JP7475839B2 - Method for the synthesis of zinc-containing nanoparticles - Google Patents
Method for the synthesis of zinc-containing nanoparticles Download PDFInfo
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- JP7475839B2 JP7475839B2 JP2019205642A JP2019205642A JP7475839B2 JP 7475839 B2 JP7475839 B2 JP 7475839B2 JP 2019205642 A JP2019205642 A JP 2019205642A JP 2019205642 A JP2019205642 A JP 2019205642A JP 7475839 B2 JP7475839 B2 JP 7475839B2
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- 239000002105 nanoparticle Substances 0.000 title claims description 123
- 239000011701 zinc Substances 0.000 title claims description 123
- 229910052725 zinc Inorganic materials 0.000 title claims description 102
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 title claims description 96
- 238000000034 method Methods 0.000 title claims description 45
- 230000015572 biosynthetic process Effects 0.000 title description 12
- 238000003786 synthesis reaction Methods 0.000 title description 11
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 claims description 140
- 239000002245 particle Substances 0.000 claims description 104
- 239000000463 material Substances 0.000 claims description 81
- 239000013078 crystal Substances 0.000 claims description 76
- 239000011572 manganese Substances 0.000 claims description 70
- 239000011787 zinc oxide Substances 0.000 claims description 69
- 238000006243 chemical reaction Methods 0.000 claims description 38
- 229910052984 zinc sulfide Inorganic materials 0.000 claims description 36
- 229910052717 sulfur Inorganic materials 0.000 claims description 31
- 230000002194 synthesizing effect Effects 0.000 claims description 31
- 239000000654 additive Substances 0.000 claims description 29
- 239000002904 solvent Substances 0.000 claims description 24
- 230000000996 additive effect Effects 0.000 claims description 22
- 150000001875 compounds Chemical class 0.000 claims description 22
- 229910052760 oxygen Inorganic materials 0.000 claims description 19
- 239000012298 atmosphere Substances 0.000 claims description 15
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 13
- 239000001301 oxygen Substances 0.000 claims description 13
- SZINCDDYCOIOJQ-UHFFFAOYSA-L manganese(2+);octadecanoate Chemical compound [Mn+2].CCCCCCCCCCCCCCCCCC([O-])=O.CCCCCCCCCCCCCCCCCC([O-])=O SZINCDDYCOIOJQ-UHFFFAOYSA-L 0.000 claims description 12
- 229910052738 indium Inorganic materials 0.000 claims description 11
- 229910052802 copper Inorganic materials 0.000 claims description 10
- YRKCREAYFQTBPV-UHFFFAOYSA-N acetylacetone Chemical compound CC(=O)CC(C)=O YRKCREAYFQTBPV-UHFFFAOYSA-N 0.000 claims description 8
- 229910052748 manganese Inorganic materials 0.000 claims description 8
- 238000009835 boiling Methods 0.000 claims description 7
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- 229910052759 nickel Inorganic materials 0.000 claims description 6
- 238000000354 decomposition reaction Methods 0.000 claims description 5
- XOOUIPVCVHRTMJ-UHFFFAOYSA-L zinc stearate Chemical compound [Zn+2].CCCCCCCCCCCCCCCCCC([O-])=O.CCCCCCCCCCCCCCCCCC([O-])=O XOOUIPVCVHRTMJ-UHFFFAOYSA-L 0.000 claims description 4
- RFVNOJDQRGSOEL-UHFFFAOYSA-N 2-hydroxyethyl octadecanoate Chemical compound CCCCCCCCCCCCCCCCCC(=O)OCCO RFVNOJDQRGSOEL-UHFFFAOYSA-N 0.000 claims description 3
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- 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
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- RDMHXWZYVFGYSF-LNTINUHCSA-N (z)-4-hydroxypent-3-en-2-one;manganese Chemical compound [Mn].C\C(O)=C\C(C)=O.C\C(O)=C\C(C)=O.C\C(O)=C\C(C)=O RDMHXWZYVFGYSF-LNTINUHCSA-N 0.000 description 3
- VNNDVNZCGCCIPA-FDGPNNRMSA-N (z)-4-hydroxypent-3-en-2-one;manganese Chemical compound [Mn].C\C(O)=C\C(C)=O.C\C(O)=C\C(C)=O VNNDVNZCGCCIPA-FDGPNNRMSA-N 0.000 description 3
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- ZVYYAYJIGYODSD-LNTINUHCSA-K (z)-4-bis[[(z)-4-oxopent-2-en-2-yl]oxy]gallanyloxypent-3-en-2-one Chemical compound [Ga+3].C\C([O-])=C\C(C)=O.C\C([O-])=C\C(C)=O.C\C([O-])=C\C(C)=O ZVYYAYJIGYODSD-LNTINUHCSA-K 0.000 description 2
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- 125000005595 acetylacetonate group Chemical group 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
- 238000011109 contamination Methods 0.000 description 2
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- CCCMONHAUSKTEQ-UHFFFAOYSA-N octadec-1-ene Chemical compound CCCCCCCCCCCCCCCCC=C CCCMONHAUSKTEQ-UHFFFAOYSA-N 0.000 description 2
- 150000002894 organic compounds Chemical class 0.000 description 2
- 239000004065 semiconductor Substances 0.000 description 2
- 150000003752 zinc compounds Chemical class 0.000 description 2
- WRIDQFICGBMAFQ-UHFFFAOYSA-N (E)-8-Octadecenoic acid Natural products CCCCCCCCCC=CCCCCCCC(O)=O WRIDQFICGBMAFQ-UHFFFAOYSA-N 0.000 description 1
- 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
- OVRQXQSDQWOJIL-UHFFFAOYSA-N 1,1-dibutylthiourea Chemical compound CCCCN(C(N)=S)CCCC OVRQXQSDQWOJIL-UHFFFAOYSA-N 0.000 description 1
- CNLHIRFQKMVKPX-UHFFFAOYSA-N 1,1-diethylthiourea Chemical compound CCN(CC)C(N)=S CNLHIRFQKMVKPX-UHFFFAOYSA-N 0.000 description 1
- ZQGWBPQBZHMUFG-UHFFFAOYSA-N 1,1-dimethylthiourea Chemical compound CN(C)C(N)=S ZQGWBPQBZHMUFG-UHFFFAOYSA-N 0.000 description 1
- XWAMHGPDZOVVND-UHFFFAOYSA-N 1,2-octadecanediol Chemical compound CCCCCCCCCCCCCCCCC(O)CO XWAMHGPDZOVVND-UHFFFAOYSA-N 0.000 description 1
- JXUKLFVKZQETHF-UHFFFAOYSA-N 1-$l^{1}-selanyl-n,n'-dimethylmethanimidamide Chemical compound CNC([Se])=NC JXUKLFVKZQETHF-UHFFFAOYSA-N 0.000 description 1
- LQJBNNIYVWPHFW-UHFFFAOYSA-N 20:1omega9c fatty acid Natural products CCCCCCCCCCC=CCCCCCCCC(O)=O LQJBNNIYVWPHFW-UHFFFAOYSA-N 0.000 description 1
- QSBYPNXLFMSGKH-UHFFFAOYSA-N 9-Heptadecensaeure Natural products CCCCCCCC=CCCCCCCCC(O)=O QSBYPNXLFMSGKH-UHFFFAOYSA-N 0.000 description 1
- QTBSBXVTEAMEQO-UHFFFAOYSA-M Acetate Chemical compound CC([O-])=O QTBSBXVTEAMEQO-UHFFFAOYSA-M 0.000 description 1
- 229910021592 Copper(II) chloride Inorganic materials 0.000 description 1
- 229910005555 GaZnO Inorganic materials 0.000 description 1
- 229910021621 Indium(III) iodide Inorganic materials 0.000 description 1
- 229910052493 LiFePO4 Inorganic materials 0.000 description 1
- VLCDUOXHFNUCKK-UHFFFAOYSA-N N,N'-Dimethylthiourea Chemical compound CNC(=S)NC VLCDUOXHFNUCKK-UHFFFAOYSA-N 0.000 description 1
- NBMOASIYCXHBNT-UHFFFAOYSA-N N,N'-diethylcarbamimidoselenoic acid Chemical compound C(C)NC(NCC)=[Se] NBMOASIYCXHBNT-UHFFFAOYSA-N 0.000 description 1
- FLVIGYVXZHLUHP-UHFFFAOYSA-N N,N'-diethylthiourea Chemical compound CCNC(=S)NCC FLVIGYVXZHLUHP-UHFFFAOYSA-N 0.000 description 1
- ZHILTVUWDGCQFD-UHFFFAOYSA-N N,N-diethylcarbamimidoselenoic acid Chemical compound CCN(CC)C(N)=[Se] ZHILTVUWDGCQFD-UHFFFAOYSA-N 0.000 description 1
- VCUFZILGIRCDQQ-KRWDZBQOSA-N N-[[(5S)-2-oxo-3-(2-oxo-3H-1,3-benzoxazol-6-yl)-1,3-oxazolidin-5-yl]methyl]-2-[[3-(trifluoromethoxy)phenyl]methylamino]pyrimidine-5-carboxamide Chemical compound O=C1O[C@H](CN1C1=CC2=C(NC(O2)=O)C=C1)CNC(=O)C=1C=NC(=NC=1)NCC1=CC(=CC=C1)OC(F)(F)F VCUFZILGIRCDQQ-KRWDZBQOSA-N 0.000 description 1
- 206010028980 Neoplasm Diseases 0.000 description 1
- 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
- BUGBHKTXTAQXES-UHFFFAOYSA-N Selenium Chemical compound [Se] BUGBHKTXTAQXES-UHFFFAOYSA-N 0.000 description 1
- UWHCKJMYHZGTIT-UHFFFAOYSA-N Tetraethylene glycol, Natural products OCCOCCOCCOCCO UWHCKJMYHZGTIT-UHFFFAOYSA-N 0.000 description 1
- 239000005083 Zinc sulfide Substances 0.000 description 1
- 125000000217 alkyl group Chemical group 0.000 description 1
- 229910045601 alloy Inorganic materials 0.000 description 1
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- 229960002903 benzyl benzoate Drugs 0.000 description 1
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- 150000003842 bromide salts Chemical class 0.000 description 1
- 201000011510 cancer Diseases 0.000 description 1
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- 150000003841 chloride salts Chemical class 0.000 description 1
- 239000004020 conductor Substances 0.000 description 1
- ORTQZVOHEJQUHG-UHFFFAOYSA-L copper(II) chloride Chemical compound Cl[Cu]Cl ORTQZVOHEJQUHG-UHFFFAOYSA-L 0.000 description 1
- 238000002425 crystallisation Methods 0.000 description 1
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- 238000013461 design Methods 0.000 description 1
- WNAHIZMDSQCWRP-UHFFFAOYSA-N dodecane-1-thiol Chemical compound CCCCCCCCCCCCS WNAHIZMDSQCWRP-UHFFFAOYSA-N 0.000 description 1
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- ORTRWBYBJVGVQC-UHFFFAOYSA-N hexadecane-1-thiol Chemical compound CCCCCCCCCCCCCCCCS ORTRWBYBJVGVQC-UHFFFAOYSA-N 0.000 description 1
- 238000010348 incorporation Methods 0.000 description 1
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- 238000003541 multi-stage reaction Methods 0.000 description 1
- NRTHBQJARHPPAU-UHFFFAOYSA-N n,n-dimethylcarbamimidoselenoic acid Chemical compound CN(C)C([SeH])=N NRTHBQJARHPPAU-UHFFFAOYSA-N 0.000 description 1
- 150000002823 nitrates Chemical class 0.000 description 1
- 238000010899 nucleation Methods 0.000 description 1
- 230000006911 nucleation Effects 0.000 description 1
- ZQPPMHVWECSIRJ-KTKRTIGZSA-N oleic acid Chemical compound CCCCCCCC\C=C/CCCCCCCC(O)=O ZQPPMHVWECSIRJ-KTKRTIGZSA-N 0.000 description 1
- 230000005693 optoelectronics Effects 0.000 description 1
- 238000010587 phase diagram Methods 0.000 description 1
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- 229910052698 phosphorus Inorganic materials 0.000 description 1
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- WGPCGCOKHWGKJJ-UHFFFAOYSA-N sulfanylidenezinc Chemical compound [Zn]=S WGPCGCOKHWGKJJ-UHFFFAOYSA-N 0.000 description 1
- 238000001308 synthesis method Methods 0.000 description 1
- 150000003573 thiols Chemical class 0.000 description 1
- RMUKCGUDVKEQPL-UHFFFAOYSA-K triiodoindigane Chemical compound I[In](I)I RMUKCGUDVKEQPL-UHFFFAOYSA-K 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
- NWONKYPBYAMBJT-UHFFFAOYSA-L zinc sulfate Chemical compound [Zn+2].[O-]S([O-])(=O)=O NWONKYPBYAMBJT-UHFFFAOYSA-L 0.000 description 1
- 229910000368 zinc sulfate Inorganic materials 0.000 description 1
- 229960001763 zinc sulfate Drugs 0.000 description 1
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- Inorganic Compounds Of Heavy Metals (AREA)
Description
本発明は、ウルツ鉱構造のナノ粒子とその製造方法に関し、特に亜鉛以外の元素の導入率を高めたナノ粒子に関する。 The present invention relates to nanoparticles with a wurtzite structure and a method for producing the same, and in particular to nanoparticles with an increased incorporation rate of elements other than zinc.
酸化亜鉛（ＺｎＯ）やその混晶組成のナノ粒子は、可視から紫外にエネルギーギャップを持つため、太陽電池やガス・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。さらに、ＺｎＯナノ粒子に元素を添加することで、光学特性だけでなく、電気的特性、磁気特性、触媒効果などを大きく変えることができ、様々な分野で応用が期待されている。 Zinc oxide (ZnO) and nanoparticles of its mixed crystal composition have an energy gap from the visible to the ultraviolet, making them promising optoelectronic materials for solar cells and gas, chemical, and biological sensors. Furthermore, by adding elements to ZnO nanoparticles, it is possible to significantly change not only their optical properties, but also their electrical properties, magnetic properties, catalytic effects, and other properties, and applications in a variety of fields are expected.
亜鉛ナノ粒子などの金属ナノ粒子の製造方法としては、金属錯体等の金属材料を液相で熱分解して合成する方法（熱分解法、錯体熱分解法とも言われる）が一般的であり、熱分解法により一種以上の金属を含むナノ粒子の合成方法も提案されている（特許文献１）。 The most common method for producing metal nanoparticles such as zinc nanoparticles is to synthesize metal materials such as metal complexes by thermal decomposition in a liquid phase (also called the thermal decomposition method or complex thermal decomposition method), and a method for synthesizing nanoparticles containing one or more metals by thermal decomposition has also been proposed (Patent Document 1).
しかし、ＺｎＯナノ粒子は、非混和性が高いため添加元素を粒子結晶内に均一に混合することが困難である。すなわち、ＺｎＯ１－ｘＳｘ結晶は、熱力学的な安定性からＯ及びＳを均一に含む結晶とすることが非常に困難であることが理論的に示されおり、１０００Ｋ以下の温度においては、ＺｎＯ結晶に対するＳの固溶限界は２％以下、同様にＺｎＳに対するＯの固溶限界は２％以下、と予測されている。従って、一般的な熱分解法による合成では、均一で高いＯ組成或いはＳ組成を持つＺｎＯ１－ｘＳｘナノ粒子を製造することは困難であり、ｘ＝０．０２以下のＺｎＯ１－ｘＳｘとｘ＝０．９８のＺｎＯ１－ｘＳｘの二つの相に分離される。 However, since ZnO nanoparticles are highly immiscible, it is difficult to uniformly mix the additive elements into the particle crystals. That is, it has been theoretically shown that it is very difficult to make ZnO 1-x S x crystals into crystals that uniformly contain O and S due to thermodynamic stability, and it is predicted that at temperatures below 1000K, the solid solubility limit of S in ZnO crystals is 2% or less, and similarly, the solid solubility limit of O in ZnS is 2% or less. Therefore, in synthesis by a general thermal decomposition method, it is difficult to manufacture ZnO 1-x S x nanoparticles having a uniform and high O composition or S composition, and they are separated into two phases, ZnO 1-x S x with x = 0.02 or less and ZnO 1-x S x with x = 0.98.
特許文献１には、反応系に塩基を導入することにより、ＧａをドープしたＺｎＯナノ粒子を合成する技術が開示されているが、Ｇａドープ量はたかだか２．４原子％である（段落０５０）。
また非特許文献１には、異なる結晶系であるＭｎＯ（ロックソルト型）とＺｎＯ（ウルツ鉱型）との三元化合物（ＭｎｘＺｎ１－ｘＯ）では、Ｍｎの割合（ｘ）が０．６を越えると理論的にウルツ鉱型の構造を安定的に保てないことが報告されている。さらに、三元化合物の酸素の一部を硫黄に置換した四元系では、ロックソルト型結晶（ＭｎＯ）と、ウルツ鉱型結晶（ＺｎＯ）及び閃亜鉛鉱型結晶（ＺｎＳ）との混晶が生成しやすくなるため、単一のウルツ鉱型結晶を製造することは困難である。
Also,
一方、非特許文献２には、非混和性の高いナノ粒子の混和性が、その粒子サイズを小さくすることによって高められことが報告されている。非特許文献１では、ＬｉＦｅＰＯ４等のナノ粒子の数学的モデルを用いて、異なる相間の混和ギャップが粒子サイズを小さくすることにより縮むことを理論的に示している。
On the other hand, Non-Patent
しかし、現在、ナノ粒子の製造に広く用いられている熱分解法によりＺｎＯナノ粒子を合成した場合、原料に用いる化合物の種類によってサイズに違いがあるものの、粒子サイズ（平均粒子径）は１８ｎｍ～２００ｎｍ程度であり、混和性を高められると考えられる１０ｎｍ以下のナノ粒子を合成することはできない。 However, when ZnO nanoparticles are synthesized by the thermal decomposition method currently widely used to manufacture nanoparticles, the particle size (average particle diameter) is about 18 nm to 200 nm, although the size varies depending on the type of compound used as the raw material, and it is not possible to synthesize nanoparticles of 10 nm or less, which is thought to improve miscibility.
本発明は、従来の亜鉛含有ナノ粒子よりもサイズの小さい、具体的には１０ｎｍ以下のナノ粒子を合成する方法を提供すること、亜鉛含有ナノ粒子を基本として、基本元素以外の元素を比較的高い割合で含む亜鉛含有ナノ粒子を提供することを課題とする。 The present invention aims to provide a method for synthesizing nanoparticles smaller than conventional zinc-containing nanoparticles, specifically nanoparticles of 10 nm or less, and to provide zinc-containing nanoparticles that are based on zinc-containing nanoparticles and contain a relatively high proportion of elements other than the basic elements.
上記課題を解決するため、本発明者らは熱分解法を基本とする亜鉛含有ナノ粒子の合成の条件について鋭意研究し、特定の反応条件及び添加剤を用いることで、従来得ることができなかった１０ｎｍ以下のナノ粒子を製造できること、また亜鉛及び酸素以外の元素の含有率が高く、均一性の高い亜鉛含有ナノ粒子を製造できることを見出し、本発明に至ったものである。 In order to solve the above problems, the inventors conducted extensive research into the conditions for synthesizing zinc-containing nanoparticles based on a thermal decomposition method, and discovered that by using specific reaction conditions and additives, it is possible to produce nanoparticles of 10 nm or less that were previously unobtainable, and that it is possible to produce zinc-containing nanoparticles that have a high content of elements other than zinc and oxygen and are highly uniform, which led to the present invention.
さらに本発明者らは、亜鉛と置換される元素を含む三元系あるいは四元系の亜鉛含有ナノ粒子について、置換元素の材料として、酸化亜鉛の結晶核が生成する初期の段階で結晶粒子の周囲に配位する材料を用いることにより、ウルツ鉱型の結晶系を保ちながら、亜鉛以外の元素の含有率が高い亜鉛含有ナノ粒子を製造できることを見出したものである。 Furthermore, the inventors have discovered that for ternary or quaternary zinc-containing nanoparticles containing an element that is substituted for zinc, by using a material that coordinates around the crystalline particles at the early stage of the formation of zinc oxide crystal nuclei as the material for the substitution element, it is possible to produce zinc-containing nanoparticles that have a high content of elements other than zinc while maintaining the wurtzite crystal system.
すなわち本発明の亜鉛含有ナノ粒子の合成方法は、亜鉛を含む化合物を溶媒中で熱分解してウルツ鉱型結晶構造の亜鉛含有ナノ粒子を合成する方法であり、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、反応中に前記亜鉛含有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。反応は、亜鉛を含む化合物から粒子を形成する温度より低い第一の温度で反応を行い、粒子結晶の核を生成する第一のステップと、前記第一の温度より高い第二の温度で、反応を継続し亜鉛含有ナノ粒子を生成する第二のステップとを含む。第一のステップは減圧下で行い、第二のステップは大気圧下で行うことが好ましい。 That is, the method for synthesizing zinc-containing nanoparticles of the present invention is a method for synthesizing zinc-containing nanoparticles having a wurtzite crystal structure by thermally decomposing a zinc-containing compound in a solvent, and 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 zinc-containing nanoparticles during the reaction and suppresses the particle size are added to the reaction system. The reaction includes a first step of performing a reaction at a first temperature lower than the temperature at which particles are formed from the zinc-containing compound to generate nuclei of particle crystals, and a second step of continuing the reaction at a second temperature higher than the first temperature to generate zinc-containing nanoparticles. It is preferable that the first step is performed under reduced pressure, and the second step is performed under atmospheric pressure.
さらに本発明の亜鉛含有ナノ粒子の合成方法は、上述した合成方法であって、且つ、前記反応系に、亜鉛を含む化合物及び亜鉛以外の元素Ｍを含む化合物を加えて反応を行い、酸化亜鉛の結晶格子における亜鉛及び／又は酸素の一部が元素Ｍで置換したＭドープ酸化亜鉛ナノ粒子を合成し、その際、前記元素Ｍを含む化合物として、前記粒子結晶の核の周りに配位する配位系材料を用いることを特徴とする。配位系材料の代表的なものとして、ステアリン酸塩が挙げられる。 The method for synthesizing zinc-containing nanoparticles of the present invention is the above-mentioned synthesis method, and further comprises adding a compound containing zinc and a compound containing an element M other than zinc to the reaction system to carry out a reaction, synthesizing M-doped zinc oxide nanoparticles in which part of the zinc and/or oxygen in the zinc oxide crystal lattice is replaced with element M, and using a coordination material that coordinates around the core of the particle crystal as the compound containing element M. A representative example of the coordination material is stearate.
また本発明の亜鉛含有ナノ粒子は、下記一般式で表されるウルツ鉱型結晶構造の亜鉛含有化合物のナノ粒子であって、
（Ｚｎ１－ｘＭ１
ｘ）（Ｏ１－ｙＭ２
ｙ）
（但し、Ｍ１は、Ｇａ、Ｉｎ、Ｃｕ、Ｆｅ、Ｎｉ、Ｃｏ、Ｍｎ、Ｍｇから選ばれる１種以上の元素、Ｍ２は、Ｓ、Ｓｅから選ばれる１種以上の元素を表し、ｘ及びｙは、それぞれｘ≧０、ｙ≧０を満たす。但しｘ＝ｙ＝０を除く。）
平均粒子径が３０ｎｍ以下である。
The zinc-containing nanoparticles of the present invention are nanoparticles of a zinc-containing compound having a wurtzite crystal structure represented by the following general formula:
(Zn1 - xM1x )( O1 - yM2y )
(wherein M1 represents one or more elements selected from Ga, In, Cu, Fe, Ni, Co, Mn, and Mg, M2 represents one or more elements selected from S and Se, and x and y respectively satisfy x≧0 and y≧0, except for x=y=0.)
The average particle size is 30 nm or less.
また本発明の亜鉛含有ナノ粒子は、下記一般式で表されるウルツ鉱型結晶構造の亜鉛含有化合物のナノ粒子であって、
（Ｚｎ１－ｘＭｎｘ）（Ｏ１－ｙＭ２
ｙ）
（但し、Ｍ２は、Ｓ、Ｓｅから選ばれる１種以上の元素で、ｘ及びｙは、それぞれ０．９＞ｘ≧０．２、ｙ≧０を満たす。）である。
The zinc-containing nanoparticles of the present invention are nanoparticles of a zinc-containing compound having a wurtzite crystal structure represented by the following general formula:
(Zn1 - xMnx )(O1 - yM2y )
(wherein M2 is one or more elements selected from S and Se, and x and y satisfy 0.9>x≧0.2 and y≧0, respectively).
なお本発明において「亜鉛含有ナノ粒子」とは、亜鉛酸化物、亜鉛硫化物または亜鉛硫酸化物など、亜鉛と酸素及び硫黄の少なくとも一方とを含む亜鉛化合物のナノ粒子、及び、それに加えて亜鉛／酸素／硫黄以外の元素を含む亜鉛化合物のナノ粒子を意味する。 In the present invention, "zinc-containing nanoparticles" refers to nanoparticles of zinc compounds that contain zinc and at least one of oxygen and sulfur, such as zinc oxide, zinc sulfide, or zinc sulfate, and also nanoparticles of zinc compounds that contain elements other than zinc, oxygen, and sulfur.
本発明によれば、所定の添加剤を組み合わせて結晶成長条件を制御することにより、熱分解法を基本として、従来の熱分解法では得られなかった１０ｎｍ以下の亜鉛含有ナノ粒子を提供することができる。また本発明によれば、亜鉛含有ナノ粒子のサイズを１０ｎｍ以下の極めて小さいサイズにすることにより、非混和性の高い元素を安定して結晶構造内に取り込むことができ、新規な３元以上の亜鉛含有ナノ粒子を提供することができる。 According to the present invention, by combining specific additives and controlling the crystal growth conditions, it is possible to provide zinc-containing nanoparticles of 10 nm or less that could not be obtained by conventional thermal decomposition methods, based on the thermal decomposition method. Furthermore, according to the present invention, by making the size of the zinc-containing nanoparticles extremely small, 10 nm or less, it is possible to stably incorporate highly immiscible elements into the crystal structure, and it is possible to provide novel zinc-containing nanoparticles with ternary or more elements.
さらに本発明によれば、亜鉛以外の元素の材料として、亜鉛含有ナノ粒子の結晶核が生成する反応の第一ステップにおいて、結晶粒子の周りに配位する配位系材料を用いることにより、ウルツ鉱の結晶構造を保ちながら、高い割合で亜鉛以外の元素を取り込んだ新規な亜鉛含有粒子を提供することができる。 Furthermore, according to the present invention, by using a coordination material that coordinates around the crystal particles as a material of an element other than zinc in the first step of the reaction in which the crystal nuclei of zinc-containing nanoparticles are generated, it is possible to provide new zinc-containing particles that incorporate elements other than zinc at a high ratio while maintaining the wurtzite crystal structure.
以下、本発明の亜鉛含有ナノ粒子の合成方法の実施形態を説明する。
酸化亜鉛（ＺｎＯ）を基本として、Ｚｎ及びＯ以外の元素を添加する場合を説明する。合成に用いる亜鉛材料としては、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）など亜鉛錯体を用いることができる。なおＺｎ及びＯ以外の元素の原料として、後述する配位系の材料を用いる場合には、亜鉛材料は、それよりも分解温度の低い配位系ではない材料であることが好ましい。具体的には、アセチルアセトナート亜鉛が好適である。このような配位系ではない材料を用いることにより、結晶生成過程でウルツ鉱型の結晶核が優先的に生成され、他の結晶系の酸化物の生成を抑制することができる。
Hereinafter, an embodiment of the method for synthesizing zinc-containing nanoparticles of the present invention will be described.
The case where elements other than Zn and O are added to zinc oxide (ZnO) will be described. As the zinc material used in the synthesis, zinc complexes such as zinc acetate (Zn(AC) 2 ), zinc stearate (ST-Zn), and zinc acetylacetonate (Zn(ACAC) 2 ) can be used. When using a coordination material described later as a raw material for elements other than Zn and O, it is preferable that the zinc material is a non-coordination material with a lower decomposition temperature. Specifically, zinc acetylacetonate is suitable. By using such a non-coordination material, wurtzite-type crystal nuclei are preferentially generated during the crystallization process, and the generation of oxides of other crystal systems can be suppressed.
Ｚｎ及びＯ以外の元素としては、Ｓ、Ｓｅ、Ｇａ、Ｉｎ、Ｃｕ、Ｆｅ、Ｎｉ、Ｃｏ、Ｍｎ、Ｍｇから選ばれる１種以上の元素を用いることができる。これら元素のうち、ＶＩ族の元素Ｓ、Ｓｅは、ウルツ鉱型の酸化亜鉛結晶構造において、酸素（Ｏ）を置換する形で酸化亜鉛ナノ粒子に取り込まれる。そしてＳ、Ｓｅを導入することで酸化亜鉛のエネルギーギャップを紫外から可視領域に変化させることができる。それ以外の元素（Ｍ１）はＺｎ置換する形で酸化亜鉛ナノ粒子に取り込まれる。Ｇａ、Ｉｎ、Ｃｕを酸化亜鉛に導入することにより、透明性などの光学的な特性を変化させることができる。またＦｅ、Ｎｉ、Ｃｏ、Ｍｎを酸化亜鉛に導入することにより、磁気的な性質を変化させることができる。 As the elements other than Zn and O, one or more elements selected from S, Se, Ga, In, Cu, Fe, Ni, Co, Mn, and Mg can be used. Among these elements, the VI group elements S and Se are incorporated into zinc oxide nanoparticles in the form of substituting oxygen (O) in the wurtzite zinc oxide crystal structure. The introduction of S and Se can change the energy gap of zinc oxide from the ultraviolet region to the visible region. The other elements (M 1 ) are incorporated into zinc oxide nanoparticles in the form of substituting Zn. The introduction of Ga, In, and Cu into zinc oxide can change optical properties such as transparency. The introduction of Fe, Ni, Co, and Mn into zinc oxide can change magnetic properties.
酸化亜鉛に添加する元素の原料化合物は、元素によって適宜選択することができるが、Ｇａ、Ｉｎ、Ｃｕ、Ｆｅ、Ｎｉ、Ｃｏの場合、例えば、塩化物、ヨウ化物、臭化物、硝酸塩、酢酸塩、ステアリン酸塩、アセチルアセトナートなどの塩或いは錯体を用いることができる。また、Ｍｎは、ステアリン酸塩、酢酸塩、アセチルアセトナート、或いはトリオクチルホスフィン（ＴＯＰ）錯体などが好ましく、特に亜鉛材料よりも分解温度が高く、合成反応の初期において、酸化亜鉛粒子の周囲に配位する配位系の材料が好ましく、中でもステアリン酸マンガンが好適である。このような配位系の材料を用いることにより、ウルツ鉱型とは異なる結晶構造を持つ金属酸化物の生成を抑制しつつ、当該金属元素のドープ量（亜鉛含有粒子中の含有割合）を増加させることができる。 The raw material compound of the element to be added to zinc oxide can be appropriately selected depending on the element. In the case of Ga, In, Cu, Fe, Ni, and Co, for example, salts or complexes such as chlorides, iodides, bromides, nitrates, acetates, stearates, and acetylacetonates can be used. In addition, for Mn, stearates, acetates, acetylacetonates, and trioctylphosphine (TOP) complexes are preferred, and in particular, coordination materials that have a higher decomposition temperature than zinc materials and are coordinated around zinc oxide particles in the early stages of the synthesis reaction are preferred, and manganese stearate is particularly suitable. By using such coordination materials, it is possible to increase the doping amount of the metal element (the content ratio in the zinc-containing particles) while suppressing the generation of metal oxides with a crystal structure different from the wurtzite type.
酸素（Ｏ）の一部を置換するＶＩ族の元素（Ｍ２）については、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－ジブチルチオ尿素などのＳ含有有機化合物、硫黄粉末、１，１－ジメチルセレノ尿素、１，３－ジメチルセレノ尿素、１，１－ジエチルセレノ尿素、１，３－ジエチルセレノ尿素などのＳｅ含有有機化合物を用いることができる。 As for the Group VI element (M 2 ) that replaces a portion of the oxygen (O), 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, and 1,3-dibutylthiourea, and Se-containing organic compounds such as sulfur powder, 1,1-dimethylselenourea, 1,3-dimethylselenourea, 1,1-diethylselenourea, and 1,3-diethylselenourea can be used.
これら元素は、例えば、ＩＩ族及びＶＩ族以外の元素と、ＶＩ族の元素を同時に用いてもよく、それにより（Ｚｎ、Ｍ１）（ＯＳ）或いは（Ｚｎ、Ｍ１）（ＯＳｅ）のような４元系の亜鉛含有ナノ粒子を合成することができる。 These elements may be used, for example, in combination with elements other than Group II and Group VI, thereby synthesizing quaternary zinc-containing nanoparticles such as (Zn, M 1 )(OS) or (Zn, M 1 )(OSe).
亜鉛原料に対する原料化合物の割合（モル比）は、目的とするナノ粒子におけるドープ元素（Ｍ１、Ｍ２）の割合（原子％）に対応する量とする。元素やその組み合わせによっても異なるが、具体的には亜鉛または酸素に対し、２０原子％以下であることが好ましい。ドープ元素の割合が過剰な場合には、酸化亜鉛のウルツ鉱型の結晶構造とは異なる晶系の結晶構造のものが生成される可能性がある。なおドープ元素（Ｍ１）がＭｎの場合には、上述したように、原料として配位系の材料を用いることにより、亜鉛に対し２０原子％以上添加してもウルツ鉱型の結晶構造を保つことができる。具体的には、酢酸塩、アセチルアセトナート、トリオクチルホスフィン（ＴＯＰ）錯体を用いた場合には、４０原子％程度まで、ステアリン酸マンガンを用いた場合には、理論的にウルツ鉱型結晶構造をとることができないとされる６２原子％を越え、９０原子％近くまで高めることができる。 The ratio (molar ratio) of the raw material compound to the zinc raw material is an amount corresponding to the ratio (atomic %) of the doping element (M 1 , M 2 ) in the target nanoparticle. Although it varies depending on the element and its combination, specifically, it is preferably 20 atomic % or less with respect to zinc or oxygen. When the ratio of the doping element is excessive, a crystal structure of a crystal system different from the wurtzite crystal structure of zinc oxide may be generated. Note that, when the doping element (M 1 ) is Mn, as described above, by using a coordination material as the raw material, the wurtzite crystal structure can be maintained even if 20 atomic % or more is added to zinc. Specifically, when acetate, acetylacetonate, or trioctylphosphine (TOP) complex is used, it can be increased to about 40 atomic %, and when manganese stearate is used, it can be increased to nearly 90 atomic %, exceeding 62 atomic %, which is theoretically considered impossible to obtain a wurtzite crystal structure.
添加剤には、結晶構造を維持する機能を持つ第一の添加剤と、生成するナノ粒子の結晶の表面に配位することで、結晶粒子の成長を抑制するサイズ制御剤として機能する第二の添加剤（以下、サイズ制御剤という）と、を用いる。 The additives used are a first additive that has the function of maintaining the crystal structure, and a second additive (hereafter referred to as the size control agent) that functions as a size control agent that inhibits the growth of crystal particles by coordinating with the surface of the nanoparticle crystals that are generated.
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, 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.
サイズ制御剤としては、ＺｎＯ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ことなく、ＺｎＯ粒子の表面に配位し、サイズを抑制する機能を持つことが本発明者らによって確認された。 As the size control agent, a bulky complex that coordinates with the Zn of the ZnO 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 the inventors have confirmed that in the reaction of the present invention, it does not function as a sulfur source, but rather coordinates to the surface of the ZnO particles and has the function of suppressing the size.
サイズ制御剤の量は、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 size control agent is 0.1 to 1.0, preferably 0.2 to 0.8, and more preferably about 0.4 to 0.6, in molar ratio to the zinc raw material. When synthesizing a complex with 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。具体的には、第一のステップでは、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。このような条件で、１～３時間程度保持したのち昇温し、再び不活性雰囲気下で２００℃以上、溶媒の沸点以下の温度（例えば２５０℃）で１～２時間保持する（第二のステップ）。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）、短時間保持し反応を完了させる。 The reaction is carried out by heating in a solvent (liquid phase). In this case, it is preferable to carry out a multi-stage 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 under an inert atmosphere, and to vary the reaction time, atmosphere, and other conditions for each stage. Specifically, in the first step, the reaction is first held for a short period of time of 1 hour or less at a temperature of 100°C or less (for example, about 70°C) in an inert atmosphere such as N2 , and then heated, and the reaction is allowed to proceed at a temperature of 200°C or less (for example, 130°C) under a reduced pressure atmosphere. The pressure under the reduced pressure atmosphere is 1/100 or less of atmospheric pressure (about 100 kPa). However, in order to prevent bumping of the solvent, the pressure is set to 15 Pa or more. After holding for about 1 to 3 hours under these conditions, the temperature is raised, and again held for 1 to 2 hours at a temperature of 200°C or more and below the boiling point of the solvent (for example, 250°C) under an inert atmosphere (second step). The temperature increase rate from the first step to the second step is not limited, but is, for example, 50° C./5 min. After the second step, the temperature is further increased (but not exceeding the boiling point of the solvent) and maintained for a short period of time to complete the reaction.
このように反応を複数段階に分けることで、結晶粒子の成長を抑制し、極めてサイズの小さい、例えば１０ｎｍ以下の亜鉛含有ナノ粒子を得ることができる。これは次のような理由によるものと考えられる。まず、１００℃以下の温度（例えば７０℃程度）で１時間以下の短時間保持することにより、材料が溶解し、反応溶液が均一化する。次の、減圧雰囲気下で２００℃以下の温度（例えば１３０℃程度）で１～３時間程度保持するステップ（第一のステップ）では、粒子結晶の核が形成されていると考えられる。その次の、不活性雰囲気下で２００℃以上、溶媒の沸点以下の温度（例えば２５０℃）で１～２時間保持するステップ（第二のステップ）では、粒子結晶の核から粒子が成長すると考えられる。その後、更に温度を上げて（ただし、溶媒の沸点以下）、短時間保持するステップでは、結晶性を高めるとともに、粒子内に均一に元素を添加されていると考えられる。 By dividing the reaction into multiple stages in this way, the growth of crystal particles can be suppressed, and zinc-containing nanoparticles with extremely small sizes, for example, 10 nm or less, can be obtained. This is believed to be due to the following reasons. First, by holding the temperature at 100°C or less (for example, about 70°C) for a short time of 1 hour or less, the materials are dissolved and the reaction solution becomes homogenous. In the next step (first step), in which the temperature is held at 200°C or less (for example, about 130°C) for about 1 to 3 hours in a reduced pressure atmosphere, it is believed that the nuclei of particle crystals are formed. In the next step (second step), in which the temperature is held at 200°C or more and below the boiling point of the solvent (for example, 250°C) for 1 to 2 hours in an inert atmosphere, it is believed that particles grow from the nuclei of particle crystals. Then, in the step of further increasing the temperature (but below the boiling point of the solvent) and holding for a short time, it is believed that the crystallinity is increased and the elements are uniformly added within the particles.
また添加元素がＭｎであって、Ｍｎ材料が亜鉛材料よりも分解温度が高い配位系の材料の場合、第一のステップでウルツ鉱型の酸化亜鉛粒子の結晶核が生成すると、配位系材料が粒子表面に配位しながら分解と結晶成長が進むと考えられる。その結果、ウルツ鉱型酸化亜鉛の結晶構造を引き継ぎながら結晶成長が進行し、結晶構造を維持しながらＭｎドープＭｎＺｎＯ或いはＭｎＺｎＯＳを合成することが可能となる。特に配位系の材料がステアリン酸マンガンの場合、同じ配位系の溶媒であるオレイルアミンと同様にアルキル鎖を持つ材料であるため、粒子形成過程においてお互いが阻害されることなくい、粒子表面に配位できる。そのため、自発的な核生成や粒子成長が抑制され、ロックソルト（ＲＳ）型ＭｎＯの生成を抑えることができる。 In addition, when the added element is Mn and the Mn material is a coordination material with a higher decomposition temperature than the zinc material, it is thought that when the crystal nuclei of wurtzite zinc oxide particles are generated in the first step, decomposition and crystal growth proceed while the coordination material is coordinated to the particle surface. As a result, crystal growth proceeds while inheriting the crystal structure of wurtzite zinc oxide, and it becomes possible to synthesize Mn-doped MnZnO or MZnOS while maintaining the crystal structure. In particular, when the coordination material is manganese stearate, it is a material with an alkyl chain like oleylamine, which is a solvent of the same coordination system, so that they can be coordinated to the particle surface without being inhibited by each other during the particle formation process. Therefore, spontaneous nucleation and particle growth are suppressed, and the generation of rock salt (RS) type MnO can be suppressed.
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.
本発明の亜鉛含有ナノ粒子の製造方法によれば、反応系に所定の添加剤を添加するとともに、これら添加剤を機能させるように反応条件を段階的に異ならせることで、従来では得ることができないサイズ、１０ｎｍ以下ないし１０ｎｍ未満の亜鉛含有ナノ粒子を得ることができる。また亜鉛含有ナノ粒子の結晶構造内に、非混和性の高い、他の元素を取り込むことができ、他元素の割合を高めた亜鉛含有ナノ粒子を製造することができる。具体的には、他元素の割合を２０原子％まで高めることができる。 According to the method for producing zinc-containing nanoparticles of the present invention, by adding a specific additive to the reaction system and varying the reaction conditions stepwise to allow these additives to function, it is possible to obtain zinc-containing nanoparticles of a size that could not be obtained conventionally, that is, 10 nm or less or less than 10 nm. In addition, other elements that are highly immiscible can be incorporated into the crystal structure of the zinc-containing nanoparticles, and zinc-containing nanoparticles with an increased proportion of other elements can be produced. Specifically, the proportion of other elements can be increased to 20 atomic %.
また本発明の亜鉛含有ナノ粒子の製造方法によれば、ドープ元素の材料として配位系材料を用いることにより、ウルツ鉱の結晶構造を維持しながらドープ元素のドープ量を高めることができる。例えば、ドープ元素がＭｎである場合に、配位系材料を用いることにより、Ｚｎに対するＭｎの割合を８０原子％以上に高めることができる。 In addition, according to the method for producing zinc-containing nanoparticles of the present invention, by using a coordination material as the material for the doping element, it is possible to increase the doping amount of the doping element while maintaining the wurtzite crystal structure. For example, when the doping element is Mn, the ratio of Mn to Zn can be increased to 80 atomic % or more by using a coordination material.
以上、本発明の亜鉛含有化合物のナノ粒子の製造方法を、亜鉛及び酸素／硫黄以外の元素Ｍ１、Ｍ２を加える場合について説明したが、本発明の製造方法は、これら元素Ｍ１、Ｍ２を加えない場合、即ち、ＺｎＯナノ粒子を製造する場合にも適用することが可能であり、それによって従来の熱分解法では得ることができないサイズ、１０ｎｍ以下の酸化亜鉛ナノ粒子を熱分解法により得ることができる。 The method for producing nanoparticles of a zinc-containing compound of the present invention has been described above in the case where elements M 1 and M 2 other than zinc and oxygen/sulfur are added. However, the production method of the present invention can also be applied to the case where these elements M 1 and M 2 are not added, i.e., when ZnO nanoparticles are produced. As a result, zinc oxide nanoparticles of 10 nm or less, which cannot be obtained by conventional thermal decomposition methods, can be obtained by a thermal decomposition method.
本発明の亜鉛含有ナノ粒子は、従来にはない極めてサイズの小さいナノ粒子であり、数１０ｎｍオーダーの粒子とは異なる挙動を示し、従来の用途における新たな特性の付与や新たな用途への適用（例えば、透明光源、ガンマーカなどの生体ラベル、光活性のあるドラッグデリバリーシステムなど）が期待できる。また本発明の亜鉛含有ナノ粒子は、Ｚｎ以外の元素の割合が高く、ＺｎＯやＺｎＳからなるナノ粒子とは異なるエネルギーギャップを持ち、異なる物性（電気的特性、磁気特性、光学特性など）を備える。従って、ＺｎＯナノ粒子の適用範囲の拡大が期待される。 The zinc-containing nanoparticles of the present invention are nanoparticles with an unprecedentedly small size, and behave differently from particles on the order of several tens of nm. They are expected to be used to impart new properties to conventional applications and to be applied to new applications (e.g., transparent light sources, biological labels such as cancer markers, photoactive drug delivery systems, etc.). Furthermore, the zinc-containing nanoparticles of the present invention have a high proportion of elements other than Zn, a different energy gap from nanoparticles made of ZnO or ZnS, and different physical properties (electrical properties, magnetic properties, optical properties, etc.). Therefore, it is expected that the range of applications of ZnO nanoparticles will be expanded.
以下、本発明の亜鉛含有化合物のナノ粒子の製造方法の実施例を説明する。以下の実施例において、元素の割合について示す「％」は、特に限定しない限り「原子％」である。 Below, examples of the method for producing nanoparticles of zinc-containing compounds according to the present invention are described. In the following examples, the percentages shown for the proportions of elements are atomic percentages unless otherwise specified.
＜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、第一の添加剤としてエチレングリコール（ＥＧ） １．０ｍｍｏｌ、サイズ制御剤としてＴＯＰ １．２ｍｍｏｌ及び硫黄 ０．６ｍｍｏｌを用いた。
Example 1
10 mL of oleylamine was used as the solvent, 2.0 mmol of Zn(ACAC) 2 as the zinc material, 1.0 mmol of ethylene glycol (EG) as the first additive, 1.2 mmol of TOP as the size control agent, and 0.6 mmol of sulfur were used.
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℃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、Ｎ２雰囲気下で２５０℃に２時間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). Then, the material was heated at a rate of 50 ° C / 5 minutes and held at 250 ° C for 2 hours under a N 2 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、ＺｎＯ分散液を得た。 After cooling, 5 ml of hexane was added to the reaction solution, which was then stirred and 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 ZnO dispersion.
得られた粒子の透過型電子顕微鏡像（ＴＥＭ像）を図１に、ＸＲＤ回折パターンを図２に示す。粒子の粒子径は、ＴＥＭ像から３～７ｎｍであることが確認された。またＸＲＤから、ＺｎＯのピークが確認され、ピークの半値幅から算出した平均粒子径は５ｎｍであった。 A transmission electron microscope (TEM) image of the obtained particles is shown in Figure 1, and an XRD diffraction pattern is shown in Figure 2. The TEM image confirmed that the particles had a particle size of 3 to 7 nm. Furthermore, XRD confirmed a ZnO peak, and the average particle size calculated from the half-width of the peak was 5 nm.
＜比較例１～３＞
添加剤（ＥＧ及びＴＯＰ：Ｓ）を加えない以外は実施例１と同様の方法でＺｎＯ粒子を合成した（比較例１）。また添加剤としてＴＯＰ：Ｓのみを加えた場合（比較例２）及びＥＧのみを加えた場合（比較例３）についても実施例１と同様の方法でＺｎＯ粒子を合成した。結果を実施例１の結果と併せて、図２及び図３に示す。
<Comparative Examples 1 to 3>
ZnO particles were synthesized in the same manner as in Example 1 except that no additives (EG and TOP:S) were added (Comparative Example 1). ZnO particles were also synthesized in the same manner as in Example 1 when only TOP:S was added as an additive (Comparative Example 2) and when only EG was added (Comparative Example 3). The results are shown in Figures 2 and 3 together with the results of Example 1.
また実施例１及び比較例１～３のＺｎＯ粒子について、ＴＥＭ像及びＸＲＤから求めた粒子径の結果を表１に示す。 Table 1 also shows the particle size results obtained from TEM images and XRD for the ZnO particles of Example 1 and Comparative Examples 1 to 3.
表１に示す結果からもわかるように、第一の添加剤（ＥＧ）及び／またはサイズ制御剤（ＴＯＰ：Ｓ）を添加していない場合は１０ｎｍ以上のＺｎＯ粒子が析出しているのに対し、第一の添加剤及びサイズ制御剤の両方を添加した場合は平均粒径５ｎｍのＺｎＯ粒子が析出していた。また図２のＸＲＤからもわかるように、実施例１のＺｎＯのピークは、比較例１～３のピークに比べブロードで且つ強度が小さくなっており、粒子サイズが大幅に小さくなっていることが確認された。このように２種類の添加剤を加えることで初めて１０ｎｍ未満の小さなＺｎＯ粒子を得ることができた。 As can be seen from the results shown in Table 1, when the first additive (EG) and/or size control agent (TOP:S) was not added, ZnO particles of 10 nm or more were precipitated, whereas when both the first additive and the size control agent were added, ZnO particles with an average particle size of 5 nm were precipitated. Also, as can be seen from the XRD in Figure 2, the ZnO peak in Example 1 was broader and less intense than the peaks in Comparative Examples 1 to 3, confirming that the particle size was significantly smaller. In this way, it was only by adding two types of additives that small ZnO particles of less than 10 nm were obtained.
粒子サイズが１０ｎｍ以下のＺｎＯナノ粒子ができたことで、その他元素を添加した際の非混和性を解消することができると予想されたので、次に、ＺｎＯへの固溶度が低く、非混和性の高い元素を添加した実施例を行った。 Since it was expected that the creation of ZnO nanoparticles with a particle size of 10 nm or less would eliminate the immiscibility that occurs when other elements are added, we next carried out an example in which an element that has low solid solubility in ZnO and is highly immiscible was added.
＜実施例２＞
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、Ｇａ材料としてＧａ（ＡＣＡＣ）３ ０．１ｍｍｏｌ（５％）または０．２ｍｍｏｌ（１０％）を用いた。また第一の添加剤としてエチレングリコール（ＥＧ） １．０ｍｍｏｌ、サイズ制御剤としてＴＯＰ １．２ｍｍｏｌ及び硫黄 ０．６ｍｍｏｌを用いた。
容器に材料充填後、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℃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、Ｎ２雰囲気下で２５０℃に２時間保持し、さらに昇温してＮ２雰囲気下で３００℃に１５分保持して合成を行った。
Example 2
10 mL of oleylamine was used as a solvent, 2.0 mmol of Zn(ACAC) 2 was used as a zinc material, 0.1 mmol (5%) or 0.2 mmol (10%) of Ga(ACAC) 3 was used as a Ga material, 1.0 mmol of ethylene glycol (EG) was used as a first additive, and 1.2 mmol of TOP and 0.6 mmol of sulfur were used as size control agents.
After filling the container with the material, the material was held at 70°C for 30 minutes in a nitrogen atmosphere, and then heated and held at 130°C for 2 hours in 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 material was held at 250°C for 2 hours in a N2 atmosphere at a temperature rise rate of 50°C/5 minutes, and further heated and held at 300°C for 15 minutes in 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、ＧａＺｎＯ粒子を得た。 After cooling, 5 mL of hexane was added to the reaction solution, which was then stirred and 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 GaZnO particles.
得られたナノ粒子のＴＥＭ像を図３（ａ）に示す。図３（ａ）において、上側はＧａの添加量が５％の場合、下側は添加量が１０％の場合である。これらＴＥＭ像から測定したナノ粒子の粒子径は、３～４ｎｍであり、１０ｎｍ以下であることが確認された。またナノ粒子のＸＲＤ及びＸＲＦ測定を行い、Ｇａが材料の混合比通りに均一に結晶構造内に取り込まれていることを確認した。 The TEM image of the obtained nanoparticles is shown in Figure 3(a). In Figure 3(a), the upper side is when the Ga addition amount is 5%, and the lower side is when the Ga addition amount is 10%. The particle diameter of the nanoparticles measured from these TEM images was confirmed to be 3-4 nm, less than 10 nm. In addition, XRD and XRF measurements were performed on the nanoparticles, and it was confirmed that Ga was uniformly incorporated into the crystal structure in accordance with the mixture ratio of the materials.
＜実施例３、４＞
Ｇａの代わりに、ＩｎまたはＣｕの原料を添加して、実施例２と同様に（ＺｎＩｎ）Ｏ及び（ＺｎＣｕ）Ｏのナノ粒子を合成した。原料として、Ｉｎを添加する場合（実施例３）はＩｎ（ＡＣ）３を、Ｃｕを添加する場合（実施例４）はＣｕＣｌ２を、使用した。添加量は、いずれも、０．１ｍｍｏｌ（５％）又は０．２ｍｍｏｌ（１０％）とした。
<Examples 3 and 4>
Instead of Ga, the raw material In or Cu was added, and nanoparticles of (ZnIn)O and (ZnCu)O were synthesized in the same manner as in Example 2. When In was added (Example 3), In(AC) 3 was used as the raw material, and when Cu was added (Example 4), CuCl2 was used. The amount of addition was 0.1 mmol (5%) or 0.2 mmol (10%) in both cases.
得られたＺｎＩｎＯナノ粒子及びＺｎＣｕＯ粒子のＴＥＭ像を、それぞれ図３（ｂ）、（ｃ）に示す。これら図面においても上側はＩｎまたはＣｕの添加量が５％の場合、下側は添加量が１０％の場合である。これらＴＥＭ像から、粒子径が１０ｎｍ以下であることが確認された。またＸＲＤ及びＸＲＦ測定結果から、Ｉｎ或いはＣｕが材料の混合比通りに結晶構造内に取り込まれていることを確認した。実施例３において、Ｉｎの材料としてＩｎ（ＡＣ）３の代わりに、ＩｎＩ３を用いた場合にも同様の結果が得られた。 TEM images of the obtained ZnInO nanoparticles and ZnCuO particles are shown in Figures 3(b) and (c), respectively. In these figures, the upper side shows the case where the amount of In or Cu added is 5%, and the lower side shows the case where the amount added is 10%. From these TEM images, it was confirmed that the particle diameter was 10 nm or less. Furthermore, from the results of XRD and XRF measurements, it was confirmed that In or Cu was incorporated into the crystal structure according to the mixture ratio of the materials. In Example 3, similar results were obtained when InI 3 was used as the In material instead of In(AC) 3 .
実施例２～４により、ＺｎＯ粒子が直径１０ｎｍ以下になるように成長条件を制御することによって、非混和性の高いＧａ、Ｉｎ、ＣｕをＺｎＯの結晶構造内に取り込むことができることが確認された。Ｇａ、Ｉｎ、Ｃｕは、いずれもＺｎＯの電気的特性を変化させる元素であり、これら元素を導入したナノ粒子はＺｎＯの応用範囲を広げることが期待される。 Examples 2 to 4 confirmed that highly immiscible elements Ga, In, and Cu can be incorporated into the crystal structure of ZnO by controlling the growth conditions so that the ZnO particles have a diameter of 10 nm or less. Ga, In, and Cu are all elements that change the electrical properties of ZnO, and nanoparticles incorporating these elements are expected to broaden the range of applications of ZnO.
＜実施例５＞
溶媒としてオレイルアミン１０ｍＬ、亜鉛材料としてＺｎ（ＡＣＡＣ）２、Ｍｎ材料としてステアリン酸マンガン（ｓｔ－Ｍｎ）を表２に示す割合で用いた（表中、ｓｔ－Ｍｎの％は、ＺｎとＭｎの合計に対するＭｎの割合（モル％）を表す）。また第一の添加剤としてエチレングリコール（ＥＧ） １．０ｍｍｏｌ、サイズ制御剤としてＴＯＰ １．２ｍｍｏｌ及び硫黄 ０．６ｍｍｏｌを用いた。
Example 5
10 mL of oleylamine was used as a solvent, Zn(ACAC) 2 as a zinc material, and manganese stearate (st-Mn) as a Mn material in the proportions shown in Table 2 (in the table, the % of st-Mn represents the proportion (mol %) of Mn to the total of Zn and Mn). 1.0 mmol of ethylene glycol (EG) was used as the first additive, and 1.2 mmol of TOP and 0.6 mmol of sulfur were used as size control agents.
得られたＺｎＭｎＯ粒子のＴＥＭ像を図４に、ＸＲＤパターンを図５に示す。図５において、Ｍｎ添加量０％はウルツ鉱型ＺｎＯのＸＲＤパターンである。Ｍｎの添加量が９０％である実験例５及び１００％である実験例６のＭｎＯ粒子は、図４に示すＴＥＭ像から、ロックソルト型の結晶構造に特徴的な四角形の粒子であることがわかり、またＸＲＤパターンでもロックソルト（ＲＳ）のピーク（４２度付近及び５８．５度付近）が観察された。一方、Ｍｎ材料の添加割合が８０％以下では、いずれもＴＥＭ像からウルツ鉱型の球状粒子であることが確認され、ＸＲＤパターンにもロックソルトのピークはなくウルツ鉱構造が保たれていることが確認された。ＴＥＭから測定した粒子径は、Ｍｎの割合が多くなるにつれて大きくなる傾向が見られ、４０％以下では５ｎｍ以下、６０％では８～１０ｎｍ、８０％では７～３０ｎｍであった。 The TEM image of the obtained ZnMnO particles is shown in FIG. 4, and the XRD pattern is shown in FIG. 5. In FIG. 5, the XRD pattern of 0% Mn addition is that of wurtzite-type ZnO. The MnO particles of Experimental Example 5, in which the amount of Mn added is 90%, and Experimental Example 6, in which the amount of Mn added is 100%, are found to be square particles characteristic of a rock salt-type crystal structure from the TEM image shown in FIG. 4, and rock salt (RS) peaks (near 42 degrees and 58.5 degrees) were also observed in the XRD pattern. On the other hand, when the amount of Mn added was 80% or less, it was confirmed that all of them were wurtzite-type spherical particles from the TEM image, and there was no rock salt peak in the XRD pattern, confirming that the wurtzite structure was maintained. The particle size measured from the TEM showed a tendency to increase as the amount of Mn added increased, being 5 nm or less at 40% or less, 8 to 10 nm at 60%, and 7 to 30 nm at 80%.
またＺｎＭｎＯ粒子の組成を、ＸＲＤ及びＸＲＦ測定により分析した結果、原料におけるＭｎの割合が２０％、４０％、６０％、８０％において、生成した粒子におけるＭｎの割合（Ｚｎ１－ｘＭｎｘのｘ×１００）は、それぞれ、１８．４％、４０．１％、６１．０％、８５．７％であり、原料の混合比通りに結晶構造内に取り込まれていることを確認した。 In addition, the composition of the ZnMnO particles was analyzed by XRD and XRF measurements. As a result, when the ratio of Mn in the raw materials was 20%, 40%, 60%, and 80%, the ratio of Mn in the generated particles (Zn1 - xMnx x x 100) was 18.4%, 40.1%, 61.0%, and 85.7%, respectively, and it was confirmed that Mn was incorporated into the crystal structure according to the mixing ratio of the raw materials.
＜実施例６＞
Ｍｎの原料として、ステアリン酸マンガンの代わりに、Ｍｎ（ＡＣＡＣ）３、Ｍｎ（ＡＣＡＣ）２、Ｍｎ（ＡＣ）２、ＴＯＰ：Ｍｎをそれぞれ用いて、実施例５と同様に、Ｍｎ原料の割合を２０％、４０％、６０％及び８０％と異ならせて、ＺｎＭｎＯ粒子を合成した。但し、ＴＯＰ：Ｍｎについては、Ｍｎの割合が２０％、６０％の２つの実験例で合成を行った。
Example 6
Instead of manganese stearate, Mn(ACAC) 3 , Mn(ACAC) 2 , Mn(AC) 2 , and TOP:Mn were used as the Mn raw material, and ZnMnO particles were synthesized at different ratios of the Mn raw material, 20%, 40%, 60%, and 80%, in the same manner as in Example 5. However, for TOP:Mn, synthesis was performed in two experimental examples with Mn ratios of 20% and 60%.
得られたＺｎＭｎＯ粒子のＴＥＭ像及びＸＲＤパターンを、図６及び図７に示す。図６において、ＴＥＭ像の下側にＴＥＭ像から算出した粒径を示す。また図７のＸＲＤの下側に、参考としてウルツ鉱型ＺｎＯのパターン（点線四角）を示すとともに、ロックソルト（ＲＳ）型のＭｎＯのピークが生じる領域を四角で囲って示す。 The TEM image and XRD pattern of the obtained ZnMnO particles are shown in Figures 6 and 7. In Figure 6, the particle size calculated from the TEM image is shown below the TEM image. Also, for reference, the pattern of wurtzite-type ZnO (dotted square) is shown below the XRD in Figure 7, and the area where the peak of rock salt (RS)-type MnO occurs is enclosed in a square.
これらの結果から、Ｍｎ（ＡＣＡＣ）３、Ｍｎ（ＡＣＡＣ）２、Ｍｎ（ＡＣ）２を用いた場合にはＭｎの割合が４０％まで、またＴＯＰ：Ｍｎを用いた場合にはＭｎの割合が２０％まで、安定して粒子径１０ｎｍ以下のウルツ鉱型ＺｎＭｎＯ粒子が得られることが確認された。また、ＸＲＤパターンから、Ｍｎの割合が異なるいずれの実験例でも、生成しているウルツ鉱型ＺｎＭｎＯ粒子には、原料の混合比とほぼ同じ割合でＭｎが取り込まれていることが確認された。ただし、Ｍｎの割合が６０％以上の場合には、ＭｎＯの安定な結晶系であるロックソルト型の粒子も生成し、添加量に対するウルツ鉱型粒子生成量が低下していた。 From these results, it was confirmed that wurtzite ZnMnO particles with a particle size of 10 nm or less could be obtained stably when the Mn ratio was up to 40% when Mn(ACAC) 3 , Mn(ACAC) 2 , or Mn(AC) 2 was used, and when the Mn ratio was up to 20% when TOP:Mn was used. Furthermore, from the XRD patterns, it was confirmed that in all experimental examples with different Mn ratios, Mn was incorporated in the wurtzite ZnMnO particles produced at approximately the same ratio as the raw material mixing ratio. However, when the Mn ratio was 60% or more, rock salt type particles, which is a stable crystal system of MnO, were also produced, and the amount of wurtzite particles produced relative to the amount added was reduced.
Ｍｎの添加量ごとのウルツ鉱型ナノ粒子の生成量を、ＸＲＤパターンのＲｉｅｔｖｅｌｄ解析によって算出した結果を、ステアリン酸マンガンを用いた実施例５の結果とともに図８に示す。図８の結果から、ステアリン酸マンガンを用いた場合に、Ｍｎ割合を最も高くすることができ、且つ他の結晶系の混入がないＺｎＭｎＯ粒子を得られることがわかる。 The amount of wurtzite nanoparticles produced for each amount of Mn added was calculated by Rietveld analysis of the XRD pattern, and the results are shown in Figure 8 along with the results of Example 5, in which manganese stearate was used. The results in Figure 8 show that when manganese stearate is used, the Mn ratio can be maximized and ZnMnO particles without contamination with other crystal systems can be obtained.
以上、実施例５、６では、第四周期の元素の代表例としてＭｎをドープした亜鉛含有ナノ粒子の製造例と、それに好適なＭｎ材料の検討結果を示したが、これら実施例５、６の結果から、Ｚｎと同じ第四周期の元素Ｍｎについても、ＺｎＯの結晶構造内に取り込むことが十分可能であることが確認された。ＭｎやＦｅ、Ｃｏ、Ｎｉなどの元素は、ＺｎＯの磁気的な性質を変化させる元素であり、磁気的用途での適用範囲を広げることが期待される。 Above, in Examples 5 and 6, we have shown examples of manufacturing zinc-containing nanoparticles doped with Mn as a representative example of an element in the fourth period, and the results of examining suitable Mn materials for such nanoparticles. The results of Examples 5 and 6 confirmed that Mn, an element in the fourth period like Zn, can be fully incorporated into the crystal structure of ZnO. Elements such as Mn, Fe, Co, and Ni change the magnetic properties of ZnO, and are expected to expand the range of applications in magnetic applications.
＜実施例７＞
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Ｓの材料として１，３－ジブチルチオ尿素を０．２ｍｍｏｌ（１０％）用いた。また第一の添加剤としてエチレングリコール（ＥＧ） １．０ｍｍｏｌ、サイズ制御剤としてＴＯＰ １．２ｍｍｏｌ及び硫黄 ０．６ｍｍｏｌを用いた。
Example 7
10 mL of oleylamine was used as a solvent, 2.0 mmol of Zn(ACAC) 2 was used as a zinc material, and 0.2 mmol (10%) of 1,3-dibutylthiourea was used as a sulfur S material. 1.0 mmol of ethylene glycol (EG) was used as a first additive, and 1.2 mmol of TOP and 0.6 mmol of sulfur were used as size control agents.
容器に材料充填後、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、Ｎ２雰囲気下で２５０℃に２時間保持し、さらに昇温してＮ２雰囲気下で３００℃に１５分保持して合成を行った。 After filling the container with the material, the material was held at 70°C for 30 minutes in a nitrogen atmosphere, and then heated and held at 130°C for 2 hours in 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 material was held at 250°C for 2 hours in a N2 atmosphere at a temperature rise rate of 50°C/5 minutes, and further heated and held at 300°C for 15 minutes in 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、ＺｎＯＳ粒子を得た。 After cooling, 5 mL of hexane was added to the reaction solution, which was then stirred and 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 ZnOS particles.
得られたＺｎＯＳ粒子（Ｓ：１０％）のＴＥＭ像を図９に示す。これらＴＥＭ像から測定した粒子径は３～４ｎｍであった。またＸＲＤ及びＸＲＦ測定結果から、Ｓが材料の混合比通りに結晶構造内に取り込まれていることを確認した。 Figure 9 shows TEM images of the obtained ZnOS particles (S: 10%). The particle diameter measured from these TEM images was 3 to 4 nm. Furthermore, the results of XRD and XRF measurements confirmed that S was incorporated into the crystal structure in accordance with the mixture ratio of the materials.
＜実施例８＞
硫黄Ｓ材料の代わりに、セレンＳｅ材料を用いて、実施例６と同様の方法で、ＺｎＯＳｅ粒子を合成した。Ｓｅ材料として、Ｓｅ（Ｃ（ＮＨ）２）２を０．１ｍｍｏｌ（５％）又は０．２ｍｍｏｌ（１０％）を用いた。
Example 8
ZnOSe particles were synthesized using selenium (Se) material instead of sulfur (S) material in the same manner as in Example 6. As the Se material, 0.1 mmol (5%) or 0.2 mmol (10%) of Se(C(NH) 2 ) 2 was used.
得られたＺｎＯＳｅ粒子のＴＥＭ像を図１０に示す。図１０左側が添加量５％の場合、右側が１０％の場合である。これらＴＥＭ像から粒子径が１０ｎｍ以下であることが確認された。またＸＲＤ及びＸＲＦ測定結果から、Ｓｅが材料の混合比通りに結晶構造内に取り込まれていることを確認した。 TEM images of the obtained ZnOSe particles are shown in Figure 10. The left side of Figure 10 shows the case where the additive amount was 5%, and the right side shows the case where the additive amount was 10%. These TEM images confirmed that the particle diameter was 10 nm or less. Furthermore, the results of XRD and XRF measurements confirmed that Se was incorporated into the crystal structure in accordance with the mixing ratio of the materials.
実施例７、８の結果から、粒子サイズが１０ｎｍ以下となる成長条件で反応させることにより、ＺｎＯの結晶構造内の酸素についてもＩＩ族の元素で置換された結晶粒子が合成できることが確認された。ＺｎＯの酸素をＳ又はＳｅで置換することにより、エネルギーギャップを紫外域から可視領域に変化させることができ、半導体としての利用範囲を広げることができる。 The results of Examples 7 and 8 confirmed that by carrying out the reaction under growth conditions that result in a particle size of 10 nm or less, it is possible to synthesize crystal particles in which the oxygen in the ZnO crystal structure is replaced with a Group II element. By replacing the oxygen in ZnO with S or Se, it is possible to change the energy gap from the ultraviolet range to the visible range, expanding the range of use as a semiconductor.
＜実施例９＞
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、Ｇａ材料としてＧａ（ＡＣＡＣ）３ ０．１ｍｍｏｌ（５％）、硫黄Ｓの材料として１，３－ジブチルチオ尿素 ０．２ｍｍｏｌ（１０％）を用いた。また第一の添加剤としてエチレングリコール（ＥＧ） １．０ｍｍｏｌ、サイズ制御剤としてＴＯＰ １．２ｍｍｏｌ及び硫黄 ０．６ｍｍｏｌを用いた。
<Example 9>
10 mL of oleylamine was used as a solvent, 2.0 mmol of Zn(ACAC) 2 was used as a zinc material, 0.1 mmol (5%) of Ga(ACAC) 3 was used as a Ga material, and 0.2 mmol (10%) of 1,3-dibutylthiourea was used as a sulfur S material. 1.0 mmol of ethylene glycol (EG) was used as a first additive, and 1.2 mmol of TOP and 0.6 mmol of sulfur were used as size control agents.
容器に材料充填後、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℃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、Ｎ２雰囲気下で２５０℃に２時間保持し、さらに昇温してＮ２雰囲気下で３００℃に１５分保持して合成を行った。 After filling the container with the material, the material was held at 70°C for 30 minutes in a nitrogen atmosphere, and then heated and held at 130°C for 2 hours in 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 material was held at 250°C for 2 hours in a N2 atmosphere at a temperature rise rate of 50°C/5 minutes, and further heated and held at 300°C for 15 minutes in 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、ＧａＺｎＯＳ粒子（４元系結晶粒子）を得た。 After cooling, 5 mL of hexane was added to the reaction solution, which was then stirred and 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 GaZnOS particles (quaternary crystal particles).
得られたＧａＺｎＯＳ粒子（Ｇａ：５％、Ｓ：１０％）のＴＥＭ像を図１１（ａ）に示す。このＴＥＭ像から測定した粒子径は３～４ｎｍであった。またＸＲＤ及びＸＲＦ測定結果から、Ｇａ及びＳが材料の混合比通りに結晶構造内に取り込まれていることを確認した。 Figure 11(a) shows a TEM image of the obtained GaZnOS particles (Ga: 5%, S: 10%). The particle diameter measured from this TEM image was 3 to 4 nm. Furthermore, the results of XRD and XRF measurements confirmed that Ga and S were incorporated into the crystal structure in the correct mixture ratio of the materials.
＜実施例１０＞
Ｇａ材料の代わりに、Ｉｎ材料としてＩｎＩ３を用いた以外は実施例９と同様に、ＩｎＺｎＯＳ粒子（４元系結晶粒子）を得た。得られたＩｎＺｎＯＳ粒子（Ｉｎ：５％、Ｓ：１０％）のＴＥＭ像を図１１（ｂ）に示す。このＴＥＭ像から測定した粒子径は５～６ｎｍであった。またＸＲＤ及びＸＲＦ測定結果から、Ｉｎ及びＳが材料の混合比通りに結晶構造内に取り込まれていることを確認した。
Example 10
InZnOS particles (quaternary crystal particles) were obtained in the same manner as in Example 9, except that InI3 was used as the In material instead of the Ga material. The TEM image of the obtained InZnOS particles (In: 5%, S: 10%) is shown in FIG. 11(b). The particle diameter measured from this TEM image was 5 to 6 nm. Furthermore, from the results of XRD and XRF measurements, it was confirmed that In and S were incorporated into the crystal structure according to the mixing ratio of the materials.
＜実施例１１＞
亜鉛材料としてＺｎ（ＡＣＡＣ）２を（２－ｘ）ｍｍｏｌ（但し、ｘは０．４、０．８、１．２、１．６のいずれか）を用い、Ｍｎ材料としてＭｎ（ＡＣＡＣ）３、Ｍｎ（ＡＣＡＣ）２、Ｍｎ（ＡＣ）２、ステアリン酸マンガン（ｓｔ－Ｍｎ）、及びＴＯＰ：Ｍｎのいずれかをｘｍｍｏｌ用いた以外は、実施例９と同様にして、ＭｎＺｎＯＳ粒子（４元系結晶粒子）を合成した。但し、ＴＯＰ：Ｍｎについては、Ｍｎの割合がｘ＝０．４（２０％）、１．２（６０％）の２つの実験例で合成を行った。
Example 11
MnZnOS particles (quaternary crystal particles) were synthesized in the same manner as in Example 9, except that (2-x) mmol of Zn(ACAC) 2 (where x is any one of 0.4, 0.8, 1.2, and 1.6 ) was used as the zinc material, and x mmol of any one of Mn(ACAC) 3 , Mn(ACAC) 2 , Mn(AC)2, manganese stearate (st-Mn), and TOP:Mn was used as the Mn material. However, for TOP:Mn, synthesis was performed in two experimental examples where the Mn ratio was x=0.4 (20%) and 1.2 (60%).
得られたＭｎＺｎＯＳ粒子のＴＥＭ像及びＸＲＤパターンを、図１２及び図１３に示す。図１２において、ＴＥＭ像の下側にＴＥＭ像から算出した粒径を示し、ウルツ鉱型の粒子が概ね単一相で得られたＴＥＭ像を四角で囲って示している。また図１３のＸＲＤの下側に、参考としてウルツ鉱型ＺｎＯのパターン（点線四角）を示すとともに、ロックソルト（ＲＳ）型のＭｎＯのピークが生じる領域を四角で囲って示す。 The TEM image and XRD pattern of the obtained MnZnOS particles are shown in Figures 12 and 13. In Figure 12, the particle size calculated from the TEM image is shown below the TEM image, and the TEM image in which the wurtzite type particles are obtained in a roughly single phase is shown enclosed in a square. Also, below the XRD in Figure 13, the wurtzite type ZnO pattern (dotted square) is shown for reference, and the region where the peak of rock salt (RS) type MnO occurs is enclosed in a square.
図１２及び図１３に示す結果からわかるように、いずれのＭｎ材料を用いても、Ｍｎの割合を２０％とした場合には、ロックソルトのＸＲＤピークは観察されず、概ね単一相のウルツ鉱型の１０ｎｍ未満のナノ粒子が得られた。特にＭｎ材料としてステアリン酸マンガン（ｓｔ－Ｍｎ）を用いた場合には、Ｍｎの割合を６０％にしても、他の結晶系の粒子の混入が全くなく、均一な結晶構造のウルツ鉱型ナノ粒子が生成していることが確認された。またＸＲＦ測定により算出したナノ粒子におけるＭｎの割合（Ｚｎ＋Ｍｎに対する％）は、Ｍｎの添加量を６０％としたときに６０．９％であり、ほぼ材料の混合比通りに結晶構造内に取り込まれていることを確認した。 As can be seen from the results shown in Figures 12 and 13, no rock salt XRD peak was observed when the Mn ratio was 20%, regardless of which Mn material was used, and single-phase wurtzite nanoparticles less than 10 nm were obtained. In particular, when manganese stearate (st-Mn) was used as the Mn material, it was confirmed that even when the Mn ratio was 60%, there was no contamination with particles of other crystal systems and wurtzite nanoparticles with a uniform crystal structure were produced. In addition, the Mn ratio in the nanoparticles calculated by XRF measurement (% relative to Zn + Mn) was 60.9% when the amount of Mn added was 60%, confirming that it was incorporated into the crystal structure almost according to the mixing ratio of the materials.
さらに、ＸＲＤパターンのＲｉｅｔｖｅｌｄ解析により算出したウルツ鉱型ナノ粒子（ＭｎＺｎＯＳ）の生成量を、各Ｍｎ材料について、Ｍｎの割合毎に示すグラフを図１４に示す。図１４の結果からも、Ｍｎ原料として、ステアリン酸マンガンを用いたときに、ウルツ鉱型の結晶系を保ちながらＭｎのドープ量を６０％以上まで高められることがわかる。 Furthermore, Figure 14 shows a graph showing the amount of wurtzite nanoparticles (MnZnOS) produced for each Mn material by Mn ratio, calculated by Rietveld analysis of the XRD pattern. The results in Figure 14 also show that when manganese stearate is used as the Mn raw material, the Mn doping amount can be increased to 60% or more while maintaining the wurtzite crystal system.
実施例９～１１の結果から、ＺｎＯのＺｎ及びＯの一部がそれぞれ異なる元素で置き換わった４元系の結晶についても、２種類の添加剤を用いるとともに成長条件を制御することで、混合割合で結晶中にＺｎ及びＯ以外の元素が導入された結晶粒子が得られること、また平均粒子径が１０ｎｍ未満の極めてサイズの小さいナノ粒子が得られることが確認された。このような４元系の結晶は、上述した二元系或いは三元系のナノ粒子の用途に加え、導電材料や蛍光体としても適用することができる。 From the results of Examples 9 to 11, it was confirmed that, even for quaternary crystals in which some of the Zn and O in ZnO are replaced with different elements, by using two types of additives and controlling the growth conditions, it is possible to obtain crystal particles in which elements other than Zn and O are introduced into the crystals in a mixed ratio, and to obtain extremely small nanoparticles with an average particle size of less than 10 nm. In addition to the applications of the binary or ternary nanoparticles described above, such quaternary crystals can also be used as conductive materials and phosphors.
また実施例５、６及び１１の結果から、ドープ元素がＭｎの場合、原料化合物として配位系材料、特にステアリン酸マンガンを用いることで、均一なウルツ鉱型の結晶構造を保ちながら、Ｍｎドープ量を大幅に増加することができることが確認された。 In addition, the results of Examples 5, 6, and 11 confirmed that when the doping element is Mn, the amount of Mn doping can be significantly increased while maintaining a uniform wurtzite crystal structure by using a coordination material, particularly manganese stearate, as the raw material compound.
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 (10)
前記亜鉛を含む化合物を不活性雰囲気で１００℃以下の温度で１時間以下の時間保持したのち昇温し、大気圧の１／１００以下の減圧雰囲気下で２００℃以下の温度で反応を進行させ、粒子結晶の核を生成する第一のステップと、
不活性雰囲気下で第一のステップの反応温度より高い２００℃以上で且つ溶媒の沸点以下の温度で１～２時間保持し、亜鉛含有ナノ粒子を生成する第二のステップと、を含み、
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、反応中に前記亜鉛含有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・スルフィドを添加することを特徴とする亜鉛含有ナノ粒子の合成方法。 A method for synthesizing zinc-containing nanoparticles having a wurtzite crystal structure, comprising thermally decomposing at least one of zinc-containing compounds selected from zinc acetate (Zn(AC) 2 ), zinc stearate (ST-Zn), and zinc acetylacetonate (Zn(ACAC) 2 ) in a solvent, the method comprising the steps of:
a first step of holding the zinc-containing compound in an inert atmosphere at a temperature of 100° C. or less for one hour or less, and then raising the temperature to proceed with a reaction at a temperature of 200° C. or less under a reduced pressure atmosphere of 1/100 or less of atmospheric pressure to generate nuclei of particle crystals;
a second step of maintaining the temperature at 200° C. or higher, which is higher than the reaction temperature of the first step, and lower than the boiling point of the solvent, for 1 to 2 hours under an inert atmosphere to produce zinc-containing nanoparticles;
A method for synthesizing zinc-containing nanoparticles, comprising adding to a reaction system 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 zinc-containing nanoparticles during the reaction and suppresses the particle size.
前記第二のステップを大気圧下で行うことを特徴とする亜鉛含有ナノ粒子の合成方法。 2. A method for synthesizing zinc-containing nanoparticles according to claim 1, comprising:
The method for synthesizing zinc-containing nanoparticles, characterized in that the second step is carried out under atmospheric pressure.
前記反応系に、亜鉛を含む化合物及び亜鉛以外の元素Ｍを含む化合物を加えて反応を行い、酸化亜鉛の結晶格子における亜鉛及び／又は酸素の一部が元素Ｍで置換したＭドープ酸化亜鉛ナノ粒子を合成することを特徴とする亜鉛含有ナノ粒子の合成方法。 A method for synthesizing zinc-containing nanoparticles according to claim 1 or 2, comprising the steps of:
A method for synthesizing zinc-containing nanoparticles, comprising adding a compound containing zinc and a compound containing an element M other than zinc to the reaction system and carrying out a reaction to synthesize M-doped zinc oxide nanoparticles in which part of the zinc and/or oxygen in the crystal lattice of zinc oxide is replaced with the element M.
元素Ｍは、Ｓ、Ｓｅ、Ｇａ、Ｉｎ、Ｃｕ、Ｆｅ、Ｎｉ、Ｃｏ、Ｍｎ、Ｍｇから選ばれる１種以上であることを特徴とする亜鉛含有ナノ粒子の合成方法。 4. A method for synthesizing zinc-containing nanoparticles according to claim 3, comprising the steps of:
1. A method for synthesizing zinc-containing nanoparticles, wherein element M is one or more selected from the group consisting of S, Se, Ga, In, Cu, Fe, Ni, Co, Mn, and Mg.
前記第一の添加剤は、溶媒に対し２容量％以下添加されることを特徴とする亜鉛含有ナノ粒子の合成方法。 A method for synthesizing zinc-containing nanoparticles according to any one of claims 1 to 4, comprising the steps of:
The method for synthesizing zinc-containing nanoparticles, wherein the first additive is added in an amount of 2% by volume or less relative to the solvent.
前記第二の添加剤は、前記亜鉛を含む化合物に対しモル比で０．３～１．０添加することを特徴とする亜鉛含有ナノ粒子の合成方法。 A method for synthesizing zinc-containing nanoparticles according to any one of claims 1 to 5, comprising the steps of:
The method for synthesizing zinc-containing nanoparticles is characterized in that the second additive is added in a molar ratio of 0.3 to 1.0 relative to the zinc-containing compound.
前記元素Ｍを含む化合物が、前記粒子結晶の核の周りに配位する配位系材料であることを特徴とする亜鉛含有ナノ粒子の合成方法。 4. A method for synthesizing zinc-containing nanoparticles according to claim 3, comprising the steps of:
A method for synthesizing zinc-containing nanoparticles, characterized in that the compound containing the element M is a coordination system material that coordinates around the core of the particle crystal.
前記配位系材料は、前記亜鉛を含む化合物よりも分解温度が高く、前記第一のステップの反応温度で分解しないことを特徴とする亜鉛含有ナノ粒子の合成方法。 8. A method for synthesizing zinc-containing nanoparticles according to claim 7, comprising the steps of:
A method for synthesizing zinc-containing nanoparticles, characterized in that the coordination material has a higher decomposition temperature than the zinc-containing compound and does not decompose at the reaction temperature of the first step.
前記配位系材料がステアリン酸塩であることを特徴とする亜鉛含有ナノ粒子の合成方法。 8. A method for synthesizing zinc-containing nanoparticles according to claim 7, comprising the steps of:
A method for synthesizing zinc-containing nanoparticles, characterized in that the coordination material is a stearate.
元素Ｍは、Mｎであって、前記配位系材料がステアリン酸マンガンであることを特徴とする亜鉛含有ナノ粒子の合成方法。 10. A method for synthesizing zinc-containing nanoparticles according to claim 9, comprising the steps of:
11. A method for synthesizing zinc-containing nanoparticles, wherein the element M is Mn and the coordination material is manganese stearate.
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