおける順方向電圧（駆動電圧：Ｖｆ）を測定した。その結果、駆動電圧は３．１Ｖであり、低電圧駆動が可能であることを確認した。また、一般的な積分球で測定されたチップの発光出力（Ｐｏ）は１１ｍＷであり、発光面の発光分布は、透光性導電酸化膜の全面で発光していることを確認した。チップを１００時間の連続発光させたところ、チップ内の発光にバラツキがなく、安定した発光が確認された。非晶質透明導電膜の伝導率が２．５×１０Ｅ＋３（Ｓ／ｃｍ）の時の、チップの熱拡散係数は３．５Ｗ／ｍＫ超であり、発光のバラツキは低減していた。 The obtained chip was energized using a probe needle, and the forward voltage (drive voltage: Vf) at a current application value of 20 mA was measured. As a result, the drive voltage was 3.1 V, and it was confirmed that low voltage drive was possible. Further, the light emission output (Po) of the chip measured with a general integrating sphere was 11 mW, and the light emission distribution on the light emitting surface was confirmed to emit light over the entire surface of the translucent conductive oxide film. When the chip was allowed to emit light continuously for 100 hours, there was no variation in light emission within the chip, and stable light emission was confirmed. When the conductivity of the amorphous transparent conductive film was 2.5 × 10E + 3 (S / cm), the thermal diffusion coefficient of the chip was over 3.5 W / mK, and the variation in light emission was reduced.
断面透過電子顕微鏡のＥＤＸ分析により、ｐ型ＧａＮコンタクト層及び非晶質透明導電膜（正極）の界面から透光性導電酸化膜側へ１ｎｍ及び２ｎｍの位置でのＧａの濃度を測定した。その結果、透光性導電酸化膜内のＧａ濃度は、界面から非晶質透明導電膜中へのＧａの拡散がほとんどないことが確認できた。尚、この透光性導電酸化膜内のＧａ濃度は、非晶質透明導電膜内の界面付近に存在すると考えられる金属元素（Ｉｎ＋Ｓｎ＋Ｇａ＋Ｙｂ）との比率（ａｔ％）で定義した。 The concentration of Ga at 1 nm and 2 nm positions from the interface of the p-type GaN contact layer and the amorphous transparent conductive film (positive electrode) to the translucent conductive oxide film side was measured by EDX analysis with a cross-sectional transmission electron microscope. As a result, it was confirmed that the Ga concentration in the translucent conductive oxide film hardly caused Ga diffusion from the interface into the amorphous transparent conductive film. The Ga concentration in the translucent conductive oxide film was defined by the ratio (at%) with the metal element (In + Sn + Ga + Yb) that is considered to exist near the interface in the amorphous transparent conductive film.
実施例２〜２３及び比較例１〜３
表１に示す組成を有する透明導電膜を成膜したほかは実施例１と同様にして窒化ガリウム系化合物半導体発光素子及びチップを作製し、評価した。結果を表１に示す。Examples 2 to 23 and Comparative Examples 1 to 3
A gallium nitride compound semiconductor light emitting device and a chip were prepared and evaluated in the same manner as in Example 1 except that a transparent conductive film having the composition shown in Table 1 was formed. The results are shown in Table 1.
比較例４
比較例１の窒化ガリウム系化合物半導体発光素子は、熱アニール処理を行っていないので、透過率が極端に低くいうえ、Ｐｏが４ｍＷと非常に低かった。そこで、比較例１の非晶質透明導電膜の透過率を上昇させるため、さらに約６００℃で熱アニール処理を
１分間行った。その結果、Ｖｆが３．５Ｖ、Ｐｏが１０ｍＷとなり素子特性が向上した。しかし、これら結果は実施例の結果と比べて十分な値とは言えなかった。Comparative Example 4
Since the gallium nitride compound semiconductor light emitting device of Comparative Example 1 was not subjected to thermal annealing, the transmittance was extremely low and Po was as low as 4 mW. Therefore, in order to increase the transmittance of the amorphous transparent conductive film of Comparative Example 1, a thermal annealing treatment was further performed at about 600 ° C. for 1 minute. As a result, Vf was 3.5 V, Po was 10 mW, and the device characteristics were improved. However, these results were not sufficient values compared to the results of the examples.
比較例５
熱アニール処理後、さらにレーザーアニール処理（エネルギー密度が１５０ｍＪｃｍ−２のＫｒＦエキシマレーザーを１パルス（パルス幅＝２０ｎｓ））を行ったほかは比較例４と同様にして窒化ガリウム系化合物半導体発光素子を評価した。その結果その結果、Ｖｆが３．５Ｖ、Ｐｏが１１ｍＷとなり素子特性が向上した。しかし、これら結果は、比較例４と同様に実施例の結果と比べて十分な値とは言えなかった。Comparative Example 5
A gallium nitride-based compound semiconductor light-emitting device was obtained in the same manner as in Comparative Example 4 except that after the thermal annealing treatment, laser annealing treatment (1 pulse (pulse width = 20 ns) of a KrF excimer laser having an energy density of 150 mJcm-2) was performed. evaluated. As a result, Vf was 3.5 V, Po was 11 mW, and the device characteristics were improved. However, these results could not be said to be sufficient values as compared with the results of the example as in Comparative Example 4.
本発明の窒化ガリウム系化合物半導体発光素子は駆動電圧低く、優れた光取出し効率を有するので、例えば照明用途、ディスプレイ用途及びバックライト用途の高輝度ＬＥＤランプに好適に用いることができる。 Since the gallium nitride-based compound semiconductor light-emitting device of the present invention has a low driving voltage and excellent light extraction efficiency, it can be suitably used for, for example, a high-intensity LED lamp for illumination, display, and backlight.
Claims (10)
ハフニウム、タンタル、タングステン、ビスマス及びランタノイド系元素からなる群から選ばれる１以上の元素を含む酸化物を含み、
バンドギャップが３．０ｅＶ以上であり、
波長４６０ｎｍにおける屈折率が２．１以上であり、
仕事関数が５．５ｅＶ以上である窒化ガリウム系化合物半導体発光素子用非晶質透明導電膜。One or more metal oxides selected from the group consisting of indium, zinc and tin;
An oxide containing one or more elements selected from the group consisting of hafnium, tantalum, tungsten, bismuth and lanthanoid elements,
The band gap is 3.0 eV or more,
The refractive index at a wavelength of 460 nm is 2.1 or more,
An amorphous transparent conductive film for a gallium nitride-based compound semiconductor light-emitting device having a work function of 5.5 eV or more.
ハフニウム、タンタル、タングステン、ビスマス及びランタノイド系元素からなる群から選ばれる１以上の元素を含む酸化物を含み、
バンドギャップが３．２ｅＶ以上であり、
波長４６０ｎｍにおける屈折率が２．２以上であり、
仕事関数が５．５ｅＶ以上である窒化ガリウム系化合物半導体発光素子用非晶質透明導電膜。A metal oxide based on zinc oxide,
An oxide containing one or more elements selected from the group consisting of hafnium, tantalum, tungsten, bismuth and lanthanoid elements,
The band gap is 3.2 eV or more,
The refractive index at a wavelength of 460 nm is 2.2 or more,
An amorphous transparent conductive film for a gallium nitride-based compound semiconductor light-emitting device having a work function of 5.5 eV or more.
ハフニウム、タンタル、タングステン、ビスマス及びランタノイド系元素からなる群から選ばれる１以上の元素を含む酸化物を含み、
バンドギャップが３．５ｅＶ以上であり、
波長３８０ｎｍにおける屈折率が２．３以上であり、
仕事関数が５．５ｅＶ以上である窒化ガリウム系化合物半導体発光素子用非晶質透明導電膜。A metal oxide mainly composed of tin oxide;
An oxide containing one or more elements selected from the group consisting of hafnium, tantalum, tungsten, bismuth and lanthanoid elements,
The band gap is 3.5 eV or more,
The refractive index at a wavelength of 380 nm is 2.3 or more,
An amorphous transparent conductive film for a gallium nitride-based compound semiconductor light-emitting device having a work function of 5.5 eV or more.
前記非晶質透明導電膜中の全金属元素に対する前記添加物のガリウム原子の原子比が１〜１０ａｔ％である請求項６に記載の窒化ガリウム系化合物半導体発光素子用非晶質透明導電膜。Furthermore, it contains gallium oxide as an additive,
The amorphous transparent conductive film for a gallium nitride-based compound semiconductor light emitting element according to claim 6, wherein an atomic ratio of gallium atoms of the additive to all metal elements in the amorphous transparent conductive film is 1 to 10 at%.
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| US8569754B2 (en) * | 2010-11-05 | 2013-10-29 | Semiconductor Energy Laboratory Co., Ltd. | Semiconductor device and manufacturing method thereof |
| KR101957816B1 (en) * | 2012-08-24 | 2019-03-13 | 엘지이노텍 주식회사 | Light emitting device |
| JP6869157B2 (en) * | 2017-09-29 | 2021-05-12 | 出光興産株式会社 | Oxide sintered body, sputtering target, amorphous oxide semiconductor thin film, and thin film transistor |
| JP2019064887A (en) * | 2017-10-04 | 2019-04-25 | 出光興産株式会社 | Oxide sintered body, sputtering target, oxide semiconductor thin film, and thin film transistor |
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