JP7475840B2 - Method for the synthesis of wurtzite sulfide nanoparticles - Google Patents
Method for the synthesis of wurtzite sulfide nanoparticles Download PDFInfo
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- 239000002105 nanoparticle Substances 0.000 title claims description 74
- 229910052984 zinc sulfide Inorganic materials 0.000 title claims description 53
- UCKMPCXJQFINFW-UHFFFAOYSA-N Sulphide Chemical compound [S-2] UCKMPCXJQFINFW-UHFFFAOYSA-N 0.000 title claims description 37
- 238000000034 method Methods 0.000 title claims description 21
- 238000003786 synthesis reaction Methods 0.000 title description 9
- 230000015572 biosynthetic process Effects 0.000 title description 5
- 239000000463 material Substances 0.000 claims description 49
- 239000011701 zinc Substances 0.000 claims description 37
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 claims description 33
- 239000011593 sulfur Substances 0.000 claims description 32
- 229910052717 sulfur Inorganic materials 0.000 claims description 32
- 239000002245 particle Substances 0.000 claims description 30
- 238000006243 chemical reaction Methods 0.000 claims description 27
- 239000000654 additive Substances 0.000 claims description 26
- 239000005083 Zinc sulfide Substances 0.000 claims description 24
- DRDVZXDWVBGGMH-UHFFFAOYSA-N zinc;sulfide Chemical compound [S-2].[Zn+2] DRDVZXDWVBGGMH-UHFFFAOYSA-N 0.000 claims description 24
- 239000013078 crystal Substances 0.000 claims description 19
- 230000002194 synthesizing effect Effects 0.000 claims description 19
- 230000000996 additive effect Effects 0.000 claims description 17
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- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 claims description 13
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical group [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 13
- 229910052760 oxygen Inorganic materials 0.000 claims description 13
- 239000001301 oxygen Substances 0.000 claims description 13
- 239000002904 solvent Substances 0.000 claims description 13
- 229910052725 zinc Inorganic materials 0.000 claims description 13
- 239000012298 atmosphere Substances 0.000 claims description 10
- 238000009835 boiling Methods 0.000 claims description 5
- JIAARYAFYJHUJI-UHFFFAOYSA-L zinc dichloride Chemical compound [Cl-].[Cl-].[Zn+2] JIAARYAFYJHUJI-UHFFFAOYSA-L 0.000 claims description 4
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- YRKCREAYFQTBPV-UHFFFAOYSA-N acetylacetone Chemical compound CC(=O)CC(C)=O YRKCREAYFQTBPV-UHFFFAOYSA-N 0.000 claims description 3
- 229920005862 polyol Polymers 0.000 claims description 3
- 150000003077 polyols Chemical class 0.000 claims description 3
- NHXVNEDMKGDNPR-UHFFFAOYSA-N zinc;pentane-2,4-dione Chemical compound [Zn+2].CC(=O)[CH-]C(C)=O.CC(=O)[CH-]C(C)=O NHXVNEDMKGDNPR-UHFFFAOYSA-N 0.000 claims description 3
- ZOIORXHNWRGPMV-UHFFFAOYSA-N acetic acid;zinc Chemical compound [Zn].CC(O)=O.CC(O)=O ZOIORXHNWRGPMV-UHFFFAOYSA-N 0.000 claims description 2
- 150000004763 sulfides Chemical class 0.000 claims description 2
- PIOZWDBMINZWGJ-UHFFFAOYSA-N trioctyl(sulfanylidene)-$l^{5}-phosphane Chemical compound CCCCCCCCP(=S)(CCCCCCCC)CCCCCCCC PIOZWDBMINZWGJ-UHFFFAOYSA-N 0.000 claims description 2
- 239000004246 zinc acetate Substances 0.000 claims description 2
- 239000011592 zinc chloride Substances 0.000 claims description 2
- 235000005074 zinc chloride Nutrition 0.000 claims description 2
- XOOUIPVCVHRTMJ-UHFFFAOYSA-L zinc stearate Chemical compound [Zn+2].CCCCCCCCCCCCCCCCCC([O-])=O.CCCCCCCCCCCCCCCCCC([O-])=O XOOUIPVCVHRTMJ-UHFFFAOYSA-L 0.000 claims description 2
- 125000000101 thioether group Chemical group 0.000 claims 1
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 9
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- RMZAYIKUYWXQPB-UHFFFAOYSA-N trioctylphosphane Chemical compound CCCCCCCCP(CCCCCCCC)CCCCCCCC RMZAYIKUYWXQPB-UHFFFAOYSA-N 0.000 description 5
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 4
- KFFQABQEJATQAT-UHFFFAOYSA-N N,N'-dibutylthiourea Chemical compound CCCCNC(=S)NCCCC KFFQABQEJATQAT-UHFFFAOYSA-N 0.000 description 4
- DNIAPMSPPWPWGF-UHFFFAOYSA-N Propylene glycol Chemical compound CC(O)CO DNIAPMSPPWPWGF-UHFFFAOYSA-N 0.000 description 4
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- QGLWBTPVKHMVHM-KTKRTIGZSA-N (z)-octadec-9-en-1-amine Chemical compound CCCCCCCC\C=C/CCCCCCCCN QGLWBTPVKHMVHM-KTKRTIGZSA-N 0.000 description 3
- 229910052793 cadmium Inorganic materials 0.000 description 3
- BDOSMKKIYDKNTQ-UHFFFAOYSA-N cadmium atom Chemical compound [Cd] BDOSMKKIYDKNTQ-UHFFFAOYSA-N 0.000 description 3
- MTHSVFCYNBDYFN-UHFFFAOYSA-N diethylene glycol Chemical compound OCCOCCO MTHSVFCYNBDYFN-UHFFFAOYSA-N 0.000 description 3
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- WGPCGCOKHWGKJJ-UHFFFAOYSA-N sulfanylidenezinc Chemical compound [Zn]=S WGPCGCOKHWGKJJ-UHFFFAOYSA-N 0.000 description 3
- 238000001308 synthesis method Methods 0.000 description 3
- OVRQXQSDQWOJIL-UHFFFAOYSA-N 1,1-dibutylthiourea Chemical compound CCCCN(C(N)=S)CCCC OVRQXQSDQWOJIL-UHFFFAOYSA-N 0.000 description 2
- SESFRYSPDFLNCH-UHFFFAOYSA-N benzyl benzoate Chemical compound C=1C=CC=CC=1C(=O)OCC1=CC=CC=C1 SESFRYSPDFLNCH-UHFFFAOYSA-N 0.000 description 2
- YKYOUMDCQGMQQO-UHFFFAOYSA-L cadmium dichloride Chemical compound Cl[Cd]Cl YKYOUMDCQGMQQO-UHFFFAOYSA-L 0.000 description 2
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- POILWHVDKZOXJZ-ARJAWSKDSA-M (z)-4-oxopent-2-en-2-olate Chemical compound C\C([O-])=C\C(C)=O POILWHVDKZOXJZ-ARJAWSKDSA-M 0.000 description 1
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- LQJBNNIYVWPHFW-UHFFFAOYSA-N 20:1omega9c fatty acid Natural products CCCCCCCCCCC=CCCCCCCCC(O)=O LQJBNNIYVWPHFW-UHFFFAOYSA-N 0.000 description 1
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- 239000005642 Oleic acid Substances 0.000 description 1
- ZQPPMHVWECSIRJ-UHFFFAOYSA-N Oleic acid Natural products CCCCCCCCC=CCCCCCCCC(O)=O ZQPPMHVWECSIRJ-UHFFFAOYSA-N 0.000 description 1
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- 229960002903 benzyl benzoate Drugs 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- GWOWVOYJLHSRJJ-UHFFFAOYSA-L cadmium stearate Chemical compound [Cd+2].CCCCCCCCCCCCCCCCCC([O-])=O.CCCCCCCCCCCCCCCCCC([O-])=O GWOWVOYJLHSRJJ-UHFFFAOYSA-L 0.000 description 1
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- ORTRWBYBJVGVQC-UHFFFAOYSA-N hexadecane-1-thiol Chemical compound CCCCCCCCCCCCCCCCS ORTRWBYBJVGVQC-UHFFFAOYSA-N 0.000 description 1
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- 230000005693 optoelectronics Effects 0.000 description 1
- 150000002894 organic compounds Chemical class 0.000 description 1
- 150000002897 organic nitrogen compounds Chemical class 0.000 description 1
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- 125000004437 phosphorous atom Chemical group 0.000 description 1
- 229910052698 phosphorus Inorganic materials 0.000 description 1
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- JBQYATWDVHIOAR-UHFFFAOYSA-N tellanylidenegermanium Chemical compound [Te]=[Ge] JBQYATWDVHIOAR-UHFFFAOYSA-N 0.000 description 1
- YUKQRDCYNOVPGJ-UHFFFAOYSA-N thioacetamide Chemical compound CC(N)=S YUKQRDCYNOVPGJ-UHFFFAOYSA-N 0.000 description 1
- DLFVBJFMPXGRIB-UHFFFAOYSA-N thioacetamide Natural products CC(N)=O DLFVBJFMPXGRIB-UHFFFAOYSA-N 0.000 description 1
- 150000003573 thiols Chemical class 0.000 description 1
- ZMBHCYHQLYEYDV-UHFFFAOYSA-N trioctylphosphine oxide Chemical compound CCCCCCCCP(=O)(CCCCCCCC)CCCCCCCC ZMBHCYHQLYEYDV-UHFFFAOYSA-N 0.000 description 1
- 150000003751 zinc Chemical class 0.000 description 1
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Description
本発明は、ウルツ鉱型（ＷＺ型）硫化物ナノ粒子とその合成方法に関し、特に１０ｎｍ以下のＷＺ型硫化亜鉛ナノ粒子を高純度で製造する技術に関する。 The present invention relates to wurtzite (WZ) sulfide nanoparticles and a method for synthesizing the same, and in particular to a technology for producing high-purity WZ zinc sulfide nanoparticles of 10 nm or less.
ＩＩ－ＶＩ族化合物半導体材料である硫化亜鉛や、及び硫化亜鉛に酸素を添加したＺｎＯＳのナノ粒子は、可視から紫外にエネルギーギャップを持つため、蛍光体、ＥＬ（エレクトロルミネッセンス）材料、太陽電池、ガス・化学・生体センサ等のオプトエレクトロニクス材料として有望な材料である。 Zinc sulfide, a II-VI compound semiconductor material, and ZnOS nanoparticles, which are zinc sulfide with added oxygen, have an energy gap from the visible to the ultraviolet range, making them promising materials for use as optoelectronic materials in applications such as phosphors, electroluminescent (EL) materials, solar cells, and gas, chemical, and biological sensors.
一般に半導体ナノ粒子は、粒子サイズをボーア半径以下にすることで量子効果が発現し、エネルギーギャップを広げることができる。ＺｎＳは、ボーア半径が２．５ｎｍであり、粒子サイズを５ｎｍ以下にすることで、発光・受光材料として幅広い波長範囲を実現することができる。硫化亜鉛ナノ粒子の合成方法としては、化学合成による製造方法が確立されており、５ｎｍ以下の硫化亜鉛ナノ粒子の製造例が例えば特許文献１に報告されている。特許文献１に記載された技術では、合成時の添加剤として有機カルボン酸、有機窒素化合物或いは有機硫黄化合物等の界面活性剤を用いて、ナノ粒子表面に化学結合させることにより、粒子径をコントロールすることが開示されている。 In general, semiconductor nanoparticles can exhibit quantum effects and widen the energy gap by reducing the particle size to less than the Bohr radius. ZnS has a Bohr radius of 2.5 nm, and by reducing the particle size to 5 nm or less, a wide wavelength range can be achieved as a light-emitting/light-receiving material. A chemical synthesis method has been established as a method for synthesizing zinc sulfide nanoparticles, and an example of manufacturing zinc sulfide nanoparticles of 5 nm or less is reported in, for example, Patent Document 1. The technology described in Patent Document 1 discloses that the particle size is controlled by using a surfactant such as an organic carboxylic acid, an organic nitrogen compound, or an organic sulfur compound as an additive during synthesis and chemically bonding it to the nanoparticle surface.
ところでＺｎＳは、安定な結晶構造として閃亜鉛鉱型と呼ばれる立方晶系の構造結晶と、準安定な結晶構造としてウルツ鉱型の六方晶系の結晶構造とが知られている。立方晶系の硫化亜鉛は、対称性が高いため結晶内の欠陥などが伝播されやすく熱や湿度などによる劣化が激しいのに対し、ウルツ鉱型の硫化亜鉛は閃亜鉛鉱型に比べ対称性が低いため、欠陥の伝播などが抑制され高い信頼性を持つ光学材料として期待されている。 ZnS is known to have a stable cubic crystal structure called zinc blende, and a metastable hexagonal crystal structure called wurtzite. Cubic zinc sulfide has a high degree of symmetry, which makes it easy for defects within the crystal to propagate, and it is subject to rapid deterioration due to heat and humidity, whereas wurtzite zinc sulfide has a lower degree of symmetry than zinc blende, which suppresses the propagation of defects and is therefore expected to be a highly reliable optical material.
ウルツ鉱型の硫化亜鉛は、閃亜鉛鉱型の硫化亜鉛を１０２０℃以上の温度で熱処理することで得られることが知られているが、従来のナノ粒子の合成方法（例えば特許文献１記載の合成方法）では、安定な結晶構造である閃亜鉛鉱型の硫化亜鉛が生成し、ウルツ鉱型の硫化亜鉛ナノ粒子を得ることはできない。 It is known that wurtzite-type zinc sulfide can be obtained by heat treating zinc blende-type zinc sulfide at a temperature of 1020°C or higher, but conventional nanoparticle synthesis methods (such as the synthesis method described in Patent Document 1) produce zinc blende-type zinc sulfide, which has a stable crystal structure, and it is not possible to obtain wurtzite-type zinc sulfide nanoparticles.
一方、硫化亜鉛に酸素を混晶化したＺｎＯＳ粒子は、酸素の添加量を変化させることで、幅広くエネルギーギャップを変化させることが期待されるが、ＺｎＳ粒子は非混和性が高いため添加元素を粒子内に均一に混合を添加することが困難である。具体的には、１０００Ｋ以下の温度では、ＺｎＳへの酸素の固溶限界は５％以下と予測されており、従来の合成方法で酸素の比率を高めた場合、ＺｎＯの相とＺｎＳの相に分離してしまい、均一で高い酸素組成を持つＺｎＯＳナノ粒子を得ることはできていない。 On the other hand, ZnOS particles, which are made by mixing oxygen with zinc sulfide, are expected to have a wide range of energy gap changes by changing the amount of oxygen added. However, ZnS particles are highly immiscible, making it difficult to uniformly mix the added element within the particle. Specifically, at temperatures below 1000K, the solid solubility limit of oxygen in ZnS is predicted to be 5% or less. When the oxygen ratio is increased using conventional synthesis methods, separation occurs into a ZnO phase and a ZnS phase, making it impossible to obtain ZnOS nanoparticles with a uniform, high oxygen composition.
本発明の第一の課題は、化学合成によってウルツ鉱型の硫化物ナノ粒子を合成すること、第二の課題は、均一で高い酸素組成を持つＺｎＯＳナノ粒子を合成することである。 The first objective of the present invention is to synthesize wurtzite-type sulfide nanoparticles by chemical synthesis, and the second objective is to synthesize ZnOS nanoparticles with a uniform and high oxygen composition.
上記課題を解決するため、本発明者らは鋭意研究した結果、亜鉛材料及び硫黄材料との化学合成によって硫化亜鉛ナノ粒子を合成する際に、添加剤として２種類の添加剤を同時に用いることによって、ウルツ鉱型であって平均粒子径が１０ｎｍ以下の硫化亜鉛ナノ粒子が得られること、さらに、亜鉛材料と硫黄材料との比率を調整することで、ウルツ鉱型の均一な結晶構造を持つＺｎＯＳナノ粒子が得られることを見出し、本発明に至ったものである。 In order to solve the above problems, the inventors conducted extensive research and discovered that when synthesizing zinc sulfide nanoparticles by chemical synthesis of zinc material and sulfur material, it is possible to obtain zinc sulfide nanoparticles that are wurtzite type and have an average particle size of 10 nm or less by simultaneously using two types of additives as additives, and further, by adjusting the ratio of zinc material to sulfur material, it is possible to obtain ZnOS nanoparticles that have a uniform wurtzite crystal structure, which led to the present invention.
なお本明細書において、硫化物ナノ粒子は、ＩＩ族元素の硫化物からなるナノ粒子とそれに他元素をドープした硫化物ナノ粒子とを含めていう。 In this specification, sulfide nanoparticles include nanoparticles made of sulfides of Group II elements and sulfide nanoparticles doped with other elements.
即ち、本発明の第一の態様は、少なくとも亜鉛を含むＩＩ族元素材料と硫黄材料とを溶媒中で熱分解してウルツ鉱型結晶構造の硫化物ナノ粒子を合成する方法であって、反応系に、添加剤として、ポリオール系材料及びステアリン酸エチレングリコール系材料の少なくとも１種からなる第一の添加剤と、反応中に前記ナノ粒子の表面に配位し、粒子サイズを抑制する第二の添加剤とを添加することを特徴とする。 That is, the first aspect of the present invention is a method for synthesizing sulfide nanoparticles with a wurtzite crystal structure by thermally decomposing a Group II element material containing at least zinc and a sulfur material in a solvent, characterized in that a first additive consisting of at least one of a polyol-based material and an ethylene glycol stearate-based material, and a second additive that coordinates to the surface of the nanoparticles during the reaction and suppresses the particle size are added to the reaction system as additives.
また本発明の第二の態様は、下記一般式で表されるウルツ鉱型結晶構造の硫化物ナノ粒子であって、
（Ｚｎ）（Ｓ１－ｘＯｘ）
（但し、ｘ＞０）
平均粒子径が１０ｎｍ以下である硫化物ナノ粒子である。
A second aspect of the present invention is a sulfide nanoparticle having a wurtzite crystal structure represented by the following general formula:
(Zn) (S1 - xOx )
(However, x>0)
The sulfide nanoparticles have an average particle size of 10 nm or less.
また下記一般式で表されるウルツ鉱型結晶構造の硫化物ナノ粒子であって、
Ｚｎ（Ｓ１－ｘＯｘ）
（但し、０．４＞ｘ≧０）
短径４ｎｍ以下、長径５０ｎｍ以下、アスペクト比５以上２５以下のワイヤー状の硫化物ナノ粒子である。
The sulfide nanoparticles have a wurtzite crystal structure represented by the following general formula:
Zn( S1-xOx )
(However, 0.4>x≧0)
The wire-shaped sulfide nanoparticles have a short diameter of 4 nm or less, a long diameter of 50 nm or less, and an aspect ratio of 5 to 25.
本発明によれば、光学特性等の信頼性の高いウルツ鉱型の硫化物ナノ粒子を合成することができる。また本発明によれば、結晶中の硫黄を比較的高い比率で酸素に置換した硫化物ナノ粒子が提供される。これにより硫化亜鉛のエネルギーギャップのコントロールが可能となり、用途の幅を広げることができる。 According to the present invention, it is possible to synthesize wurtzite-type sulfide nanoparticles with highly reliable optical properties. In addition, according to the present invention, it is possible to provide sulfide nanoparticles in which a relatively high ratio of sulfur in the crystal is replaced with oxygen. This makes it possible to control the energy gap of zinc sulfide, thereby expanding the range of applications.
以下、本発明の硫化物ナノ粒子の合成方法について説明する。
本発明の硫化物ナノ粒子の合成方法は、ＩＩ族元素（Ｍと記載する）材料及び硫黄材料との化学合成によって硫化物ナノ粒子（ＭＳ、ＭＯＳ）を合成する際に、添加剤として２種類の添加剤を同時に用いる。
The method for synthesizing sulfide nanoparticles of the present invention will now be described.
In the method for synthesizing sulfide nanoparticles of the present invention, when synthesizing sulfide nanoparticles (MS, MOS) by chemical synthesis of a Group II element (referred to as M) material and a sulfur material, two types of additives are used simultaneously as additives.
ＩＩ族元素（Ｍ）としては、亜鉛（Ｚｎ）、カドミウム（Ｃｄ）が挙げられ、これらの錯体を用いることが好ましい。例えば、亜鉛材料としては、酢酸亜鉛（Ｚｎ（ＡＣ）２）、ステアリン酸亜鉛（ＳＴ－Ｚｎ）、アセチルアセトナート亜鉛（Ｚｎ（ＡＣＡＣ）２）、塩化亜鉛（ＺｎＣｌ２）など亜鉛錯体を用いることができ、特にアセチルアセトナート亜鉛が好ましい。カドミウムについても同様にジステアリン酸カドミウムやアセチルアセトナートカドミウム、塩化カドミウムなどの錯体を用いることができる。以下の説明では、ＩＩ族元素がＺｎである場合を例に説明する。 Examples of the Group II element (M) include zinc (Zn) and cadmium (Cd), and it is preferable to use complexes of these. For example, as the zinc material, zinc complexes such as zinc acetate (Zn(AC) 2 ), zinc stearate (ST-Zn), zinc acetylacetonate (Zn(ACAC) 2 ), and zinc chloride (ZnCl 2 ) can be used, and zinc acetylacetonate is particularly preferable. Similarly, complexes such as cadmium distearate, cadmium acetylacetonate, and cadmium chloride can be used for cadmium. In the following explanation, an example in which the Group II element is Zn will be explained.
硫黄材料としては、ドデカンチオール、ヘキサデカンチオール等チオール系材料、１，１－ジメチルチオ尿素、１，３－ジメチルチオ尿素、１，１－ジエチルチオ尿素、１，３－ジエチルチオ尿素、１，１－ジブチルチオ尿素、１，３－ジブチルチオ尿素、チオアセトアミド、テトラメチルチオ尿素などのＳ含有有機化合物や、硫黄粉末を用いることができる。特に、１，１－ジブチルチオ尿素、或いは、１，３－ジブチルチオ尿素が好ましい。 Examples of sulfur materials that can be used include thiol-based materials such as dodecanethiol and hexadecanethiol, S-containing organic compounds such as 1,1-dimethylthiourea, 1,3-dimethylthiourea, 1,1-diethylthiourea, 1,3-diethylthiourea, 1,1-dibutylthiourea, 1,3-dibutylthiourea, thioacetamide, and tetramethylthiourea, and sulfur powder. In particular, 1,1-dibutylthiourea or 1,3-dibutylthiourea is preferable.
ＩＩ族元素材料（亜鉛材料）と硫黄材料との割合は、硫化物ナノ粒子の化学量論的割合とすることができるが、Ｓ／Ｚｎ比を制御することで、同時にナノ粒子の形状をワイヤー状から球状に制御することができる。具体的にはＳ／Ｚｎ比が１のときに、短辺が２～４ｎｍ、長辺が５～５０ｎｍ、アスペクト比５～２５のワイヤー状粒子を製造することができ、Ｓ／Ｚｎ比が２のときに粒子径２～５ｎｍ、アスペクト比５以下の球状粒子を製造することができる。ワイヤー状の粒子は、長辺方向を揃えることで、その形状に依存して偏光性を持たせることができ、従来の球状粒子とは異なる光学用途に応用することができる。 The ratio of the Group II element material (zinc material) and the sulfur material can be set to the stoichiometric ratio of sulfide nanoparticles, but by controlling the S/Zn ratio, the shape of the nanoparticles can be controlled from wire-like to spherical. Specifically, when the S/Zn ratio is 1, wire-like particles with short sides of 2-4 nm, long sides of 5-50 nm, and an aspect ratio of 5-25 can be produced, and when the S/Zn ratio is 2, spherical particles with particle diameters of 2-5 nm and aspect ratios of 5 or less can be produced. By aligning the long side direction, wire-like particles can be made polarizable depending on their shape, and can be used for optical applications different from conventional spherical particles.
一方、Ｓ／Ｚｎ比を１未満、即ちＳの量をＺｎより少なくすることで、Ｓの一部が酸素に入れ替わった硫化物ナノ粒子を得ることができる。具体的には、Ｓ／Ｚｎ比をｙ（但し、１＞ｙ）とすることで、不足したＳ分だけＯが取り込まれる。この場合、Ｓ／Ｚｎが０．４以下になると、ＺｎＳの相とＺｎＯの相とが混在した硫化物ナノ粒子が生成するため、Ｓ／Ｚｎ比は０．４より多いことが好ましく、０．６以上であることがより好ましい。Ｓ／Ｚｎを０．６以上とすることで、サイズ１０ｎｍ以下のナノ粒子を得ることができる。 On the other hand, by setting the S/Zn ratio to less than 1, i.e., by making the amount of S less than that of Zn, it is possible to obtain sulfide nanoparticles in which some of the S has been replaced with oxygen. Specifically, by setting the S/Zn ratio to y (where 1>y), O is incorporated to make up for the lack of S. In this case, if the S/Zn ratio is 0.4 or less, sulfide nanoparticles in which ZnS phases and ZnO phases are mixed are generated, so the S/Zn ratio is preferably greater than 0.4, and more preferably 0.6 or greater. By setting the S/Zn ratio to 0.6 or greater, nanoparticles with a size of 10 nm or less can be obtained.
２種の添加剤の一つ、第一の添加剤としては、ヘキサデカンジオール、テトラエチレングリコール、プロピレングリコール、トリメチルグリコール、ジエチレングリコール、エチレングリコール、ステアリルグリコール等のポリオール系材料、及び、ステアリン酸エチレングリコール系材料の少なくとも１種を用いる。これらのうち、特にエチレングリコールが好ましい。第一の添加剤の量は、極めて少量でよく、溶媒に対し０．５容量％程度とする。また添加量が多いと、反応系に留まらず突沸などの原因になるため、好ましくは１容量％以下、より好ましくは０．８容量％以下とする。 As the first additive, one of the two types of additives, at least one of polyol-based materials such as hexadecanediol, tetraethylene glycol, propylene glycol, trimethyl glycol, diethylene glycol, ethylene glycol, stearyl glycol, and ethylene glycol stearate-based materials is used. Of these, ethylene glycol is particularly preferred. The amount of the first additive may be extremely small, about 0.5% by volume relative to the solvent. If a large amount is added, it will not remain in the reaction system and may cause bumping, so the amount is preferably 1% by volume or less, and more preferably 0.8% by volume or less.
第二の添加剤としては、ＺｎＳ粒子のＺｎに配位する錯体であって嵩高いものが好ましく、例えば、トリオクチルホスフィン・スルフィド（以下、ＴＯＰ：Ｓと記す）を用いることができる。ＴＯＰ：Ｓは、トリオクチルホスフィンのリン原子（Ｐ）に硫黄（Ｓ）が配位結合によって結合した錯体であり、トリオクチルホスフィンと硫黄とから合成することができる。ＴＯＰ：Ｓは硫黄を含む錯体であり、硫黄を含むナノ粒子の原料としては知られているが、本発明の反応においては、硫黄の供給源として機能するのではなく、第一の添加剤との併用によって、ウルツ型の結晶構造を維持しながら、粒子のサイズを抑制する機能を持つものと考えられる。 As the second additive, a bulky complex that coordinates with the Zn of the ZnS particles is preferable, and for example, trioctylphosphine sulfide (hereinafter, referred to as TOP:S) can be used. TOP:S is a complex in which sulfur (S) is bonded to the phosphorus atom (P) of trioctylphosphine by a coordinate bond, and can be synthesized from trioctylphosphine and sulfur. TOP:S is a complex containing sulfur and is known as a raw material for nanoparticles containing sulfur, but in the reaction of the present invention, it does not function as a sulfur source, but rather, when used in combination with the first additive, it is thought to have the function of suppressing the size of the particles while maintaining the wurtzite crystal structure.
第二の添加剤の量は、亜鉛原料に対しモル比で０．１～１．０、好ましくは０．２～０．８、より好ましくは約０．４～０．６とする。またトリオクチルホスフィンと硫黄で錯体を合成し、それを反応系に投入する場合、トリオクチルホスフィンを化学量論的な割合よりも多くすることが好ましい。これにより、余剰の硫黄が反応系に入り、意図しない酸素との置換が起こるのを防止できる。 The amount of the second additive is 0.1 to 1.0, preferably 0.2 to 0.8, and more preferably about 0.4 to 0.6, in molar ratio relative to the zinc raw material. When synthesizing a complex from trioctylphosphine and sulfur and adding it to the reaction system, it is preferable to use more trioctylphosphine than the stoichiometric ratio. This prevents excess sulfur from entering the reaction system and causing unintended replacement with oxygen.
溶媒は、反応を比較的高温で行うため、沸点（ｂ．ｐ．）が反応温度より高い溶媒を用いる。具体的には、オレイルアミン（ｂ．ｐ．：３５０℃）やベンジルベンゾエート（ｂ．ｐ．：３５０℃）、１－オクタデセン（ｂ．ｐ．：１７９℃（１５ｍｍＨｇ下））、オレイン酸（ｂ．ｐ．：３６０℃）、トリオクチルフォスフィンオキシド（ｂ．ｐ．：２０２℃（２ｍｍＨｇ下））、トリオクチルフォスフィン（ｂ．ｐ．：４４５℃）を用いることができる。特に高沸点のオレイルアミンが好適である。 Because the reaction is carried out at a relatively high temperature, a solvent with a boiling point (b.p.) higher than the reaction temperature is used. Specifically, oleylamine (b.p.: 350°C), benzyl benzoate (b.p.: 350°C), 1-octadecene (b.p.: 179°C (under 15 mmHg)), oleic acid (b.p.: 360°C), trioctylphosphine oxide (b.p.: 202°C (under 2 mmHg)), and trioctylphosphine (b.p.: 445°C) can be used. Oleylamine, which has a high boiling point, is particularly suitable.
反応は、溶媒中（液相）で加熱して行う。この際、減圧下で比較的低い温度で反応させるステップ（第一のステップ）と不活性雰囲気下で比較的高い温度で反応させるステップ（第二のステップ）とを含む複数段階の反応を行い、段階ごとに反応時間や雰囲気などの条件を異ならせることが好ましい。 The reaction is carried out by heating in a solvent (liquid phase). In this case, it is preferable to carry out a multi-step reaction including a step (first step) of reacting at a relatively low temperature under reduced pressure and a step (second step) of reacting at a relatively high temperature in an inert atmosphere, with different reaction conditions such as reaction time and atmosphere for each step.
第一のステップの反応温度は、２００℃以下とすることが好ましい。２００℃以下とすることにより、閃亜鉛鉱型の結晶が生成するのを抑制することができる。 The reaction temperature in the first step is preferably 200°C or less. By keeping the temperature at 200°C or less, the formation of zinc blende crystals can be suppressed.
第一のステップは、例えば、まずＮ２等の不活性雰囲気で１００℃以下の温度（例えば７０℃程度）で１時間以下の短時間保持したのち昇温し、減圧雰囲気下で２００℃以下の温度（例えば１３０℃）で反応を進行させる。減圧雰囲気下の圧力は大気圧（約１００ｋＰａ）の１／１００以下とする。但し溶媒の突沸を防止するために１５Ｐａ以上とする。減圧雰囲気、２００℃以下で行う反応の反応時間は、１～３時間程度とする。 In the first step, for example, the reaction is first maintained at a temperature of 100°C or less (e.g., about 70°C) for a short period of time of 1 hour or less in an inert atmosphere such as N2 , and then the temperature is raised to a temperature of 200°C or less (e.g., 130°C) in a reduced pressure atmosphere to allow the reaction to proceed. The pressure in the reduced pressure atmosphere is 1/100 or less of atmospheric pressure (about 100 kPa). However, the pressure is set to 15 Pa or more to prevent bumping of the solvent. The reaction time for the reaction in a reduced pressure atmosphere at 200°C or less is about 1 to 3 hours.
第二のステップは、不活性雰囲気下で第一ステップの反応温度より高い温度、２００℃以上で且つ溶媒の沸点以下の温度（例えば２５０℃）で１～２時間保持する。第一のステップから第二のステップの昇温レートは、限定されるものではないが、例えば５０℃／５ｍｉｎとする。第二のステップでは、第一のステップで生成した結晶の核を成長させる。第一のステップで六方晶系（ＷＺ型）の結晶の核が生成していれば、その後、温度を上昇させても結晶系は保たれ、温度を上げることで残りの反応を速やかに進めることができる。第二のステップの後、さらに温度を上げて（ただし溶媒の沸点以下）、短時間保持してもよく、これにより速やかに反応を完了させることができる。 In the second step, the reaction is held in an inert atmosphere at a temperature higher than the reaction temperature in the first step, 200°C or higher and below the boiling point of the solvent (e.g., 250°C), for 1 to 2 hours. The rate of temperature rise from the first step to the second step is not limited, but may be, for example, 50°C/5 min. In the second step, the nuclei of the crystals generated in the first step are grown. If the nuclei of hexagonal crystals (WZ type) are generated in the first step, the crystal system is maintained even if the temperature is subsequently increased, and the remaining reaction can be rapidly carried out by increasing the temperature. After the second step, the temperature may be further increased (but below the boiling point of the solvent) and held for a short period of time, which allows the reaction to be rapidly completed.
反応終了後は、降温後、一般的な熱分解法によるナノ粒子の回収方法と同様の方法で、ナノ粒子を回収する。具体的には、降温後の反応液にヘキサン等の所定の溶媒を加えて拡散した後、貧溶媒を加えて粒子を凝集させて遠心分離する。この処理は、必要に応じて複数回繰り返してもよい。最後に粒子洗浄を行って、ナノ粒子の分散液を得る。 After the reaction is complete, the temperature is lowered and the nanoparticles are recovered in the same manner as in the general method of recovering nanoparticles by pyrolysis. Specifically, a specific solvent such as hexane is added to the reaction liquid after the temperature is lowered to cause dispersion, and then a poor solvent is added to cause the particles to aggregate and then centrifuged. This process may be repeated multiple times as necessary. Finally, the particles are washed to obtain a dispersion of nanoparticles.
本発明の硫化物ナノ粒子の製造方法によれば、反応系に２種類の添加剤を添加することにより、ナノ粒子の結晶系の制御と非混和性の緩和という複数の課題を一挙に解決することができ、これにより、従来の化学合成では生成することができなかったサイズ１０ｎｍ以下のウルツ鉱型の硫化物ナノ粒子を提供することができる。また他元素の取り込みについては、硫化物の酸素濃度を４０原子％程度まで高めることができる。 According to the method for producing sulfide nanoparticles of the present invention, by adding two types of additives to the reaction system, it is possible to solve multiple problems at once, such as controlling the crystal system of the nanoparticles and reducing immiscibility, and thus it is possible to provide wurtzite-type sulfide nanoparticles with a size of 10 nm or less, which could not be produced by conventional chemical synthesis. In addition, regarding the incorporation of other elements, the oxygen concentration of the sulfide can be increased to about 40 atomic %.
本発明の硫化物ナノ粒子の製造方法により得られる代表的な硫化物ナノ粒子は、粒子サイズ１０ｎｍ以下のウルツ鉱型結晶構造のＺｎ（ＯｘＳ１－ｘ）（但し、０．４＞ｘ＞０）ナノ粒子、及び、短径４ｎｍ以下、長径５０ｎｍ以下、アスペクト比５以上２５以下のワイヤー状のＺｎ（ＯｘＳ１－ｘ）（但し、０．４＞ｘ≧０）ナノ粒子を含む。 Representative sulfide nanoparticles obtainable by the method for producing sulfide nanoparticles of the present invention include Zn(O x S 1-x ) (where 0.4>x>0) nanoparticles having a wurtzite crystal structure and a particle size of 10 nm or less, and wire-shaped Zn(O x S 1-x ) (where 0.4>x≧0) nanoparticles having a short axis of 4 nm or less, a long axis of 50 nm or less, and an aspect ratio of 5 to 25.
以下、本発明の硫化物ナノ粒子の合成例を説明する。 The following describes an example of the synthesis of sulfide nanoparticles of the present invention.
＜実施例１＞
溶媒としてオレイルアミン１０ｍＬ、亜鉛材料としてＺｎ（ＡＣＡＣ）２ ２．０ｍｍｏｌ、硫黄材料として１，３－ジブチルチオ尿素 ２．０ｍｍｏｌを用い、第一の添加剤としてエチレングリコール（ＥＧ） １．０ｍｍｏｌ、第二の添加剤としてＴＯＰ－Ｓ（ＴＯＰ １．２ｍｍｏｌ及び硫黄 ０．６ｍｍｏｌ）を用いた。なお亜鉛材料と硫黄材料（ＴＯＰ－Ｓを除く）のＳ／Ｚｎ比は１である。
Example 1
The solvent used was 10 mL of oleylamine, the zinc material was 2.0 mmol of Zn(ACAC) 2 , the sulfur material was 2.0 mmol of 1,3-dibutylthiourea, the first additive was 1.0 mmol of ethylene glycol (EG), and the second additive was TOP-S (1.2 mmol of TOP and 0.6 mmol of sulfur). The S/Zn ratio of the zinc material and the sulfur material (except for TOP-S) was 1.
容器（１００ｍＬ）に材料を充填後、窒素雰囲気下で７０℃に３０分保持したのち、昇温し減圧雰囲気下で１３０℃に２時間保持した。この時の圧力は、約１００Ｐａ（１０Ｐａ以上１０００Ｐａ以下）とした。その後、５０℃／５分の昇温レートで昇温し、Ｎ２雰囲気下で２５０℃に２時間保持した後、さらに昇温してＮ２雰囲気下で３００℃に保持して合成を行った。 After filling the container (100 mL), the material was held at 70 ° C for 30 minutes under a nitrogen atmosphere, and then heated and held at 130 ° C for 2 hours under a reduced pressure atmosphere. The pressure at this time was about 100 Pa (10 Pa or more and 1000 Pa or less). After that, the temperature was raised at a temperature rise rate of 50 ° C / 5 minutes, and the material was held at 250 ° C for 2 hours under a N2 atmosphere, and then further heated and held at 300 ° C under a N2 atmosphere to perform synthesis.
降温後の反応液にヘキサンを５ｍｌ加え撹拌した後に遠沈管に回収した。貧溶媒であるエタノールを加えて粒子を凝集させ、遠心分離機を用いて沈降させた。分離条件は１２，０００ｒｐｍで、６０分とした。上澄み液を廃棄した後、ヘキサンを５ｍＬ加えて振とう機で３０分撹拌して粒子を分散させた。もう一度エタノールを加え、同様の工程をもう１回繰り返して粒子洗浄を行い、ＺｎＳナノ粒子の分散液を得た。 After cooling, 5 ml of hexane was added to the reaction solution, which was stirred and then collected in a centrifuge tube. Ethanol, a poor solvent, was added to aggregate the particles, which were then allowed to settle using a centrifuge. Separation conditions were 12,000 rpm and 60 minutes. After discarding the supernatant, 5 ml of hexane was added and the particles were dispersed by stirring for 30 minutes using a shaker. Ethanol was added once more, and the same process was repeated once more to wash the particles, yielding a dispersion of ZnS nanoparticles.
＜比較例１＞
２種の添加剤を用いないこと以外は、実施例１と同様にして、硫化亜鉛ナノ粒子を合成した。
<Comparative Example 1>
Zinc sulfide nanoparticles were synthesized in the same manner as in Example 1, except that the two additives were not used.
実施例１及び比較例１で、それぞれ得られた粒子の透過型電子顕微鏡像（ＴＥＭ像）を図１（Ａ）、（Ｂ）に示す。図１（Ａ）に示すように、粒子の形状はワイヤー状であり、短径が２～３ｎｍ、長径が２０～５０ｎｍであることが確認された。一方、添加剤を用いない場合には、図１（Ｂ）に示すように、粒子サイズ４～５ｎｍの球状の粒子が得られた。 Transmission electron microscope images (TEM images) of the particles obtained in Example 1 and Comparative Example 1 are shown in Figures 1(A) and (B), respectively. As shown in Figure 1(A), it was confirmed that the particles were wire-shaped with a short diameter of 2 to 3 nm and a long diameter of 20 to 50 nm. On the other hand, when no additive was used, spherical particles with a particle size of 4 to 5 nm were obtained, as shown in Figure 1(B).
また実施例１及び比較例１で得られた粒子のＸＲＤ回折パターンを図２に示す。図２に示すように、比較例１の粒子は、立方晶系の（１１１）、（２２０）及び（３１１）の３つのピークが見られ、閃亜鉛鉱型の硫化亜鉛であることが確認された。一方、実施例１の粒子は、六方晶系の（１００）（００２）（１０１）（１０２）（１１０）（１０３）（１１２）の６つのピークが見られ、ウルツ鉱型のＺｎＳであることが確認された。 The XRD diffraction patterns of the particles obtained in Example 1 and Comparative Example 1 are shown in Figure 2. As shown in Figure 2, the particles of Comparative Example 1 showed three peaks of cubic crystal system (111), (220), and (311), and were confirmed to be zinc blende-type zinc sulfide. On the other hand, the particles of Example 1 showed six peaks of hexagonal crystal system (100), (002), (101), (102), (110), (103), and (112), and were confirmed to be wurtzite-type ZnS.
＜実施例２、３及び参考例＞
硫黄材料である１，３－ジブチルチオ尿素の使用量を、１．６ｍｍｏｌ（実施例２）、１．２ｍｍｏｌ（実施例３）、及び０．８ｍｍｏｌ（参考例）に、それぞれ変えて、それ以外は、実施例１と同様にして、硫化亜鉛ナノ粒子を合成した。
<Examples 2 and 3 and Reference Example>
Zinc sulfide nanoparticles were synthesized in the same manner as in Example 1, except that the amount of the sulfur material, 1,3-dibutylthiourea, was changed to 1.6 mmol (Example 2), 1.2 mmol (Example 3), and 0.8 mmol (Reference Example), respectively.
実施例２及び実施例３のＴＥＭ像を図３に、実施例２、３及び参考例のＸＲＤを図４に示す。ＴＥＭ像から、実施例２、３のいずれにおいても、球状のナノ粒子が確認され、粒子サイズはそれぞれ２～３ｎｍ（実施例２）、３～４ｎｍ（実施例３）であった。またＸＲＤパターンから、実施例２、３のナノ粒子は均一なウルツ鉱型のＺｎＯＳ粒子であることが確認された。さらにＸＲＤ分析の結果、実施例１を硫黄材料濃度１００％としたとき、硫黄材料濃度８０％である実施例２はＺｎＯ０．１Ｓ０．９が生成され、硫黄材料濃度６０％である実施例３はＺｎＯ０．２Ｓ０．８が生成され、いずれも原料の使用量に応じてＺｎＯＳ粒子の硫黄が酸素に置き換わった粒子であることが確認された。一方、参考例（硫黄材料濃度４０％）では、ウルツ鉱型のＺｎＯＳはほとんど生成されず、図４のＸＲＤパターンからわかるように、立方晶系であるＺｎＳのピークと六方晶ＺｎＯのピークが観察された。
TEM images of Examples 2 and 3 are shown in FIG. 3, and XRD of Examples 2, 3, and Reference Example are shown in FIG. 4. From the TEM images, spherical nanoparticles were confirmed in both Examples 2 and 3, with particle sizes of 2-3 nm (Example 2) and 3-4 nm (Example 3), respectively. From the XRD patterns, it was confirmed that the nanoparticles in Examples 2 and 3 were uniform wurtzite-type ZnOS particles. Furthermore, as a result of the XRD analysis, when Example 1 was taken as having a sulfur material concentration of 100%, Example 2 , which had a sulfur material concentration of 80%, produced ZnO 0.1 S 0.9 , and Example 3 , which had a sulfur material concentration of 60%, produced ZnO 0.2 S 0.8 , and it was confirmed that in both cases, the sulfur of the ZnOS particles was replaced with oxygen depending on the amount of raw material used. On the other hand, in the reference example (
本発明によれば、光学材料、磁気材料、電気材料或いは蛍光体等として適用可能な新規なナノ粒子が提供される。 The present invention provides novel nanoparticles that can be used as optical materials, magnetic materials, electrical materials, phosphors, etc.
Claims (6)
前記亜鉛を含むＩＩ族元素材料と硫黄材料との割合Ｓ／Ｚｎ比は、０．６以上２以下であり、
反応系に、添加剤として、ポリオール系材料及びステアリン酸エチレングリコール系材料の少なくとも１種からなる第一の添加剤と、反応中に前記ナノ粒子の表面に配位し、粒子サイズを抑制する第二の添加剤としてトリオクチルホスフィン・スルフィドとを添加し、
不活性雰囲気かつ減圧下で１００℃以下の温度かつ１時間以下の時間保持し、その後２００℃より低い第一の温度で反応を行う第一のステップと、
不活性雰囲気下で前記第一の温度より高い２００℃以上かつ溶媒の沸点以下である第二の温度で、１～２時間反応を継続し硫化物ナノ粒子を生成する第二のステップと、を含むことを特徴とする硫化物ナノ粒子の合成方法。 A method for synthesizing sulfide nanoparticles having a wurtzite crystal structure, comprising thermally decomposing at least one of zinc-containing Group II element materials selected from zinc acetate (Zn(AC) 2 ), zinc stearate (ST-Zn), zinc acetylacetonate (Zn(ACAC) 2 ), and zinc chloride (ZnCl 2 ) and a sulfur material in a solvent, the method comprising the steps of:
a ratio (S/Zn) of the zinc-containing Group II element material to the sulfur material is 0.6 or more and 2 or less;
Adding, to the reaction system, as additives, a first additive consisting of at least one of a polyol-based material and an ethylene glycol stearate-based material, and trioctylphosphine sulfide as a second additive that coordinates to the surface of the nanoparticles during the reaction and suppresses the particle size;
a first step of maintaining the reaction at a temperature of 100° C. or less for a period of 1 hour or less under an inert atmosphere and reduced pressure, followed by a reaction at a first temperature of less than 200° C.;
and a second step of continuing the reaction for 1 to 2 hours in an inert atmosphere at a second temperature that is 200° C. or higher, which is higher than the first temperature, and is lower than the boiling point of the solvent, to produce sulfide nanoparticles.
前記第二のステップは、大気圧下で反応を継続し硫化物ナノ粒子を生成するステップを含むことを特徴とする硫化物ナノ粒子の合成方法。 A method for synthesizing sulfide nanoparticles according to claim 1, comprising the steps of:
The method for synthesizing sulfide nanoparticles, wherein the second step includes continuing the reaction under atmospheric pressure to produce sulfide nanoparticles.
前記第一の添加剤が、エチレングリコールであることを特徴とする硫化物ナノ粒子の合成方法。 A method for synthesizing sulfide nanoparticles according to claim 1, comprising the steps of:
The method for synthesizing sulfide nanoparticles, characterized in that the first additive is ethylene glycol.
硫化亜鉛の化学量論的割合で、前記ＩＩ族元素材料と前記硫黄材料（前記添加剤に含まれる硫黄を除く）とを用い、ワイヤー形状のナノ粒子を生成することを特徴とする硫化物ナノ粒子の合成方法。 A method for synthesizing sulfide nanoparticles according to claim 1, comprising the steps of:
A method for synthesizing sulfide nanoparticles, comprising using the Group II element material and the sulfur material (excluding the sulfur contained in the additive) in a stoichiometric ratio of zinc sulfide to produce wire-shaped nanoparticles.
前記ＩＩ族元素材料に対する前記硫黄材料（前記添加剤に含まれる硫黄を除く）の割合が、ＩＩ族元素硫化物の化学量論的割合以上であって、球状のナノ粒子を生成することを特徴とする硫化物ナノ粒子の合成方法。 A method for synthesizing sulfide nanoparticles according to claim 1, comprising the steps of:
A method for synthesizing sulfide nanoparticles, characterized in that the ratio of the sulfur material (excluding sulfur contained in the additive) to the Group II element material is equal to or greater than the stoichiometric ratio of Group II element sulfides, and spherical nanoparticles are produced.
前記ＩＩ族元素材料に対する前記硫黄材料（前記添加剤に含まれる硫黄を除く）の割合が、硫化亜鉛の化学量論的割合よりも少なく、硫化物における硫黄の一部が酸素に置換されたナノ粒子を製造することを特徴とする硫化物ナノ粒子の合成方法。 A method for synthesizing sulfide nanoparticles according to claim 1, comprising the steps of:
A method for synthesizing sulfide nanoparticles, characterized in that a ratio of the sulfur material (excluding sulfur contained in the additive) to the Group II element material is less than a stoichiometric ratio of zinc sulfide, and nanoparticles are produced in which a portion of the sulfur in the sulfide is substituted with oxygen.
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| JP2018069399A (en) | 2016-11-01 | 2018-05-10 | スタンレー電気株式会社 | Quantum dot |
| JP2018070423A (en) | 2016-11-01 | 2018-05-10 | スタンレー電気株式会社 | PROCESS FOR MANUFACTURING MIX CRYSTAL PARTICLE OF ZnOS IN WURTZITE STRUCTURE |
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| JP2018069399A (en) | 2016-11-01 | 2018-05-10 | スタンレー電気株式会社 | Quantum dot |
| JP2018070423A (en) | 2016-11-01 | 2018-05-10 | スタンレー電気株式会社 | PROCESS FOR MANUFACTURING MIX CRYSTAL PARTICLE OF ZnOS IN WURTZITE STRUCTURE |
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