WO2017065294A1 - 窒化亜鉛系化合物およびその製造方法 - Google Patents

窒化亜鉛系化合物およびその製造方法 Download PDF

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WO2017065294A1
WO2017065294A1 PCT/JP2016/080597 JP2016080597W WO2017065294A1 WO 2017065294 A1 WO2017065294 A1 WO 2017065294A1 JP 2016080597 W JP2016080597 W JP 2016080597W WO 2017065294 A1 WO2017065294 A1 WO 2017065294A1
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zinc nitride
chemical formula
compound represented
cazn
zinc
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French (fr)
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史康 大場
細野　秀雄
秀典 平松
日出也 雲見
悠 熊谷
壮史 飯村
善行 村場
リー アラン バートン
田中　功
洋陽 日沼
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国立大学法人 東京工業大学
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Priority to JP2017545497A priority Critical patent/JP6773666B2/ja
Priority to US15/767,550 priority patent/US10308521B2/en
Publication of WO2017065294A1 publication Critical patent/WO2017065294A1/ja
Priority to US16/387,155 priority patent/US10737947B2/en

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Definitions

  • the present invention relates to a zinc nitride compound and a method for producing the same.
  • GaN is widely used in LED light sources, but cannot emit light in the visible light region because of its wide band gap. InN has a narrow band gap and cannot emit light in the visible light region. Furthermore, Ga is expensive and In is a rare element.
  • Various zinc nitride-based compounds have been proposed. For example, ZnSnN 2 is difficult to realize p-type, and Ca 2 ZnN 2 is an indirect transition type, which can be applied to light-emitting elements and high-efficiency solar cells. (Non-patent Document 1).
  • An object of the present invention is to solve the above-mentioned problems and provide a zinc nitride compound suitable for an electronic device such as a high-speed transistor, a high-efficiency visible light emitting device, a high-efficiency solar cell, or a high-sensitivity visible light sensor. .
  • a zinc nitride-based compound represented by the chemical formula CaZn 2 N 2 (2) A zinc nitride-based compound represented by the chemical formula X 1 2 ZnN 2 (X 1 is Be or Mg). (3) A zinc nitride compound represented by the chemical formula Zn 3 LaN 3 . (4) A zinc nitride compound represented by the chemical formula ZnTiN 2 . (5) A zinc nitride compound represented by the chemical formula ZnX 2 N 2 (X 2 is Zr or Hf). (6) A zinc nitride compound represented by a chemical formula Zn 2 X 3 N 3 (X 3 is V, Nb or Ta).
  • the zinc nitride compound of the present invention can provide a zinc nitride compound suitable for electronic devices such as high-speed transistors, high-efficiency visible light emitting elements, high-efficiency solar cells, and high-sensitivity visible light sensors.
  • a is a crystal structure of a zinc nitride compound represented by the chemical formula CaZn 2 N 2
  • b is a calculated phase diagram of the Ca—Zn—N system
  • c is a band structure of the zinc nitride compound represented by CaZn 2 N 2 (conductivity). Band and valence band)
  • d is a phase diagram in the chemical potential space of the Ca—Zn—N system. It illustrates the crystal structure of a typical zinc nitride-based compound of the present invention other than those represented by A) Formula CaZn 2 N 2.
  • the zinc nitride-based compound of the present invention can be represented by any of the following chemical formulas.
  • These zinc nitride compounds according to the present invention of A) to G) are novel compounds not recorded in ICSD (inorganic crystal structure database).
  • the basic electronic properties of these zinc nitride compounds according to the present invention of A) to G) are shown in FIG.
  • a is a band gap ( ⁇ is a direct gap, ⁇ is an indirect gap), and b is an effective mass of holes and electrons.
  • the zinc nitride compound according to the present invention is a compound semiconductor, and in particular, the zinc nitride compound according to the present invention represented by A) chemical formula CaZn 2 N 2 or C) chemical formula Zn 3 LaN 3 is a direct transition type. It is a compound semiconductor and is suitable for applications such as light emitting elements and thin film solar cells.
  • the space groups to which these zinc nitride compounds according to the present invention belong are as follows. A) It belongs to the space group P - 3m1. B) It belongs to the space group I4 / mmm. C) It belongs to the space group P6 3 / m. D) belong to the space group Pna2 1. E) Belongs to space group P3m1. F) It belongs to the space group Cmc2 1 . G) belong to the space group Pmn2 1.
  • A) a zinc nitride-based compound represented by the chemical formula CaZn 2 N 2 suitable as a direct transition type compound semiconductor will be described below.
  • the zinc nitride-based compound represented by) can be similarly understood from the entire detailed description.
  • a is A) a crystal structure of a zinc nitride compound represented by the chemical formula CaZn 2 N 2
  • b is a calculated phase diagram of the Ca—Zn—N system
  • c is zinc nitride represented by CaZn 2 N 2.
  • d is a phase diagram in the chemical potential space of the Ca—Zn—N system.
  • CaZn 2 N 2 exists stably under a high nitrogen chemical potential, that is, under a high nitrogen partial pressure.
  • a zinc nitride-based compound represented by the chemical formula CaZn 2 N 2 has a band gap of 1.9 eV, but by adding Mg, Sr, Ba or Cd, the chemical formula CaM 1 2x Zn 2 (1-x) N 2 (M 1 is Mg or Cd. 0 ⁇ x ⁇ 1) or M 2 x Ca 1-x Zn 2 N 2 (M 2 is Sr or Ba. 0 ⁇ x ⁇ 1),
  • the band gap can be controlled as a compound semiconductor having a band gap of 0.4 eV to 3.2 eV.
  • CaZn 2 N 2 easily forms nitrogen vacancies that become shallow donors, it can be n-type even when undoped, but it is preferable to form n-type by doping. Further, for example, carrier compensation by nitrogen vacancies is suppressed under a high nitrogen partial pressure, and a p-type can be formed by doping.
  • the zinc nitride compound represented by the chemical formula CaZn 2 N 2 is preferably synthesized under a high pressure of 1 GPa or more.
  • the raw material compounds preferably Ca 3 N 2 and 2Zn 3 N 2
  • the reaction is usually performed at 800 to 1500 ° C. and 1 to 10 GPa for 30 minutes to 5 hours. Is done.
  • the resulting high-pressure synthesis reaction product can be further purified by removing zinc in the product.
  • the resulting high-pressure synthesis reaction product powder and I 2 are placed in a glass container, for example, at about 15 to 30 ° C., preferably at room temperature for 5 to 10 minutes in an inert atmosphere such as argon or nitrogen.
  • an inert atmosphere such as argon or nitrogen.
  • zinc is converted to zinc iodide (ZnI 2 ).
  • the produced zinc iodide is dissolved in a solvent such as dimethyl ether to remove the solution.
  • the inert atmosphere is used to suppress oxidation of Zn 2+ and I ⁇ .
  • the zinc nitride-based compound of the present invention is a chemical vapor deposition method such as a physical vapor deposition method such as a sputtering method, a pulse laser deposition method, or a vacuum evaporation method, and a metal organic vapor deposition method. It can be obtained by depositing a thin film on a substrate using the method. As the substrate, an oxide substrate or the like can be appropriately selected according to the purpose.
  • CaZn 2 N 2 is composed of common elements on earth, directly a bandgap, further effective mass of small charge (0.17 m 0 in electronic, 0.91 m 0 with holes) are particularly useful in that it has a is there.
  • the direct band gap of 1.9 eV possessed by CaZn 2 N 2 corresponds to the red region of visible light, and high theoretical conversion efficiency can be expected as a solar cell light absorption layer.
  • an electronic element using CaZn 2 N 2 as an active layer is an electronic element (light emitting element) that emits light by injecting current in the visible light region, or an electronic element (solar cell) that absorbs visible light and generates a photovoltage or a photocurrent. Or an optical sensor).
  • FIGS. 3a to 3e show the crystal structures of other typical zinc nitride compounds of the present invention, as shown in FIG. 2a, for the zinc nitride compounds represented by the chemical formula CaZn 2 N 2 .
  • FIGS. 4a to 4g show A) a zinc nitride compound represented by the chemical formula CaZn 2 N 2 in the same manner as shown in FIG. 2b.
  • Other representative zinc nitride compounds of the present invention include Mg—Zn— The calculation state diagram of N system etc. is shown.
  • FIGS. 5a to 5g show the band structures (conduction bands) of other typical zinc nitride compounds of the present invention, as shown in FIG. 2c, for the zinc nitride compound represented by the chemical formula CaZn 2 N 2 . And valence band).
  • a zinc nitride compound suitable for electronic devices such as high-speed transistors, high-efficiency visible light emitting elements, high-efficiency solar cells, and high-sensitivity visible light sensors.
  • Example 1 Synthesis of zinc nitride compound represented by CaZn 2 N 2
  • the high-pressure synthesizer used is a belt-type high-pressure synthesizer, which is a sample holder: a high-pressure cell, a pressure control range: 2-5.5 GPa, and a temperature control range: room temperature to 1600 ° C.
  • the X-ray diffraction pattern of the resulting high pressure synthesis reaction product is shown in FIG. 6a.
  • About 69 wt% of the product was CaZn 2 N 2 and the rest was Zn.
  • the X-ray diffraction pattern of the obtained reaction product is shown in FIG. 6b.
  • the product was Ca 2 ZnN 2 .
  • Ca 2 ZnN 2 had an indirect gap of 1.6 eV (calculated value of 1.65 eV) and a direct gap of 1.9 eV (calculated value of 1.92 eV).
  • the high-pressure synthesizer used is a belt-type high-pressure synthesizer, which is a sample holder: a high-pressure cell, a pressure control range: 2-5.5 GPa, and a temperature control range: room temperature to 1600 ° C.
  • the X-ray diffraction pattern of the obtained high-pressure synthesis reaction product is shown in FIG.
  • About 80 wt% of the product was CaZn 2 N 2 and the rest was Zn or the like.
  • Photo which is light emission generated from CaZn 2 N 2 of the resulting high-pressure synthesis reaction product by photon excitation (wavelength: 355 nm, energy density: ⁇ 7 mJ / cm 2 ) using a Nd: YAG third harmonic pulse laser Luminescence was measured. The red photoluminescence was clearly observed visually at 10K. The result is shown in FIG. a shows the photoluminescence spectrum in 10, 100, 200, and 300K, b shows the temperature dependence of a spectrum peak position.

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Abstract

本発明は、高速トランジスタ、高効率可視光発光素子、高効率太陽電池、高感度可視光センサー等の電子素子に好適な窒化亜鉛系化合物を提供する。　化学式ＣａＺｎ２Ｎ２、化学式Ｘ１ ２ＺｎＮ２（Ｘ１はＢｅまたはＭｇである）等で表される窒化亜鉛系化合物。好適には、1 GPa以上の高圧下で合成される。

Description

窒化亜鉛系化合物およびその製造方法
　本発明は、窒化亜鉛系化合物およびその製造方法に関する。
　ＧａＮはＬＥＤ光源で広く実用化されているが、バンドギャップが広いために、そのまま可視光域で発光させることはできない。ＩｎＮはバンドギャップが狭すぎて、可視光域で発光できない。さらに、Gaは高コストであり、Ｉｎは希少元素である。また、種々の窒化亜鉛系化合物が提案されているが、たとえばＺｎＳｎＮ２はｐ型の実現が困難であり、Ｃａ２ＺｎＮ２は間接遷移型であって、発光素子や高効率太陽電池への応用に適さない等の課題がある（非特許文献１）。
J.Solid State Chem.88,528-533(1990)
　本発明は、上記課題を解決して、高速トランジスタ、高効率可視光発光素子、高効率太陽電池、高感度可視光センサー等の電子素子に好適な窒化亜鉛系化合物を提供することを目的とする。
　本発明は上記の問題を解決するために、以下の発明を提供するものである。
（１）化学式ＣａＺｎ２Ｎ２で表される窒化亜鉛系化合物。
（２）化学式Ｘ１ ２ＺｎＮ２（Ｘ１はＢｅまたはＭｇである）で表される窒化亜鉛系化合物。
（３）化学式Ｚｎ３ＬａＮ３で表される窒化亜鉛系化合物。
（４）化学式ＺｎＴｉＮ２で表される窒化亜鉛系化合物。
（５）化学式ＺｎＸ２Ｎ２（Ｘ２はＺｒまたはＨｆである）で表される窒化亜鉛系化合物。
（６）化学式Ｚｎ２Ｘ３Ｎ３（Ｘ３はＶ、ＮｂまたはＴａである）で表される窒化亜鉛系化合物。
（７）化学式Ｚｎ３ＷＮ４で表される窒化亜鉛系化合物。
（８）化合物半導体である上記（１）～（７）のいずれかに記載の窒化亜鉛系化合物。
（９）直接遷移型化合物半導体である上記（１）または（３）に記載の窒化亜鉛系化合物。
（１０）化学式ＣａＭ１ ２ｘＺｎ２（１－ｘ）Ｎ２(Ｍ１はＭｇまたはＣｄである。０≦ｘ≦１)またはＭ２ ｘＣａ１－ｘＺｎ２Ｎ２ (Ｍ２はＳｒまたはＢａである。０≦ｘ≦１)で表され、バンドギャップが0.4eV～3.２eVである化合物半導体。
（１１）上記（８）～（１０）のいずれかに記載の化合物半導体を活性層に有する電子素子。
（１２）可視光域で電流注入発光する上記（１１）に記載の電子素子。
（１３）可視光を吸収し光電圧あるいは光電流を発生する上記（１１）に記載の電子素子。
（１４）１GPa以上の高圧下で合成する上記（１）～（７）のいずれかに記載の窒化亜鉛系化合物の製造方法。
　本発明の窒化亜鉛系化合物は、高速トランジスタ、高効率可視光発光素子、高効率太陽電池、高感度可視光センサー等の電子素子に好適な窒化亜鉛系化合物を提供し得る。
本発明に係る窒化亜鉛系化合物の基礎電子的特性を示す図。 ａは化学式ＣａＺｎ２Ｎ２で表される窒化亜鉛系化合物の結晶構造、ｂはＣａ－Ｚｎ－Ｎ系の計算状態図、ｃはＣａＺｎ２Ｎ２表される窒化亜鉛系化合物のバンド構造（伝導帯および価電子帯）、ｄはＣａ－Ｚｎ－Ｎ系の化学ポテンシャル空間での状態図、を示す。 Ａ）化学式ＣａＺｎ２Ｎ２で表される以外の本発明の代表的な窒化亜鉛系化合物の結晶構造を示す図。 Ａ）化学式ＣａＺｎ２Ｎ２で表される以外の本発明の代表的な窒化亜鉛系化合物の、Ｍｇ－Ｚｎ－Ｎ系等の計算状態図を示す図。 Ａ）化学式ＣａＺｎ２Ｎ２で表される以外の本発明の代表的な窒化亜鉛系化合物のバンド構造（伝導帯および価電子帯）を示す図。 実施例１および比較例１で得られた合成反応生成物のＸ線回折図形。 実施例１および比較例１で得られた合成反応生成物の吸収スペクトル図。 実施例２で得られた合成反応生成物のＸ線回折図形。 実施例２で得られた合成反応生成物のフォトルミネッセンス。 実施例２で得られた高純度化粉末生成物のＸ線回折図形。
　本発明の窒化亜鉛系化合物は、次の化学式のいずれかで表され得る。
Ａ）化学式ＣａＺｎ２Ｎ２で表される窒化亜鉛系化合物。
Ｂ）化学式Ｘ１ ２ＺｎＮ２（Ｘ１はＢｅまたはＭｇである）で表される窒化亜鉛系化合物。
Ｃ）化学式Ｚｎ３ＬａＮ３で表される窒化亜鉛系化合物。
Ｄ）化学式ＺｎＴｉＮ２で表される窒化亜鉛系化合物。
Ｅ）化学式ＺｎＸ２Ｎ２（Ｘ２はＺｒまたはＨｆである）で表される窒化亜鉛系化合物。
Ｆ）化学式Ｚｎ２Ｘ３Ｎ３（Ｘ３はＶ、ＮｂまたはＴａである）で表される窒化亜鉛系化合物。
Ｇ）化学式Ｚｎ３ＷＮ４で表される窒化亜鉛系化合物。
　これらのＡ）～Ｇ）の本発明に係る窒化亜鉛系化合物は、ＩＣＳＤ（無機結晶構造データベース）に未収録の新規化合物である。これらのＡ）～Ｇ）の本発明に係る窒化亜鉛系化合物の基礎電子的特性を図１に示す。図１において、ａはバンドギャップ（●は直接ギャップ、○は間接ギャップ）、ｂはホールおよび電子の有効質量を示す。本発明に係る窒化亜鉛系化合物は、化合物半導体であり、特に、Ａ）化学式ＣａＺｎ２Ｎ２またはＣ）化学式Ｚｎ３ＬａＮ３で表される、本発明に係る窒化亜鉛系化合物は、直接遷移型化合物半導体であり、発光素子、薄膜太陽電池等の応用に好適である。
　これらの本発明に係る窒化亜鉛系化合物が属する空間群は次のとおりである。
Ａ）空間群P-3m1に属する。
Ｂ）空間群I4/mmmに属する。
Ｃ）空間群P63/mに属する。
Ｄ）空間群Pna21に属する。
Ｅ）空間群P3m1に属する。
Ｆ）空間群Cmc21に属する。
Ｇ）空間群Pmn21に属する。
　本発明の窒化亜鉛系化合物のうち、直接遷移型化合物半導体として好適なＡ）化学式ＣａＺｎ２Ｎ２で表される窒化亜鉛系化合物について、代表的に以下に説明するが、その他のＢ）～Ｇ）で表される窒化亜鉛系化合物についても詳細な説明の全体から同様に理解され得る。
　図２において、ａはＡ）化学式ＣａＺｎ２Ｎ２で表される窒化亜鉛系化合物の結晶構造、ｂはＣａ－Ｚｎ－Ｎ系の計算状態図、ｃはＣａＺｎ２Ｎ２で表される窒化亜鉛系化合物のバンド構造（伝導帯および価電子帯）、ｄはＣａ－Ｚｎ－Ｎ系の化学ポテンシャル空間での状態図、を示す。ｄからわかるように、ＣａＺｎ２Ｎ２は高い窒素化学ポテンシャルの下、すなわち高い窒素分圧の下で安定に存在する。
　Ａ）化学式ＣａＺｎ２Ｎ２で表される窒化亜鉛系化合物は、バンドギャップ１．９ｅＶを有するが、Ｍｇ、Ｓｒ，ＢａまたはＣｄを添加することにより、化学式ＣａＭ１ ２ｘＺｎ２（１－ｘ）Ｎ２(Ｍ１はＭｇまたはＣｄである。０≦ｘ≦１)またはＭ２ ｘＣａ１－ｘＺｎ２Ｎ２ (Ｍ２はＳｒまたはＢａである。０≦ｘ≦１)で表され、バンドギャップが0.4eV～3.２eVである化合物半導体として、バンドギャップを制御し得る。また、ＣａＺｎ２Ｎ２は、浅いドナーになる窒素空孔が形成されやすいため、アンドープでもｎ型になり得るが、ドーピングにより、ｎ型を形成するのが好適である。さらに、たとえば高窒素分圧下では窒素空孔によるキャリア補償が抑えられ、ドーピングによりｐ型を形成し得る。
　Ａ）化学式ＣａＺｎ２Ｎ２で表される窒化亜鉛系化合物は、好適には、1 GPa以上の高圧下で合成される。この場合、高圧合成装置内に、好適にはＣａ３Ｎ２および２Ｚｎ３Ｎ２である原料化合物を導入し、通常８００～１５００℃、１～１０GPaで、３０分間から５時間程度、反応に供される。
　得られる高圧合成反応生成物は、生成物中の亜鉛を除去することによりさらに高純度化し得る。好適には、得られる高圧合成反応生成物粉末とＩ２を、たとえばガラス製容器に入れ、アルゴン、窒素等の不活性雰囲気下に、１５～３０℃程度、好ましくは室温で、５～１０分間程度、保持して、亜鉛をヨウ化亜鉛（ＺｎＩ２）に変換させる。ついで、生成したヨウ化亜鉛をジメチルエーテル等の溶媒に溶解させて、溶液を除去する。不活性雰囲気を用いるのは、Ｚｎ２＋、Ｉ-の酸化を抑制するためである。
　本発明の窒化亜鉛系化合物は、上記の高圧合成法以外にも、スパッタ法、パルスレーザー堆積法、真空蒸着法等の物理的気相堆積法および有機金属気相堆積法等の化学気相堆積法を用いて、基板上に薄膜を堆積することにより、得られ得る。基板は、目的に応じて、酸化物基板等を適宜選択し得る。
　ＣａＺｎ２Ｎ２は、地球上にありふれた元素から構成され、直接バンドギャップであり、さらに小さな電荷の有効質量（電子で０．１７ｍ０、ホールで０．９１ｍ０）を有する点で特に有用である。ＣａＺｎ２Ｎ２が有する１．９ｅＶの直接バンドギャップは、可視光の赤色領域に相当し、太陽電池光吸収層として高い理論変換効率が期待され得る。このように、ＣａＺｎ２Ｎ２を活性層とする電子素子は、可視光域で電流注入発光する電子素子（発光素子）、可視光を吸収し光電圧あるいは光電流を発生する電子素子（太陽電池、あるいは光センサー）として有用である。
　図３ａ～eは、Ａ）化学式ＣａＺｎ２Ｎ２で表される窒化亜鉛系化合物について図２ａに示されると同様に、それ以外の本発明の代表的な窒化亜鉛系化合物の結晶構造を示す。
　図４ａ～ｇは、Ａ）化学式ＣａＺｎ２Ｎ２で表される窒化亜鉛系化合物について図２ｂに示されると同様に、それ以外の本発明の代表的な窒化亜鉛系化合物の、Ｍｇ－Ｚｎ－Ｎ系等の計算状態図を示す。
　図５ａ～ｇは、Ａ）化学式ＣａＺｎ２Ｎ２で表される窒化亜鉛系化合物について図２ｃに示されると同様に、それ以外の本発明の代表的な窒化亜鉛系化合物のバンド構造（伝導帯および価電子帯）を示す。
　本発明によれば、高速トランジスタ、高効率可視光発光素子、高効率太陽電池、高感度可視光センサー等の電子素子に好適な窒化亜鉛系化合物を提供し得る。
　以下、実施例により、さらに本発明を詳細に説明する。
実施例１
　ＣａＺｎ２Ｎ２で表される窒化亜鉛系化合物の合成
高圧合成装置内に、モル比でＣａ３Ｎ２：Ｚｎ３Ｎ２＝１：２となるように混合した原料化合物を導入し、２．５GPaで、１１００℃、１時間保持した。用いた高圧合成装置は、ベルト式高圧合成装置であり、試料ホルダ：高圧セル、圧力制御範囲：２-５．５GPa、および温度制御範囲：室温～１６００℃である。
　得られた高圧合成反応生成物のＸ線回折図形を図６ａに示す。生成物の約６９ｗｔ％はＣａＺｎ２Ｎ２であり、残りはＺｎであった。ＣａＺｎ２Ｎ２の格子パラメータは、ａ＝３．４６３１５０（４４）Å、ｃ＝６．０１０５５（１１）Åであり、理論値であるａ＝３．４５４Å、ｃ＝５．９９０Åとの差異は０．３％であった。
　図７ａ～ｃに、拡散反射測定とKubelka-Munkの関係式による吸収スペクトルを比較例１のＣａ２ＺｎＮ２とともに示す。ＣａＺｎ２Ｎ２は、急峻に立ち上がることがわかる。なお、ＣａＺｎ２Ｎ２は、直接ギャップ１．９ｅＶ（計算値１．８３ｅＶ）であった。
比較例１
　Ｃａ２ＺｎＮ２で表される窒化亜鉛系化合物の合成
電気炉内で、モル比でＣａ３Ｎ２：Ｚｎ３Ｎ２＝２：１となるように混合した原料化合物をＳＵＳ管にＡｒ封入して常圧で６８０℃、４０時間保持した。試料ホルダは、SUSガス配管とスウェッジロックを用いた反応菅であった。
　得られた反応生成物のＸ線回折図形を図６ｂに示す。生成物はＣａ２ＺｎＮ２であった。Ｃａ２ＺｎＮ２の格子パラメータは、ａ＝３．５８３６４６（６５）Å、ｃ＝１２．６６３３４６（２６）Åであり、理論値であるａ＝３．５７５Å、ｃ＝１２．６０７Åとの差異はそれぞれ０．２％、０．４％であった。
　図７ａ～ｃに、拡散反射測定とKubelka-Munkの関係式による吸収スペクトルを示す。なお、Ｃａ２ＺｎＮ２は、間接ギャップ１．６ｅＶ（計算値１．６５ｅＶ）、直接ギャップ１．９ｅＶ（計算値１．９２ｅＶ）であった。
　因みに、上記実施例１の混合比の原材料を、本比較例１と同じ方法で合成を試みた場合、本発明のＣａＺｎ２Ｎ２を得ることはできなかった。
実施例２
　ＣａＺｎ２Ｎ２で表される窒化亜鉛系化合物の合成
高圧セル内に、モル比でＣａ３Ｎ２：Ｚｎ３Ｎ２＝１：２となるように混合した原料化合物を導入し、高圧合成にて５．０GPaを印加し、１２００℃、１時間保持した。用いた高圧合成装置は、ベルト式高圧合成装置であり、試料ホルダ：高圧セル、圧力制御範囲：２-５．５GPa、および温度制御範囲：室温～１６００℃である。
　得られた高圧合成反応生成物のＸ線回折図形を図８に示す。生成物の約８０ｗｔ％はＣａＺｎ２Ｎ２であり、残りはＺｎ等であった。ＣａＺｎ２Ｎ２の格子パラメータは、ａ＝３．４６３８０（１１）Å、ｃ＝６．００９６９（３０）Åであり、理論値であるａ＝３．４５４Å、ｃ＝５．９９０Åとの差異は０．３％であった。
　Ｎｄ：ＹＡＧ第３高調波パルスレーザーを使用する光子励起（波長：３５５ｎｍ、エネルギー密度：～７ｍＪ/ｃｍ２）によって、得られた高圧合成反応生成物のＣａＺｎ２Ｎ２から生じる光放射であるフォトルミネッセンスを測定した。赤色のフォトルミネッセンスは１０Ｋにおいて目視で明瞭に観測されるものであった。その結果を図９に示す。ａは、１０、１００、２００および３００Ｋにおけるフォトルミネッセンススペクトルを示し、ｂは、スペクトルピーク位置の温度依存性を示す。
　（ＣａＺｎ２Ｎ２の高純度化）
　得られた高圧合成反応生成物（ＣａＺｎ２Ｎ２、Ｚｎ等）粉末とＩ２をガラス製容器に入れ、アルゴン雰囲気下に約５分間、室温に保持し、亜鉛をヨウ化亜鉛に変換させた。ついで、生成したヨウ化亜鉛をジメチルエーテルに溶解させて、溶液を除去した。得られた粉末のＣａＺｎ２Ｎ２は約８７．３ｗｔ％、亜鉛等は約１２．７ｗｔ％であった。得られた高純度化粉末生成物のＸ線回折図形を図１０に示す。得られた高純度化粉末生成物約１ｇを用いて、冷間等方性加圧装置（ＣＩＰ）により、パルスレーザー堆積ターゲット用のペレットが形成された。

Claims (14)

  1. 　化学式ＣａＺｎ２Ｎ２で表される窒化亜鉛系化合物。
  2. 　化学式Ｘ１ ２ＺｎＮ２（Ｘ１はＢｅまたはＭｇである）で表される窒化亜鉛系化合物。
  3. 　化学式Ｚｎ３ＬａＮ３で表される窒化亜鉛系化合物。
  4. 　化学式ＺｎＴｉＮ２で表される窒化亜鉛系化合物。
  5. 　化学式ＺｎＸ２Ｎ２（Ｘ２はＺｒまたはＨｆである）で表される窒化亜鉛系化合物。
  6. 　化学式Ｚｎ２Ｘ３Ｎ３（Ｘ３はＶ、ＮｂまたはＴａである）で表される窒化亜鉛系化合物。
  7. 　化学式Ｚｎ３ＷＮ４で表される窒化亜鉛系化合物。
  8. 　化合物半導体である請求項１～７のいずれか１項に記載の窒化亜鉛系化合物。
  9. 　直接遷移型化合物半導体である請求項１または３に記載の窒化亜鉛系化合物。
  10. 　化学式ＣａＭ１ ２ｘＺｎ２（１－ｘ）Ｎ２(Ｍ１はＭｇまたはＣｄである。０≦ｘ≦１)またはＭ２ ｘＣａ１－ｘＺｎ２Ｎ２ (Ｍ２はＳｒまたはＢａである。０≦ｘ≦１)で表され、バンドギャップが0.4eV～3.2eVである化合物半導体。
  11. 　請求項８～１０のいずれか１項に記載の化合物半導体を活性層に有する電子素子。
  12. 　可視光域で電流注入発光する請求項１１に記載の電子素子。
  13. 　可視光を吸収し光電圧あるいは光電流を発生する請求項１１に記載の電子素子。
  14. 　1 GPa以上の高圧下で合成する請求項1～７のいずれか１項に記載の窒化亜鉛系化合
    物の製造方法。
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