JP2012219194A - Nano particle group and method for producing the same - Google Patents
Nano particle group and method for producing the same Download PDFInfo
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本発明は、吸収した光とは異なる波長の光を発生する波長変換ナノ粒子が凝集してなるナノ粒子群、及び、その製造方法に関する。 The present invention relates to a group of nanoparticles formed by aggregation of wavelength conversion nanoparticles that generate light having a wavelength different from that of absorbed light, and a method for producing the same.
吸収した光とは異なる波長の光を発生する波長変換ナノ粒子は、ＬＥＤの表面に配設されて当該ＬＥＤの発光色を変更したり、太陽電池の表面に設けられて入射光の波長を変換することにより当該太陽電池の効率を向上させたりと、種々の用途に応用されている。 Wavelength-converting nanoparticles that generate light with a wavelength different from the absorbed light are placed on the surface of the LED to change the emission color of the LED, or provided on the surface of the solar cell to convert the wavelength of incident light This improves the efficiency of the solar cell and is applied to various applications.
従来、このような波長変換ナノ粒子としては、ＣｄＳを含むものが提案されているが、波長変換ナノ粒子の廃棄処理を容易にするために、ＺｎＳｅ等を使用して波長変換ナノ粒子を製造することが提案されている（例えば、非特許文献１参照）。 Conventionally, as such wavelength conversion nanoparticles, those containing CdS have been proposed. In order to facilitate disposal of the wavelength conversion nanoparticles, the wavelength conversion nanoparticles are manufactured using ZnSe or the like. (For example, refer nonpatent literature 1).
非特許文献１に記載の製造方法では、有機溶媒中で波長変換ナノ粒子を製造しているが、溶媒の廃棄処理を容易にするために、水系溶媒中で波長変換ナノ粒子を製造することも提案されている（例えば、非特許文献２，３参照）。 In the manufacturing method described in Non-Patent Document 1, wavelength conversion nanoparticles are manufactured in an organic solvent. However, in order to facilitate disposal of the solvent, the wavelength conversion nanoparticles may be manufactured in an aqueous solvent. It has been proposed (see, for example, Non-Patent Documents 2 and 3).
ところが、前記各非特許文献では、波長変換ナノ粒子の製造後の特性変化については何ら検証されていない。また、従来は、製造された波長変換ナノ粒子ができるだけ安定して溶液中に分散するように研究がなされたり、製造後の波長変換ナノ粒子が凝集等によって特性変化する前にできるだけ早く使用することに努力が払われたりしていた。 However, in each of the non-patent documents, any change in characteristics after the production of the wavelength conversion nanoparticles is not verified. Also, in the past, research has been done to disperse the produced wavelength conversion nanoparticles in the solution as stably as possible, or use them as soon as possible before the wavelength conversion nanoparticles after production change their properties due to aggregation, etc. Efforts have been made.
これに対して、本願出願人は、波長変換ナノ粒子がある程度凝集した方が、却って発光強度が向上することを発見した。そこで、本発明は、波長変換ナノ粒子が適度に凝集して良好な発光強度を有するナノ粒子群、及びその製造方法を提供することを目的としてなされた。 In contrast, the applicant of the present application has found that the light emission intensity is improved when the wavelength conversion nanoparticles are aggregated to some extent. Then, this invention was made | formed for the purpose of providing the nanoparticle group which the wavelength conversion nanoparticle aggregates moderately, and has favorable light emission intensity, and its manufacturing method.
前記目的を達するためになされた本発明は、粒子経が１０ｎｍ以下で、吸収した光とは異なる波長の光を発生する複数の波長変換ナノ粒子によって構成され、前記各波長変換ナノ粒子は、各々の周囲に配位子が配位したことによって互いに一体化することなく、直径２０〜１００ｎｍの大きさに凝集したことを特徴とするナノ粒子群を要旨としている。 The present invention made to achieve the above-mentioned object is composed of a plurality of wavelength-converting nanoparticles having a particle diameter of 10 nm or less and generating light having a wavelength different from the absorbed light. The gist of the present invention is a group of nanoparticles characterized in that they are aggregated to a size of 20 to 100 nm in diameter without being integrated with each other due to coordination of ligands around.
このように構成された本発明のナノ粒子群は、各波長変換ナノ粒子が分散した状態よりも、良好な発光強度を呈した。この理由は、次のように推察することができる。すなわち、粒子経が１０ｎｍ以下の波長変換ナノ粒子が、一体化することなく直径２０〜１００ｎｍの大きさに凝集しているので、各波長変換ナノ粒子が発生した光が重なって、良好な発光強度が得られる。また、各波長変換ナノ粒子は吸収した光とは異なる波長の光を発生するので、各波長変換ナノ粒子が互いに発生した光を吸収し合うこともない。 The nanoparticle group of the present invention configured as described above exhibited better emission intensity than the state where each wavelength conversion nanoparticle was dispersed. The reason can be inferred as follows. That is, since the wavelength conversion nanoparticles having a particle size of 10 nm or less are aggregated to a diameter of 20 to 100 nm without being integrated, the light generated by each wavelength conversion nanoparticle is overlapped, resulting in good emission intensity. Is obtained. In addition, since each wavelength conversion nanoparticle generates light having a wavelength different from that of the absorbed light, each wavelength conversion nanoparticle does not absorb light generated by each other.
更に、多数の波長変換ナノ粒子が凝集によって一体化してしまうと、吸収する光の波長が長波長化するなどの特性変化が生じるが、本発明では、各波長変換ナノ粒子の周囲に配位子が配位することによってそのような一体化を抑制している。従って、前記凝集によって、特性変化を生じることなく発光強度を向上させることができる。 Furthermore, when a large number of wavelength conversion nanoparticles are integrated by aggregation, a characteristic change such as a longer wavelength of light to be absorbed occurs. In the present invention, a ligand is formed around each wavelength conversion nanoparticle. Coordination suppresses such integration. Therefore, the light emission intensity can be improved by the aggregation without causing a characteristic change.
なお、本発明において、前記波長変換ナノ粒子は、Ｚｎ，Ｓｅ，Ｓ，Ｃｄ，またはＴｅの少なくともいずれかを含んでもよい。その場合、前記発光強度を一層良好に向上させることができる。 In the present invention, the wavelength conversion nanoparticles may include at least one of Zn, Se, S, Cd, and Te. In that case, the emission intensity can be further improved.
また、前記波長変換ナノ粒子は、Ｍｎ，Ｅｒ，Ｅｕ，Ｙｂの少なくともいずれかによってドープされてもよい。その場合、各波長変換ナノ粒子は、一層良好に、吸収した光とは異なる波長の光を発生する。 The wavelength conversion nanoparticles may be doped with at least one of Mn, Er, Eu, and Yb. In that case, each wavelength converting nanoparticle generates light of a wavelength different from the absorbed light even better.
また、前記配位子が親水性の配位子であってもよい。その場合、水系溶媒中で前記波長変換ナノ粒子を生成して凝集させることが容易にでき、ナノ粒子群製造後の溶媒の廃棄も一層容易になる。 Further, the ligand may be a hydrophilic ligand. In this case, the wavelength conversion nanoparticles can be easily generated and aggregated in an aqueous solvent, and the disposal of the solvent after the production of the nanoparticle group is further facilitated.
そして、その場合、前記配位子は、親水性官能基としてのＯＨ基を有するものであってもよい。ＯＨ基は良好な親水性を呈するので、前述のように水系溶媒中で前記波長変換ナノ粒子を生成して凝集させることが一層容易にできる。なお、ここでいうＯＨ基は、カルボキシル基に属するものであってもよい。 In that case, the ligand may have an OH group as a hydrophilic functional group. Since the OH group exhibits good hydrophilicity, the wavelength conversion nanoparticles can be more easily generated and aggregated in an aqueous solvent as described above. The OH group referred to here may belong to a carboxyl group.
また、前記目的を達するためになされた本発明は、Ｍｎを提供するイオン源と、無機ナノ粒子を構成する原子を提供するイオン源と、親水性の配位子と、を水系溶媒中で混合し、得られた溶液のｐＨ調整を行う混合工程と、前記ｐＨ調整後の前記溶液を加熱して粒子経が１０ｎｍ以下の波長変換ナノ粒子を生成する加熱工程と、前記生成された波長変換ナノ粒子を含む溶液を放置することによって、その波長変換ナノ粒子を直径２０〜１００ｎｍの大きさに凝集させた後、基材に塗布する凝集工程と、を備えたことを特徴とするナノ粒子群の製造方法を要旨としている。 Further, the present invention made to achieve the above object is to mix an ion source that provides Mn, an ion source that provides atoms constituting the inorganic nanoparticles, and a hydrophilic ligand in an aqueous solvent. A mixing step for adjusting the pH of the obtained solution, a heating step for heating the solution after the pH adjustment to generate wavelength conversion nanoparticles having a particle size of 10 nm or less, and the generated wavelength conversion nano An aggregating step of aggregating the wavelength-converting nanoparticles to a size of 20 to 100 nm by allowing the solution containing the particles to stand, and then applying the agglomeration step to a substrate; The manufacturing method is the gist.
本発明の方法では、先ず、混合工程にて、Ｍｎを提供するイオン源と、無機ナノ粒子を構成する原子を提供するイオン源と、親水性の配位子と、を水系溶媒中で混合し、得られた溶液のｐＨ調整する。続いて、加熱工程にて、前記ｐＨ調整後の前記溶液を加熱して粒子経が１０ｎｍ以下の波長変換ナノ粒子を生成する。更に、凝集工程にて、前記生成された波長変換ナノ粒子を含む溶液を放置することによって、その波長変換ナノ粒子を直径２０〜１００ｎｍの大きさに凝集させた後、基材に塗布する。 In the method of the present invention, first, in the mixing step, an ion source that provides Mn, an ion source that provides atoms constituting the inorganic nanoparticles, and a hydrophilic ligand are mixed in an aqueous solvent. The pH of the obtained solution is adjusted. Subsequently, in the heating step, the pH-adjusted solution is heated to produce wavelength conversion nanoparticles having a particle size of 10 nm or less. Furthermore, in the aggregation step, the wavelength conversion nanoparticles are agglomerated to a size of 20 to 100 nm by leaving the solution containing the generated wavelength conversion nanoparticles, and then applied to the substrate.
このため、混合工程及び加熱工程により、粒子経が１０ｎｍ以下でＭｎによるドープがなされた波長変換ナノ粒子を、水系溶媒中で良好に製造することができる。更に、凝集工程において、凝集によって得られたナノ粒子群を基材に塗布することにより、そのナノ粒子群は直径２０〜１００ｎｍの大きさを維持することができる。従って、本発明の方法では、Ｍｎによるドープがなされた波長変換ナノ粒子からなる前記発明のナノ粒子群を、容易に製造することができる。 For this reason, the wavelength conversion nanoparticles with a particle size of 10 nm or less and doped with Mn can be satisfactorily produced in an aqueous solvent by the mixing step and the heating step. Furthermore, in the aggregation step, by applying the nanoparticle group obtained by the aggregation to the base material, the nanoparticle group can maintain a size of 20 to 100 nm in diameter. Therefore, in the method of the present invention, the nanoparticle group of the present invention composed of wavelength conversion nanoparticles doped with Mn can be easily produced.
なお、本発明の方法において、前記無機ナノ粒子を構成する原子としてＺｎを含んでもよい。その場合、本発明の方法よって製造されたナノ粒子群の発光強度を、一層良好に向上させることができる。 In the method of the present invention, Zn may be included as an atom constituting the inorganic nanoparticles. In that case, the emission intensity of the nanoparticle group produced by the method of the present invention can be further improved.
そして、その場合、前記配位子がＮ−アセチル−Ｌ−システインであり、前記混合工程では、Ｍｎを提供する前記イオン源とＮ−アセチル−Ｌ−システインとを含む溶液と、Ｚｎを提供する前記イオン源とＮ−アセチル−Ｌ−システインとを含む溶液とを、混合してもよい。その場合、前記ナノ粒子群を水系溶媒中で一層良好に製造することができる。 In that case, the ligand is N-acetyl-L-cysteine, and in the mixing step, a solution containing the ion source providing Mn and N-acetyl-L-cysteine, and Zn are provided. The ion source and a solution containing N-acetyl-L-cysteine may be mixed. In that case, the said nanoparticle group can be manufactured more favorably in an aqueous medium.
また、本発明の方法において、前記無機ナノ粒子を構成する原子としてＳｅを含んでもよい。その場合、本発明の方法よって製造されたナノ粒子群の発光強度を、一層良好に向上させることができる。 In the method of the present invention, Se may be included as an atom constituting the inorganic nanoparticles. In that case, the emission intensity of the nanoparticle group produced by the method of the present invention can be further improved.
また、本発明の方法において、前記加熱工程における加熱温度が１５０℃〜２５０℃であってもよい。本願出願人は、水系溶媒中で波長変換ナノ粒子を製造する場合、１５０℃〜２５０℃に加熱して製造すると、良好な発光強度を有する波長変換ナノ粒子が得られることを発見した。これは、高温でナノ粒子を生成することにより、きれいな結晶ができるためと考えられる。 In the method of the present invention, the heating temperature in the heating step may be 150 ° C. to 250 ° C. The applicant of the present application has discovered that when wavelength-converted nanoparticles are produced in an aqueous solvent, wavelength-converted nanoparticles having good emission intensity can be obtained by heating to 150 ° C. to 250 ° C. This is thought to be because clean crystals can be formed by producing nanoparticles at a high temperature.
但し、２５０℃より高温に加熱すると、自己清浄化効果によってドープの効果が低減される傾向が生じる。すなわち、波長変換ナノ粒子では、無機ナノ粒子が吸収した例えば紫外領域の光のエネルギを、Ｍｎが可視領域の光に変換する。しかしながら、２５０℃より高温で結晶を製造した場合、無機ナノ粒子の結晶からＭｎが排除される傾向が生じるのである。また、逆に、１５０℃未満の温度で波長変換ナノ粒子した場合は、加熱の効果が十分に得られず、従来の方法で水系溶媒中で生成された波長変換ナノ粒子と余り発光強度の差が出ない。なお、このような、高温下での波長変換ナノ粒子の生成は、必要に応じて適宜の高圧下にて行われることはいうまでもない。 However, when heated to a temperature higher than 250 ° C., the dope effect tends to be reduced due to the self-cleaning effect. That is, in the wavelength conversion nanoparticles, Mn converts light energy in the ultraviolet region, for example, absorbed by the inorganic nanoparticles into light in the visible region. However, when the crystal is produced at a temperature higher than 250 ° C., there is a tendency that Mn is excluded from the crystal of the inorganic nanoparticles. On the other hand, when the wavelength conversion nanoparticles are formed at a temperature of less than 150 ° C., the effect of heating cannot be sufficiently obtained, and the difference in emission intensity from the wavelength conversion nanoparticles generated in an aqueous solvent by a conventional method is excessive. Does not come out. Needless to say, the generation of the wavelength conversion nanoparticles at a high temperature is performed under an appropriate high pressure as necessary.
従って、この場合、前述のように良好な発光強度を有する波長変換ナノ粒子によって前記ナノ粒子群を製造することができるので、得られるナノ粒子群の発光強度を一層良好に向上させることができる。 Therefore, in this case, as described above, the nanoparticle group can be produced with the wavelength conversion nanoparticles having good light emission intensity, so that the light emission intensity of the obtained nanoparticle group can be further improved.
また、本発明の方法において、前記無機ナノ粒子を構成する原子として、ＳとＳｅとを含み、前記混合工程は、前記無機ナノ粒子を構成するＳｅ以外の各原子を各々提供する前記各イオン源と、前記配位子と、を水系溶媒中で混合し、得られた溶液のｐＨ調整を行う第１混合工程と、前記無機ナノ粒子を構成するＳ以外の各原子を各々提供する前記各イオン源と、前記配位子と、を水系溶媒中で混合し、得られた溶液のｐＨ調整を行う第２混合工程と、前記第１混合工程で得られた前記ｐＨ調整後の溶液と、前記第２混合工程で得られた前記ｐＨ調整後の溶液とを混合する第３混合工程と、からなり、前記Ｍｎを提供するイオン源は、前記第１混合工程または前記第２混合工程で前記溶液に混合されてもよい。 In the method of the present invention, each ion source includes S and Se as atoms constituting the inorganic nanoparticles, and the mixing step provides each atom other than Se constituting the inorganic nanoparticles. A first mixing step in which the ligand is mixed in an aqueous solvent and the pH of the resulting solution is adjusted, and each ion that provides each atom other than S constituting the inorganic nanoparticles. A second mixing step of mixing the source and the ligand in an aqueous solvent and adjusting the pH of the resulting solution, the solution after the pH adjustment obtained in the first mixing step, And a third mixing step of mixing the pH-adjusted solution obtained in the second mixing step, wherein the ion source providing Mn is the solution in the first mixing step or the second mixing step. May be mixed.
無機ナノ粒子を構成する原子としてＳとＳｅとを含む場合、混晶からなる無機ナノ粒子が生成され、ＳとＳｅとの比率を適切に調整することで前記発光強度を極めて良好に向上させることができる。ところが、ＳとＳｅとでは、そのイオン源を反応系に追加する際に適切なｐＨが大きく異なる。 When S and Se are included as atoms constituting the inorganic nanoparticles, inorganic nanoparticles composed of mixed crystals are generated, and the emission intensity is improved extremely well by appropriately adjusting the ratio of S and Se. Can do. However, the appropriate pH differs greatly between S and Se when the ion source is added to the reaction system.
そこで、前述のように、第１混合工程にて、無機ナノ粒子を構成するＳｅ以外の各原子（Ｓも含む）を各々提供する前記各イオン源と前記配位子とを水系溶媒中で混合して得られた溶液のｐＨを調整し、第２混合工程にて、無機ナノ粒子を構成するＳ以外の各原子（Ｓｅも含む）を各々提供する前記各イオン源と前記配位子とを水系溶媒中で混合して得られた溶液のｐＨを調整し、それらのｐＨ調整後の溶液を第３混合工程で混合すればよい。なお、Ｍｎを提供するイオン源は、前記第１混合工程または前記第２混合工程で前記溶液に混合される。こうすることによって、前述のような混晶からなる波長変換ナノ粒子を良好に製造することができ、ひいては、その波長変換ナノ粒子を凝集させて得られるナノ粒子群の発光強度も一層良好に向上させることができる。 Therefore, as described above, in the first mixing step, each ion source that provides each atom (including S) other than Se constituting the inorganic nanoparticles and the ligand are mixed in an aqueous solvent. The pH of the resulting solution is adjusted, and in the second mixing step, each ion source that provides each atom (including Se) other than S constituting the inorganic nanoparticles and the ligand are provided. What is necessary is just to adjust the pH of the solution obtained by mixing in an aqueous solvent, and to mix the solution after those pH adjustments at a 3rd mixing process. The ion source that provides Mn is mixed with the solution in the first mixing step or the second mixing step. By doing so, it is possible to satisfactorily produce the wavelength conversion nanoparticles composed of the mixed crystals as described above. As a result, the emission intensity of the nanoparticle group obtained by aggregating the wavelength conversion nanoparticles is further improved. Can be made.
また、本発明の方法において、前記混合工程終了後の前記溶液はｐＨ９〜１１に調整されていてもよく、その場合、その溶液を加熱することによって、極めて良好な発光強度を有する波長変換ナノ粒子を製造することができる。従って、その波長変換ナノ粒子を凝集させて得られるナノ粒子群の発光強度も一層良好に向上させることができる。 In the method of the present invention, the solution after completion of the mixing step may be adjusted to pH 9 to 11, and in that case, the wavelength-converting nanoparticles having extremely good emission intensity by heating the solution. Can be manufactured. Therefore, the emission intensity of the nanoparticle group obtained by aggregating the wavelength conversion nanoparticles can be further improved.
次に、本発明の実施の形態を、図面と共に説明する。図１は、本発明が適用されたナノ粒子群の製造方法を表す説明図である。図１（Ａ）に示すように、本実施の形態では、先ず、Ｚｎイオン源（例えば、過塩素酸亜鉛）とＮ−アセチル−Ｌ−システイン（以下、ＮＡＣという）とを１：４．８のモル比で含む水溶液と、Ｍｎイオン源（例えば、過塩素酸マンガン）とＮＡＣとを１：１のモル比で含む水溶液とを混合した。なお、前者の水溶液と後者の水溶液とは１０：１の割合で混合し、混合後の水溶液全体に対するＭｎの濃度が２ｍｏｌ％となるようにした。 Next, embodiments of the present invention will be described with reference to the drawings. FIG. 1 is an explanatory diagram showing a method for producing a group of nanoparticles to which the present invention is applied. As shown in FIG. 1A, in this embodiment, first, a Zn ion source (for example, zinc perchlorate) and N-acetyl-L-cysteine (hereinafter referred to as NAC) are 1: 4.8. And an aqueous solution containing a Mn ion source (for example, manganese perchlorate) and NAC at a molar ratio of 1: 1 were mixed. The former aqueous solution and the latter aqueous solution were mixed at a ratio of 10: 1 so that the Mn concentration with respect to the entire aqueous solution after mixing was 2 mol%.
続いて、その水溶液にＮａＯＨを添加することによってｐＨ８．５に調整し、更に、図１（Ｂ）に示すように、Ｓｅイオン源（例えばＮａＨＳｅ）を１．２ｍｍｏｌ添加した。なお、このときのＺｎ：Ｓｅのモル比は（１：０．６）である。また、この水溶液（ＺｎＭｎＳｅのＰｒｅｃｕｒｓｏｒ）では、金属原子にＮＡＣのＳＨ基が配位し、ＮＡＣのカルボキシル基が水系溶媒への溶解を促進しているものと推察される。その水溶液に更にＮａＯＨを添加することによって、図１（Ｃ）に示すようにｐＨ１０．５に調整した後、高圧下（例えば６気圧）で２００℃に加熱することによって、波長変換ナノ粒子（ＺｎＳｅ：Ｍｎ）を製造した。なお、加熱時間は２０分とした。 Subsequently, pH was adjusted to 8.5 by adding NaOH to the aqueous solution, and 1.2 mmol of a Se ion source (for example, NaHSe) was further added as shown in FIG. In this case, the molar ratio of Zn: Se is (1: 0.6). Further, in this aqueous solution (Precursor of ZnMnSe), it is presumed that the SH group of NAC is coordinated to the metal atom, and the carboxyl group of NAC promotes dissolution in the aqueous solvent. By further adding NaOH to the aqueous solution, the pH is adjusted to 10.5 as shown in FIG. 1 (C), and then heated to 200 ° C. under high pressure (for example, 6 atm), thereby converting the wavelength conversion nanoparticles (ZnSe). : Mn). The heating time was 20 minutes.
次に、図２は、前述のように製造された波長変換ナノ粒子を、前記溶液中で放置した場合の輝度変化を表すグラフである。また、図２には、２０℃，２５℃，７０℃の各種温度で保管した場合について、輝度変化を示した。なお、輝度の測定は、波長変換ナノ粒子が凝集して出来たナノ粒子群が沈殿した時点で終了した。 Next, FIG. 2 is a graph showing the change in luminance when the wavelength conversion nanoparticles produced as described above are left in the solution. Further, FIG. 2 shows changes in luminance when stored at various temperatures of 20 ° C., 25 ° C., and 70 ° C. In addition, the measurement of luminance was completed when the nanoparticle group formed by aggregation of the wavelength conversion nanoparticles was precipitated.
図２に示すように、いずれの温度でも、放置によって発光強度は大幅に向上した。また、２０℃または２５℃で保管した例では、太い矢印で示す時点で白濁化した後、輝度は低下した。また、発光強度は、温度が高いほど短い期間で向上した。 As shown in FIG. 2, at any temperature, the emission intensity was significantly improved by being left standing. Moreover, in the example stored at 20 ° C. or 25 ° C., the brightness decreased after becoming cloudy at the time indicated by the thick arrow. Also, the emission intensity improved in a shorter period as the temperature was higher.
また、図３は、前述のように製造された波長変換ナノ粒子が分散した溶液にバインダとしてのプルランを添加し、室温でＳｉ基板上に２日放置し、固化させた後の状態を透過型電子顕微鏡（Transmission Electron Microscope）で観察したＴＥＭ像である。なお、図３（Ｂ）は図３（Ａ）の丸で囲んだ部分を拡大したＴＥＭ像であり、図３（Ｃ）は図３（Ｂ）の丸で囲んだ部分を拡大したＴＥＭ像である。前述のように製造された波長変換ナノ粒子は、製造直後は３〜５ｎｍの粒子経を有しているが、図３のＴＥＭ像から、前記放置によって波長変換ナノ粒子が凝集し、直径２０〜６０ｎｍのナノ粒子群を形成していることが分かる。 Also, FIG. 3 shows the state after adding pullulan as a binder to the solution in which the wavelength conversion nanoparticles prepared as described above are dispersed and leaving it on a Si substrate at room temperature for 2 days to solidify it. It is the TEM image observed with the electron microscope (Transmission Electron Microscope). 3B is an enlarged TEM image of the circled portion of FIG. 3A, and FIG. 3C is an enlarged TEM image of the circled portion of FIG. 3B. is there. The wavelength-converted nanoparticles produced as described above have a particle size of 3 to 5 nm immediately after production. From the TEM image of FIG. It can be seen that 60 nm nanoparticle groups are formed.
更に、図４に示す前記ナノ粒子群の発光スペクトルから、そのナノ粒子群は、５８０ｎｍに発光強度のピークを有することが分かった。Ｚｎ及びＳｅから構成された無機ナノ粒子にＭｎをドープして得られる波長変換ナノ粒子（ＺｎＳｅ：Ｍｎ）も、同様の位置に発光強度のピークを有することが知られている。従って、前記ナノ粒子群は、製造直後の粒子経を維持したまま、一体化することなく前記大きさに凝集したものと推察される。 Furthermore, from the emission spectrum of the nanoparticle group shown in FIG. 4, it was found that the nanoparticle group had a peak of emission intensity at 580 nm. It is known that wavelength conversion nanoparticles (ZnSe: Mn) obtained by doping Mn into inorganic nanoparticles composed of Zn and Se also have emission intensity peaks at similar positions. Therefore, the nanoparticle group is presumed to be aggregated to the size without being integrated while maintaining the particle size immediately after production.
これは、図５（Ａ）に模式的に示すように、波長変換ナノ粒子１０の周囲にＮＡＣからなる配位子１１が配位しており、これによって、波長変換ナノ粒子１０が凝集してナノ粒子群２０を形成した後も、各波長変換ナノ粒子１０は一体化せずに個々に光を吸収して異なる波長（５８０ｎｍ前後）の光を発生しているものと推察される。すなわち、図５（Ｂ）に模式的に示すように、波長変換ナノ粒子１０が凝集して一体化し、粒子経の大きい波長変換ナノ粒子１０を形成したと仮定すると、下記の式から導けるように吸収する光の波長が長波長化するが、図４のグラフからそのような仮定は否定される。また、図５（Ｃ）に模式的に示すように、波長変換ナノ粒子１０が製造直後と同様の分散状態を維持しているのであれば、発光強度は変化しないはずである。 As schematically shown in FIG. 5 (A), the ligand 11 made of NAC is coordinated around the wavelength conversion nanoparticle 10, and the wavelength conversion nanoparticle 10 is thereby aggregated. Even after the nanoparticle group 20 is formed, it is presumed that the wavelength conversion nanoparticles 10 are not integrated but absorb light individually and generate light of different wavelengths (around 580 nm). That is, as schematically shown in FIG. 5B, assuming that the wavelength conversion nanoparticles 10 are aggregated and integrated to form the wavelength conversion nanoparticles 10 having a large particle diameter, the following formula can be derived. Although the wavelength of light to be absorbed becomes longer, such an assumption is denied from the graph of FIG. Further, as schematically shown in FIG. 5C, if the wavelength conversion nanoparticle 10 maintains the same dispersion state as that immediately after the production, the emission intensity should not change.
そこで、本実施の形態の製造方法では、白濁する直前のナノ粒子群２０を溶媒４０と共に採取し、図６（Ａ）に示すように基材の一例としてのガラス板５０に塗布し、更にその表面にもう１枚のガラス板５１を積層してナノ粒子群２０の大きさを前記白濁する直前の状態に維持した。このように、ナノ粒子群２０を溶媒４０と共にガラス板５０，５１で挟んでなるフィルタは、紫外線を吸収して可視光に変換する特性を有する。このため、このようなフィルタを太陽電池の表面に配設すれば、その太陽電池の効率を向上させることができる。 Therefore, in the manufacturing method of the present embodiment, the nanoparticle group 20 immediately before clouding is collected together with the solvent 40 and applied to a glass plate 50 as an example of a substrate as shown in FIG. Another glass plate 51 was laminated on the surface, and the size of the nanoparticle group 20 was maintained in the state immediately before clouding. As described above, the filter in which the nanoparticle group 20 is sandwiched between the glass plate 50 and 51 together with the solvent 40 has a characteristic of absorbing ultraviolet light and converting it into visible light. For this reason, if such a filter is arrange | positioned on the surface of a solar cell, the efficiency of the solar cell can be improved.
また、このようにガラス板５０，５１に挟む実験では、波長変換ナノ粒子１０が凝集して得られたナノ粒子群２０は、ガラス板５０の表面に均一に塗布するのが容易で、しかも、挟んだ後から偏析が起こりにくいことも分かった。すなわち、製造直後の波長変換ナノ粒子１０を、図６（Ｂ）に示すように溶媒４０と共にガラス板５０，５１で挟むと、時間の経過に伴って、図６（Ｃ）に示すように波長変換ナノ粒子１０がガラス板５０，５１の周囲に偏析するが、ナノ粒子群２０ではそのような現象は確認されなかった。なお、実験では、ガラス板５０，５１の間に、プルランとナノ粒子溶液を１：１で混合した溶液１．５ｍｌを挟んで固化させた。溶液の固形物量はおよそ０．０２重量％であるが、プルランが水分を含み固化し、ガラス板５０，５１の面積が１００ｃｍ2 であるため、貼り付け直後のガラス板５０，５１の対向面の間隔は０．１５ｍｍと推定される。 Further, in the experiment sandwiched between the glass plates 50 and 51 in this way, the nanoparticle group 20 obtained by aggregating the wavelength conversion nanoparticles 10 can be easily applied uniformly to the surface of the glass plate 50, It was also found that segregation hardly occurs after sandwiching. That is, when the wavelength-converting nanoparticles 10 immediately after production are sandwiched between the glass plates 50 and 51 together with the solvent 40 as shown in FIG. 6B, the wavelength changes as shown in FIG. 6C with the passage of time. Although the conversion nanoparticles 10 segregate around the glass plates 50 and 51, such a phenomenon was not confirmed in the nanoparticle group 20. In the experiment, 1.5 ml of a solution in which pullulan and the nanoparticle solution were mixed at a ratio of 1: 1 between the glass plates 50 and 51 was solidified. The amount of solids in the solution is approximately 0.02% by weight, but pullulan solidifies with moisture, and the area of the glass plates 50 and 51 is 100 cm 2 . The spacing is estimated to be 0.15 mm.
図７は、そのようなフィルタの各波長に対する透過率を、ナノ粒子群２０の濃度を種々に変えて測定した実験結果を表すグラフである。図７に示すように、濃度倍率（１倍が０．０２重量％に相当）を高くするほど、紫外線は良好に吸収されるが、可視光線はいずれの濃度倍率でも良好に透過されることが分かった。なお、白濁した後に採取されたナノ粒子群２０では、可視光線の透過率も低下した。このように、前記フィルタは、紫外線を可視光線に変換するフィルタとして良好に使用できることが分かった。 FIG. 7 is a graph showing experimental results obtained by measuring the transmittance of each filter for each wavelength while changing the concentration of the nanoparticle group 20 in various ways. As shown in FIG. 7, the higher the concentration magnification (1 time corresponds to 0.02% by weight), the better the ultraviolet light is absorbed, but the visible light can be transmitted well at any concentration magnification. I understood. In addition, in the nanoparticle group 20 collected after becoming cloudy, the transmittance of visible light also decreased. Thus, it was found that the filter can be used favorably as a filter that converts ultraviolet light into visible light.
なお、本発明は前記実施の形態に何ら限定されるものではなく、本発明の要旨を逸脱しない範囲で種々の形態で実施することができる。例えば、Ｚｎイオン源としては、前述の過塩素酸亜鉛の他、塩化亜鉛，酢酸亜鉛，硝酸亜鉛等が使用できる。また、Ｍｎイオン源としては、前述の過塩素酸マンガンの他、塩化マンガン，酢酸マンガン，臭化マンガン等が使用できる。また、Ｓｅイオン源としては、前述のＮａＨＳｅの他、セレノウレア，セレン化水素ガス等が使用できる。更に、配位子としては、前述のＮＡＣの他、メルカプト酢酸，メルカプトプロピオン酸，メルカプトこはく酸等が使用できる。 In addition, this invention is not limited to the said embodiment at all, It can implement with a various form in the range which does not deviate from the summary of this invention. For example, as the Zn ion source, zinc chloride, zinc acetate, zinc nitrate, etc. can be used in addition to the above-described zinc perchlorate. In addition to the above-described manganese perchlorate, manganese chloride, manganese acetate, manganese bromide, and the like can be used as the Mn ion source. Further, as the Se ion source, selenourea, hydrogen selenide gas, etc. can be used in addition to the above-mentioned NaHSe. Further, as the ligand, mercaptoacetic acid, mercaptopropionic acid, mercaptosuccinic acid and the like can be used in addition to the aforementioned NAC.
また更に、Ｓｅの代わりにＳを使用してもよい。その場合も、図１（Ａ）の工程の後にはｐＨを１０．５に調整するのが望ましい。また、その場合、図１（Ｂ）の工程で用いるＳイオン源としては、硫化ナトリウム，チオ尿素，硫化水素ガス等が使用でき、Ｚｎ：Ｓのモル比が１：０．６となるようにするのが望ましい。 Furthermore, S may be used instead of Se. Even in that case, it is desirable to adjust the pH to 10.5 after the step of FIG. In that case, sodium sulfide, thiourea, hydrogen sulfide gas, or the like can be used as the S ion source used in the step of FIG. 1B so that the molar ratio of Zn: S is 1: 0.6. It is desirable to do.
また、無機ナノ粒子を構成するアニオンとしてＳｅを用いる場合とＳを用いる場合とでは、図１（Ａ）の工程の後において調整すべきｐＨの値が異なる。そこで、次のような方法により、アニオンとしてＳｅとＳとの両方を用いたいわゆる混晶半導体としての無機ナノ粒子をＭｎでドープした波長変換ナノ粒子を、製造することができる。 Moreover, the value of pH which should be adjusted after the process of FIG. 1 (A) differs by the case where Se is used as the anion which comprises an inorganic nanoparticle, and the case where S is used. Therefore, by the following method, wavelength conversion nanoparticles in which inorganic nanoparticles as so-called mixed crystal semiconductors using both Se and S as anions are doped with Mn can be produced.
すなわち、前述の図１（Ａ），（Ｂ）の工程によって製造されたＺｎＭｎＳｅの前駆体（Ｐｒｅｃｕｒｓｏｒ）溶液と、その図１（Ａ），（Ｂ）の工程において前述のようにＳｅの代わりにＳを使用して製造されたＺｎＳ：Ｍｎの前駆体溶液とを、別々に製造する。そして、ｐＨ１０．５に調整の後、両者を混合して２００℃で２０分加熱することによってＳｅとＳとの両方を含む波長変換ナノ粒子を得ることができる。この波長変換ナノ粒子では、ＳｅとＳとの比は自由に調整でき、ＺｎＳｅXＳ1-X：Ｍｎ（０＜Ｘ＜１）なる一般式で表すことができる。この波長変換ナノ粒子を、前述のように放置してガラス板５０等の基材に塗布することで、本発明の実施の形態としてのナノ粒子群を得ることができる。 That is, the ZnMnSe precursor solution prepared by the above-described steps of FIGS. 1A and 1B, and in place of Se in the steps of FIGS. 1A and 1B, as described above. A ZnS: Mn precursor solution prepared using S is prepared separately. And after adjusting to pH10.5, both can be mixed, and the wavelength conversion nanoparticle containing both Se and S can be obtained by heating at 200 degreeC for 20 minutes. In this wavelength conversion nanoparticle, the ratio of Se and S can be freely adjusted, and can be expressed by the general formula ZnSe X S 1-X : Mn (0 <X <1). By leaving the wavelength-converted nanoparticles as described above and applying them to a substrate such as the glass plate 50, a group of nanoparticles as an embodiment of the present invention can be obtained.
また、前記実施の形態では、カチオンとしてＺｎ，Ｍｎを使用しているが、Ｍｎの代わりにＣｄを用いるなど、カチオンの種類も種々に変更することができる。更に、ＳまたはＳｅと、Ｍｎと、Ｚｎとは、どういう順番で混ぜてもよい。また更に、波長変換ナノ粒子が分散された溶液には塩などを添加してもよく、その場合、ナノ粒子群の形成速度等を調整することができる。 Moreover, in the said embodiment, although Zn and Mn are used as a cation, the kind of cation can be changed variously, such as using Cd instead of Mn. Furthermore, S or Se, Mn, and Zn may be mixed in any order. Furthermore, a salt or the like may be added to the solution in which the wavelength conversion nanoparticles are dispersed. In this case, the formation rate of the nanoparticle group can be adjusted.
また、本発明のナノ粒子群を構成する波長変換ナノ粒子は、前記方法で製造されたものに限定されるものではなく、例えば、有機溶媒中で製造された波長変換ナノ粒子など、種々の波長変換ナノ粒子を利用することができる。更に、ナノ粒子群が塗布される基材としてもガラスの他、プラスチック，大理石等、種々の基材を利用することができる。 Further, the wavelength conversion nanoparticles constituting the nanoparticle group of the present invention are not limited to those produced by the above-described method, and various wavelengths such as wavelength conversion nanoparticles produced in an organic solvent, for example. Conversion nanoparticles can be utilized. Furthermore, various base materials such as plastic and marble can be used as the base material to which the nanoparticle group is applied.
１０…波長変換ナノ粒子 １１…配位子 ２０…ナノ粒子群
３０…バインダ ４０…溶媒 ５０，５１…ガラス板
DESCRIPTION OF SYMBOLS 10 ... Wavelength conversion nanoparticle 11 ... Ligand 20 ... Nanoparticle group 30 ... Binder 40 ... Solvent 50, 51 ... Glass plate
Claims (12)
前記各波長変換ナノ粒子は、各々の周囲に配位子が配位したことによって互いに一体化することなく、直径２０〜１００ｎｍの大きさに凝集したことを特徴とするナノ粒子群。 The particle diameter is 10 nm or less, and is composed of a plurality of wavelength conversion nanoparticles that generate light having a wavelength different from the absorbed light,
Each of the wavelength conversion nanoparticles is a group of nanoparticles characterized in that they are aggregated to a diameter of 20 to 100 nm without being integrated with each other by coordination of a ligand around each of the wavelength conversion nanoparticles.
前記ｐＨ調整後の前記溶液を加熱して粒子経が１０ｎｍ以下の波長変換ナノ粒子を生成する加熱工程と、
前記生成された波長変換ナノ粒子を含む溶液を放置することによって、その波長変換ナノ粒子を直径２０〜１００ｎｍの大きさに凝集させた後、基材に塗布する凝集工程と、
を備えたことを特徴とするナノ粒子群の製造方法。 An ion source that provides Mn, an ion source that provides atoms constituting the inorganic nanoparticles, and a hydrophilic ligand in an aqueous solvent, and a mixing step for adjusting the pH of the resulting solution; ,
A heating step of heating the solution after the pH adjustment to generate wavelength conversion nanoparticles having a particle size of 10 nm or less;
An aggregating step of aggregating the wavelength-converted nanoparticles into a size of 20 to 100 nm in diameter by allowing the solution containing the generated wavelength-converted nanoparticles to stand;
A method for producing a group of nanoparticles, comprising:
前記混合工程では、Ｎ−アセチル−Ｌ−システインと前記イオン源中のＭｎ原子とを１：１のモル比で含む溶液と、Ｎ−アセチル−Ｌ−システインと前記イオン源中のＺｎ原子とを１：４．８のモル比で含む溶液とを、混合することを特徴とする請求項７に記載のナノ粒子群の製造方法。 The ligand is N-acetyl-L-cysteine;
In the mixing step, a solution containing N-acetyl-L-cysteine and Mn atoms in the ion source in a molar ratio of 1: 1; N-acetyl-L-cysteine and Zn atoms in the ion source; The method for producing a group of nanoparticles according to claim 7, wherein a solution containing a molar ratio of 1: 4.8 is mixed.
前記混合工程は、
前記無機ナノ粒子を構成するＳｅ以外の各原子を各々提供する前記各イオン源と、前記配位子と、を水系溶媒中で混合し、得られた溶液のｐＨ調整を行う第１混合工程と、
前記無機ナノ粒子を構成するＳ以外の各原子を各々提供する前記各イオン源と、前記配位子と、を水系溶媒中で混合し、得られた溶液のｐＨ調整を行う第２混合工程と、
前記第１混合工程で得られた前記ｐＨ調整後の溶液と、前記第２混合工程で得られた前記ｐＨ調整後の溶液とを混合する第３混合工程と、
からなり、
前記Ｍｎを提供するイオン源は、前記第１混合工程または前記第２混合工程で前記溶液に混合されることを特徴とする請求項６〜１０のいずれか１項に記載のナノ粒子群の製造方法。 As atoms constituting the inorganic nanoparticles, S and Se are included,
The mixing step includes
A first mixing step of adjusting the pH of the resulting solution by mixing each ion source providing each atom other than Se constituting the inorganic nanoparticles and the ligand in an aqueous solvent; ,
A second mixing step of adjusting the pH of the resulting solution by mixing each ion source that provides each atom other than S constituting the inorganic nanoparticles and the ligand in an aqueous solvent; ,
A third mixing step of mixing the solution after pH adjustment obtained in the first mixing step and the solution after pH adjustment obtained in the second mixing step;
Consists of
The nanoparticle group production according to any one of claims 6 to 10, wherein the ion source providing Mn is mixed with the solution in the first mixing step or the second mixing step. Method.
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