JP5977105B2 - Brightness adjustment method for wavelength conversion nanoparticles - Google Patents
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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の輝度（発光輝度）を向上させることができる波長変換ナノ粒子の輝度調整方法に関する。 The present invention relates to absorbent luminance adjusting how the wavelength conversion nanoparticles can improve the luminance (light emission luminance) of the wavelength conversion nanoparticles for generating light of a different wavelength from the light.
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、Ｃｄは廃棄処理を誤ると環境に悪影響を与えるため、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。 Conventionally, as such wavelength conversion nanoparticles, those containing CdS have been proposed. However, since Cd has an adverse effect on the environment if the disposal process is mistaken, wavelength conversion nanoparticles are manufactured using ZnSe or the like. It has been proposed.
ところが、この種の製造方法では、有機溶媒中で波長変換ナノ粒子を製造しているため、その有機溶媒の廃棄処理を誤るとＰＲＴＲ法に抵触する可能性がある。そこで、水系溶媒中で波長変換ナノ粒子を製造することが提案されている（非特許文献１参照）。 However, since this type of production method produces wavelength conversion nanoparticles in an organic solvent, there is a possibility of conflicting with the PRTR method if the organic solvent is discarded. Therefore, it has been proposed to produce wavelength conversion nanoparticles in an aqueous solvent (see Non-Patent Document 1).
しかしながら、前記非特許文献１に記載の方法では、１００℃以下の温度で波長変換ナノ粒子を製造しており、得られた波長変換ナノ粒子は、それほど良好な発光輝度（発光強度）を有していなかった。 However, in the method described in Non-Patent Document 1, wavelength-converted nanoparticles are produced at a temperature of 100 ° C. or less, and the obtained wavelength-converted nanoparticles have a very good emission luminance (emission intensity). It wasn't.
そこで、本発明者等は、良好な発光輝度を有する波長変換ナノ粒子を、水系溶媒中で製造可能とするための研究を行って、高い発光輝度を有する波長変換ナノ粒子を開発している。 Therefore, the present inventors have conducted research to make it possible to produce wavelength conversion nanoparticles having good emission luminance in an aqueous solvent, and have developed wavelength conversion nanoparticles having high emission luminance.
ところが、最近の研究によれば、溶液中の波長変換ナノ粒子は、作成後に外部環境等の各種の影響によって輝度変動があることが分かってきており、特に、波長変換ナノ粒子の発光輝度を一層高めることができる技術が望まれている。 However, according to recent research, it has been found that wavelength-converted nanoparticles in a solution have luminance fluctuations due to various influences such as the external environment after preparation. A technology that can be enhanced is desired.
本発明は、前記課題を解決するためになされたものであり、その目的は、製造された溶液中の波長変換ナノ粒子の発光輝度を一層高めることができる波長変換ナノ粒子の輝度調整方法を提供することにある。 The present invention has been made to solve the above problems, and its object is brightness adjustment how the wavelength conversion nanoparticles can increase the emission luminance of the wavelength conversion nanoparticles prepared solution further the It is to provide.
本発明の波長変換ナノ粒子の輝度調整方法は、波長変換ナノ粒子を製造する製造工程として、Ｎ−アセチル−Ｌ−システインと発光中心となるＭｎイオンとを１：１のモル比で含む溶液と、Ｎ−アセチル−Ｌ−システインと無機ナノ粒子を構成するＺｎ原子とを１：４．８のモル比で含む溶液とを、水系溶媒で混合し、得られた溶液のｐＨ調整を行う混合工程と、ｐＨ調整後の溶液を高圧下で１５０℃〜２５０℃に加熱して、溶液中にて波長変換ナノ粒子を生成する加熱工程と、を有し、加熱工程の後に、その波長変換ナノ粒子が分散した溶液に、酸素を含むガスを供給する。 Solution containing 1 molar ratio: brightness adjustment how the wavelength conversion nanoparticles of the invention, as a manufacturing process for manufacturing the wavelength conversion nanoparticles, and Mn ions to be a luminescent center and N- acetyl -L- cysteine 1 And a solution containing N-acetyl-L-cysteine and Zn atoms constituting the inorganic nanoparticles in a molar ratio of 1: 4.8 are mixed with an aqueous solvent, and the pH of the resulting solution is adjusted. Heating the solution after pH adjustment to 150 ° C. to 250 ° C. under high pressure to generate wavelength conversion nanoparticles in the solution, and after the heating step , the wavelength conversion nano A gas containing oxygen is supplied to the solution in which the particles are dispersed.
これにより、後述する実験例からも明らかな様に、前記溶液中の波長変換ナノ粒子の発光輝度を、製造時の発光輝度よりも向上させることができる。
このように、酸素を含むガスを供給することによって発光輝度が向上する理由は、後に詳述する様に、溶液中に分散している波長変換ナノ粒子が、濃度消光によって発光輝度が低くなっている場合には、この溶液に対して酸素を供給することによって、金属イオンを酸化させて溶液中に析出させ、それによって、濃度消光の影響を低減できるからと推定される。
This makes it possible to improve the light emission luminance of the wavelength conversion nanoparticles in the solution as compared with the light emission luminance at the time of manufacture, as is clear from the experimental examples described later.
As described above, the reason why the emission luminance is improved by supplying the gas containing oxygen is that, as will be described in detail later, the wavelength conversion nanoparticles dispersed in the solution have a lower emission luminance due to concentration quenching. In this case, it is presumed that by supplying oxygen to this solution, metal ions are oxidized and precipitated in the solution, thereby reducing the influence of concentration quenching.
従って、このように輝度調整されて発光輝度が高くなった波長変換ナノ粒子を、例えば太陽電池等に応用すれば、紫外線を可視光線に変換して太陽電池の効率を向上させることができるという顕著な効果を奏する。 Therefore, if the wavelength-converted nanoparticles whose luminance is adjusted and thus the emission luminance is increased are applied to, for example, solar cells, the efficiency of the solar cells can be improved by converting ultraviolet rays into visible rays. Has an effect.
以下に、本発明の波長変換ナノ粒子の輝度調整方法と、この輝度調整方法によって発光輝度が調整された波長変換ナノ粒子の実施形態について説明する。
［実施形態］
・本発明では、波長変換ナノ粒子が分散した溶液に供給するガスの酸素濃度としては、大気中の酸素濃度を下回る濃度を採用できる。
Below, the brightness | luminance adjustment method of the wavelength conversion nanoparticle of this invention and embodiment of the wavelength conversion nanoparticle by which light emission brightness | luminance was adjusted by this brightness | luminance adjustment method are demonstrated.
[Embodiment]
In the present invention, as the oxygen concentration of the gas supplied to the solution in which the wavelength conversion nanoparticles are dispersed, a concentration lower than the oxygen concentration in the atmosphere can be adopted.
特に、後述する実験例に示す様に、酸素濃度が低いものほど、（時間がかかるものの）高い発光輝度を得ることができる。
・また、後述する実験例に示す様に、酸素を含むガスを供給した後に、波長変換ナノ粒子が分散した溶液のｐＨを低下させるｐＨ低下処理を行うと、短時間で発光輝度を高めることができる。なお、ｐＨ低下処理としては、ｐＨを６〜８の範囲に低下させると、急速に発光輝度を高めることができる。
In particular, as shown in an experimental example to be described later, the lower the oxygen concentration, the higher the emission luminance (though it takes longer).
In addition, as shown in an experimental example to be described later, after a gas containing oxygen is supplied, if the pH reduction treatment is performed to reduce the pH of the solution in which the wavelength conversion nanoparticles are dispersed, the emission luminance can be increased in a short time. it can. In addition, as pH reduction process, if pH is reduced to the range of 6-8, luminous brightness can be raised rapidly.
このｐＨ低下処理としては、「波長変換ナノ粒子が分散した溶液に、酸性溶液を加えてｐＨを低下させる方法」、「波長変換ナノ粒子が分散した溶液に、希釈溶液を加えることによって溶液を希釈して、ｐＨを低下させる方法」、「波長変換ナノ粒子が分散した溶液に、その溶液に溶解することによってｐＨを低下させるガスを供給する方法」を用いることができる。 As the pH lowering treatment, “a method of lowering pH by adding an acidic solution to a solution in which wavelength conversion nanoparticles are dispersed”, “dilution of a solution by adding a diluted solution to a solution in which wavelength conversion nanoparticles are dispersed” The method for lowering the pH "and" the method for supplying the solution in which the wavelength conversion nanoparticles are dispersed with the gas for lowering the pH by dissolving in the solution "can be used.
なお、ｐＨを低下させるために用いる酸性溶液としては、塩酸が挙げられるが、それ以外にも、硫酸や硝酸などが考えられる。このうち、塩酸は、ドープされた金属（例えばＭｎ）と沈殿物を生成する恐れがないので、好適である。 In addition, hydrochloric acid is mentioned as an acidic solution used in order to lower pH, but sulfuric acid, nitric acid, etc. can be considered besides that. Of these, hydrochloric acid is preferred because it has no fear of forming a precipitate with a doped metal (eg, Mn).
一方、ｐＨを低下させるために用いるガスとしては、炭酸ガス（二酸化炭素）が挙げられるが、それ以外にも、硫化水素や塩酸ガスなどが考えられる。このうち、炭酸ガスは、安全上扱い易いので、好適である。 On the other hand, examples of the gas used for lowering the pH include carbon dioxide (carbon dioxide), but hydrogen sulfide, hydrochloric acid gas, and the like are also conceivable. Of these, carbon dioxide is preferable because it is easy to handle for safety.
また、発光中心となる金属イオンとしては、Ｍｎイオンを採用でき、無機ナノ粒子を構成する原子としては、Ｚｎを含むことができる。Ｚｎを含む無機ナノ粒子は、紫外領域の光を良好に吸収し、その無機ナノ粒子にＭｎイオンがドープされていると、紫外領域の光を可視領域の光に変換して発生することができる。従って、その場合、太陽電池の効率を向上させるなどの用途に良好に応用することができる。 Further, Mn ions can be adopted as the metal ions that become the emission center, and Zn can be contained as the atoms constituting the inorganic nanoparticles. Inorganic nanoparticles containing Zn absorb light in the ultraviolet region well, and when the inorganic nanoparticles are doped with Mn ions, they can be generated by converting light in the ultraviolet region into light in the visible region. . Therefore, in that case, it can be favorably applied to uses such as improving the efficiency of solar cells.
・更に、波長変換ナノ粒子を製造した後に、溶液の周囲に例えばアルゴン（Ａｒ）ガス、窒素（Ｎ2）ガス等の不活性ガスを供給し、その後、ｐＨ低下処理を行ってもよい。この不活性ガスの供給により輝度変動を抑制することができるので、ｐＨ低下処理を行うまでは、その輝度を保持することができる。 Furthermore, after manufacturing the wavelength conversion nanoparticles, an inert gas such as argon (Ar) gas or nitrogen (N 2 ) gas may be supplied around the solution, and then a pH reduction treatment may be performed. Since the luminance fluctuation can be suppressed by supplying the inert gas, the luminance can be maintained until the pH lowering process is performed.
・また、上述した波長変換ナノ粒子の輝度変動を完全に停止させて、その輝度を保持する場合には、波長変換ナノ粒子が分散した溶液を固化させればよい。この固化させる方法としては、ガラスをバインダとするゾルゲル法や、ポリ水酸化ビニルに混入し固化させる方法などが挙げられる。 -Moreover, what is necessary is just to solidify the solution in which the wavelength conversion nanoparticle was disperse | distributed, when the brightness | luminance fluctuation | variation of the wavelength conversion nanoparticle mentioned above is stopped completely and the brightness | luminance is maintained. Examples of the solidification method include a sol-gel method using glass as a binder, and a method of mixing and solidifying with polyvinyl hydroxide.
・更に、波長変換ナノ粒子を製造する製造工程としては、発光中心となる金属イオン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、無機ナノ粒子に配位する親水性の配位子と、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、ｐＨ調整後の溶液を高圧下で１５０℃〜２５０℃に加熱して、溶液中にて波長変換ナノ粒子を生成する加熱工程とを採用できる。 ・ Furthermore, as a manufacturing process for producing wavelength conversion nanoparticles, an ion source that provides a metal ion serving as a luminescent center, an ion source that provides atoms constituting the inorganic nanoparticles, and a hydrophilic coordinated to the inorganic nanoparticles A mixing step of adjusting the pH of the resulting solution, and heating the pH-adjusted solution at 150 to 250 ° C. under high pressure to bring the solution into the solution. And a heating step for generating wavelength conversion nanoparticles.
つまり、水系溶媒中で波長変換ナノ粒子を製造する場合に、１５０℃〜２５０℃に加熱して製造すると、良好な発光輝度を有する波長変換ナノ粒子が得られる。
なお、配位子としては、Ｎ−アセチル−Ｌ−システインを採用できるが、Ｎ−アセチル−Ｌ−システインの他、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可能である。
That is, when the wavelength conversion nanoparticles are produced in an aqueous solvent, if they are produced by heating to 150 ° C. to 250 ° C., wavelength conversion nanoparticles having good emission luminance can be obtained.
In addition, N-acetyl-L-cysteine can be adopted as the ligand, but in addition to N-acetyl-L-cysteine, mercaptoacetic acid, mercaptopropionic acid, mercaptosuccinic acid, and the like can be used.
・ここで、無機ナノ粒子にＭｎイオンがドープされている場合は、混合工程では、Ｎ−アセチル−Ｌ−システインとイオン源中のＭｎイオンとを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してもよい。 Here, when inorganic nanoparticles are doped with Mn ions, in the mixing step, a solution containing N-acetyl-L-cysteine and Mn ions in the ion source in a molar ratio of 1: 1; A solution containing acetyl-L-cysteine and Zn atoms in the ion source in a molar ratio of 1: 4.8 may be mixed.
・また、無機ナノ粒子を構成する原子として、ＳとＳｅとを含む場合は、混合工程は、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各イオン源と、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、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各イオン源と、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、第１混合工程で得られたｐＨ調整後の溶液と、第２混合工程で得られたｐＨ調整後の溶液とを混合する第３混合工程と、からなり、発光中心となる金属イオンを提供するイオン源は、第１混合工程または第２混合工程で溶液に混合してもよい。 -Moreover, when including S and Se as an atom which comprises an inorganic nanoparticle, a mixing process, each ion source which provides each atom other than Se which comprises an inorganic nanoparticle, respectively, a ligand, A first mixing step of adjusting the pH of the resulting solution, each ion source that provides each atom other than S constituting the inorganic nanoparticles, and a ligand. A second mixing step of adjusting the pH of the solution obtained by mixing in a solvent, a solution after pH adjustment obtained in the first mixing step, and a solution after pH adjustment obtained in the second mixing step; And an ion source that provides metal ions serving as the emission center may be mixed into the solution in the first mixing step or the second mixing step.
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る。 By doing so, it is possible to satisfactorily produce wavelength conversion nanoparticles made of mixed crystals as described above.
以下に、本発明の波長変換ナノ粒子の輝度調整方法と、この輝度調整方法によって発光輝度が調整された波長変換ナノ粒子の具体的な実施例について説明する。
ａ）まず、実施例１の波長変換ナノ粒子の製造方法について説明する。
Below, the brightness | luminance adjustment method of the wavelength conversion nanoparticle of this invention and the specific Example of the wavelength conversion nanoparticle by which light emission brightness | luminance was adjusted with this brightness | luminance adjustment method are demonstrated.
a) First, the manufacturing method of the wavelength conversion nanoparticle of Example 1 is demonstrated.
図１（Ａ）に示すように、本実施例では、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。 As shown in FIG. 1 (A), in this example, first, a Zn ion source (for example, zinc perchlorate) and N-acetyl-L-cysteine (hereinafter referred to as NAC) are 1: 4.8. An aqueous solution containing a molar ratio was mixed with an aqueous solution containing a Mn ion source (eg, manganese perchlorate) and NAC at a molar ratio of 1: 1. 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%.
次に、図１（Ｂ）に示すように、その水溶液にＮａＯＨを添加することによってｐＨ８．５に調整した。
次に、図１（Ｃ）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、即ち、ＺｎＭｎＳｅの前駆体（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定される。
Next, as shown in FIG. 1 (B), the pH was adjusted to 8.5 by adding NaOH to the aqueous solution.
Next, as shown in FIG. 1C, 1.2 mmol of Se ion source (for example, NaHSe) was added. In this case, the molar ratio of Zn: Se is (1: 0.6). Further, in this aqueous solution, that is, a ZnMnSe precursor (Precursor), it is presumed that the SH group of NAC is coordinated to a metal atom, and the carboxyl group of NAC promotes dissolution in an aqueous solvent.
次に、前記水溶液に、更にＮａＯＨを添加することによって、図１（Ｄ）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１０分とした。 Next, by further adding NaOH to the aqueous solution, as shown in FIG. 1 (D), the pH is adjusted to 10.5, and then heated to 200 ° C. under high pressure (for example, 6 atmospheres), thereby changing the wavelength. Conversion nanoparticles (ZnSe: Mn) were produced. The heating time was 10 minutes.
そして、この様にして製造した波長変換ナノ粒子に対して、蛍光分光測定器（日立ハイテクノロジー社製のF2500）を用いて、波長３２５ｎｍの紫外線を当て、波長変換ナノ粒子の発光スペクトルを調べた。 Then, the wavelength conversion nanoparticles produced in this manner were irradiated with UV light having a wavelength of 325 nm using a fluorescence spectrometer (F2500, manufactured by Hitachi High-Technology Corporation), and the emission spectrum of the wavelength conversion nanoparticles was examined. .
その結果を、図２に示すが、ＺｎＳｅ系の無機ナノ粒子にＭｎイオンがドープされた実施例１の波長変換ナノ粒子（ＺｎＳｅ：Ｍｎ）では、５４０ｎｍ〜６４０ｎｍの可視領域（特に５８２ｎｍ）に、発光輝度（以下、発光スペクトルの大きさを示す場合は、発光強度と記すこともある）のピークが現れた。なお、同図ではピークの強度は１６０００である。 The results are shown in FIG. 2. In the wavelength conversion nanoparticles (ZnSe: Mn) of Example 1 in which Mn ions are doped into ZnSe-based inorganic nanoparticles, in the visible region of 540 nm to 640 nm (particularly 582 nm), A peak of emission luminance (hereinafter sometimes referred to as emission intensity when showing the size of the emission spectrum) appeared. In the figure, the peak intensity is 16000.
この様に、本実施例の波長変換ナノ粒子では、従来の水系溶媒中で製造された波長変換ナノ粒子よりも極めて強い発光輝度（発光強度）が得られた。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。 Thus, in the wavelength conversion nanoparticle of the present Example, the emission luminance (emission intensity) extremely stronger than the wavelength conversion nanoparticle produced in the conventional aqueous solvent was obtained. This is thought to be because clean crystals can be formed by producing nanoparticles at a high temperature.
なお、以下に述べる発光スペクトル及び（ピークの）発光強度の測定方法は、特に記載しない限りは、前記と同様である。
また、グラフ縦軸の発光強度は、必ずしもカンデラ等の単位と１対１に対応するものではなく、当該グラフ中で対比された強度同士を相対的に比較した値である（以下同様）。従って、同じ試料であっても、強度等の値は後述のグラフ等における値と必ずしも一致しない。
The emission spectrum and the method for measuring the (peak) emission intensity described below are the same as described above unless otherwise specified.
Also, the emission intensity on the vertical axis of the graph does not necessarily correspond to a unit such as candela, but is a value obtained by relatively comparing the intensities compared in the graph (the same applies hereinafter). Therefore, even for the same sample, values such as intensity do not always match values in graphs and the like described later.
ｂ）次に、上述の様にして製造された波長変換ナノ粒子の輝度調整方法について説明する。
この輝度調整方法とは、製造時の発光輝度を更に向上させるための処理方法であり、本実施例では、酸素（Ｏ2）を用いて発光輝度を向上させる。
b) Next, a method for adjusting the luminance of the wavelength conversion nanoparticles produced as described above will be described.
This brightness adjustment method is a processing method for further improving the light emission brightness at the time of manufacture. In this embodiment, the light emission brightness is improved by using oxygen (O 2 ).
まず、図３（Ａ）に示すように、上述した製造方法によって製造された波長変換ナノ粒子を含む水溶液、即ち、波長変換ナノ粒子が分散したｐＨ１０．５の水溶液を５ｍｌとり、容積１０ｍｌのガラス容器１に入れた。 First, as shown in FIG. 3A, 5 ml of an aqueous solution containing the wavelength conversion nanoparticles produced by the production method described above, that is, a pH 10.5 aqueous solution in which the wavelength conversion nanoparticles are dispersed, is taken, and a glass having a volume of 10 ml. Placed in container 1.
なお、ガラス容器１の容積は、投入する水溶液の量より多いので、ガラス容器１内の水溶液の上方には、ガス（ここでは空気）が存在する空間３がある。
次に、ガラス容器１の開口５をゴム栓７で封をするとともに、ゴム栓７が外れないように、ゴム栓７の周囲にパラフィルム（図示せず）を巻き、ゴム栓７をガラス容器３に固定した。
Since the volume of the glass container 1 is larger than the amount of the aqueous solution to be charged, there is a space 3 in which gas (here, air) exists above the aqueous solution in the glass container 1.
Next, the opening 5 of the glass container 1 is sealed with a rubber stopper 7, and a parafilm (not shown) is wound around the rubber stopper 7 so that the rubber stopper 7 is not removed. 3 was fixed.
また、このゴム栓７には、ガラス容器１中の水溶液のｐＨを測定できるように、ｐＨ測定器（ｐＨメータ）９が挿入されている。
なお、この時点で、ガラス容器１内に、例えばアルゴン（Ａｒ）ガス、窒素（Ｎ2）ガス等の不活性ガスを充填して密閉することにより、波長変換ナノ粒子の輝度の劣化（低下）を防止することができる。即ち、その時点の輝度を保持することができる。
In addition, a pH measuring device (pH meter) 9 is inserted into the rubber stopper 7 so that the pH of the aqueous solution in the glass container 1 can be measured.
At this point, the glass container 1 is filled with an inert gas such as argon (Ar) gas or nitrogen (N 2 ) gas and sealed, thereby degrading (decreasing) the luminance of the wavelength conversion nanoparticles. Can be prevented. That is, the brightness at that time can be maintained.
これとは別に、図３（Ｂ）に示すように、窒素ガスボンベ１１に配管１３を接続し、配管１３の先端に第１注射針１５を取り付けた。
そして、図３（Ｃ）に示すように、ガラス容器１のゴム栓７に第２注射針１７を刺し、ガラス容器３内のガスがガラス容器１外に排出されるようにした。
Separately from this, as shown in FIG. 3B, the pipe 13 was connected to the nitrogen gas cylinder 11, and the first injection needle 15 was attached to the tip of the pipe 13.
And as shown in FIG.3 (C), the 2nd injection needle 17 was stabbed into the rubber stopper 7 of the glass container 1, and the gas in the glass container 3 was discharged | emitted out of the glass container 1. FIG.
次に、図３（Ｄ）に示すように、ガラス容器１のゴム栓７に第１注射針１５を刺し、窒素ガスボンベ１３から第１注射針１５を介してガラス容器１内に窒素ガスを供給した。詳しくは、窒素ガスを毎分１０００ｃｃで５分間供給した。これにより、ガラス容器１中のガス（ここでは水溶液上方の空間３の空気）を窒素ガスに入れ替えた。 Next, as shown in FIG. 3D, the first injection needle 15 is inserted into the rubber stopper 7 of the glass container 1, and nitrogen gas is supplied into the glass container 1 from the nitrogen gas cylinder 13 through the first injection needle 15. did. Specifically, nitrogen gas was supplied at 1000 cc / min for 5 minutes. Thereby, the gas in the glass container 1 (here, the air in the space 3 above the aqueous solution) was replaced with nitrogen gas.
次に、ガラス容器１のゴム栓７にマイクロシリング（図示せず）を差し込み、空間３内に純酸素１００μｌ供給した。これにより、空間３内の酸素濃度を２％（空間３の容積の５ｍｌに対して１００μｌ）とした。 Next, microshilling (not shown) was inserted into the rubber stopper 7 of the glass container 1, and 100 μl of pure oxygen was supplied into the space 3. As a result, the oxygen concentration in the space 3 was set to 2% (100 μl with respect to 5 ml of the volume of the space 3).
そして、酸素供給後の水溶液に対して、２１日後に、波長変換ナノ粒子の発光スペクトルを調べた。
その結果、酸素を供給した溶液中の波長変換ナノ粒子の発光強度（具体的には５８２ｎｍにおける発光ピーク強度）は、ｐＨ１０．５の水溶液中の製造直後の波長変換ナノ粒子に比べて大きく（１０倍以上）向上していた。
And the emission spectrum of the wavelength conversion nanoparticle was investigated 21 days after with respect to the aqueous solution after oxygen supply.
As a result, the emission intensity of the wavelength conversion nanoparticles in the solution supplied with oxygen (specifically, the emission peak intensity at 582 nm) is larger than that of the wavelength conversion nanoparticles immediately after production in an aqueous solution at pH 10.5 (10 More than twice).
ｃ）次に、本実施例の作用効果について説明する。
本実施例では、上述したように、波長変換ナノ粒子の製造工程において、ｐＨを従来より高いｐＨ１０．５に調整した後、高圧（例えば６気圧）及び高温（例えば２００℃）にて処理することにより、従来より発光輝度を高めることができる。
c) Next, the function and effect of this embodiment will be described.
In the present embodiment, as described above, in the wavelength conversion nanoparticle production process, the pH is adjusted to pH 10.5, which is higher than before, and then treated at a high pressure (for example, 6 atmospheres) and a high temperature (for example, 200 ° C.). As a result, the emission luminance can be increased as compared with the prior art.
しかも、本実施例では、波長変換ナノ粒子を製造した後に、この波長変換ナノ粒子が分散した水溶液に酸素を供給することにより、後述する実験例からも明らかな様に、製造直後の波長変換ナノ粒子の発光輝度を更に高めることができる。 Moreover, in this example, after producing the wavelength conversion nanoparticles, by supplying oxygen to the aqueous solution in which the wavelength conversion nanoparticles are dispersed, the wavelength conversion nanoparticles immediately after the production are obtained, as is apparent from the experimental examples described later. The emission luminance of the particles can be further increased.
従って、このように輝度調整されて発光輝度が高くなった波長変換ナノ粒子を、太陽電池等に応用すれば、紫外線を可視光線に変換して太陽電池の効率を向上させることができるという顕著な効果を奏する。 Therefore, if the wavelength-converting nanoparticles whose luminance is adjusted and the emission luminance is increased in this way are applied to a solar cell or the like, it is remarkable that the efficiency of the solar cell can be improved by converting ultraviolet rays into visible light. There is an effect.
ｄ）次に、本実施例の変形例について説明する。
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。
d) Next, a modification of the present embodiment will be described.
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.
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。 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.
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.
次に、実施例２について説明するが、前記実施例１と同様な内容の説明は省略又は簡易化する。
前述のように、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。
Next, the second embodiment will be described, but the description of the same contents as the first embodiment will be omitted or simplified.
As described above, the pH value to be adjusted after the step of FIG. 1A differs between the case where Se is used as the anion constituting the inorganic nanoparticles and the case where S is used.
そこで、実施例２では、次のような方法により、アニオンとしてＳｅとＳとの両方を用いていわゆる混晶半導体としての無機ナノ粒子をＭｎイオンでドープした波長変換ナノ粒子を製造した。 Therefore, in Example 2, wavelength conversion nanoparticles in which inorganic nanoparticles as so-called mixed crystal semiconductors were doped with Mn ions using both Se and S as anions were produced by the following method.
ａ）まず、実施例２の波長変換ナノ粒子の製造方法について説明する。
本実施例では、前述の図１（Ａ），（Ｂ）の工程によって製造されたＺｎＭｎＳｅの前駆体水溶液と、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の前駆体水溶液とを、別々に製造した。
a) First, the manufacturing method of the wavelength conversion nanoparticle of Example 2 is demonstrated.
In this example, the precursor aqueous solution of ZnMnSe produced by the process of FIGS. 1A and 1B described above, and in place of Se as described above in the process of FIGS. 1A and 1B. A ZnS: Mn precursor aqueous solution prepared using S was prepared separately.
そして、ｐＨ１０．５に調整の後、両者を混合して２００℃で１０分加熱することによって波長変換ナノ粒子を得た。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。なお、以下では、ＺｎＳｅxＳ1-xをＺｎＳｅＳと記す。 And after adjusting to pH10.5, both were mixed and the wavelength conversion nanoparticle was obtained by heating at 200 degreeC for 10 minutes. In this wavelength conversion nanoparticle, the ratio of Se and S can be freely adjusted and can be expressed by a general formula of ZnSe x S 1-x : Mn (0 <X <1). Hereinafter, ZnSe x S 1-x is referred to as ZnSeS.
この製造直後の波長変換ナノ粒子の製造直後の発光スペクトルを測定した。その結果を、図４に示すが（この図４では混合比（Ｘ）が異なる例を示している）、波長変換ナノ粒子（ＺｎＳｅ：Ｍｎ）にＳを加えることで、４００ｎｍ近傍の発光強度のピークが減少し、６００ｎｍ近傍の発光強度のピークが強くなることが分かった。 The emission spectrum immediately after the production of the wavelength conversion nanoparticles immediately after the production was measured. The result is shown in FIG. 4 (in FIG. 4, an example in which the mixing ratio (X) is different) is shown. By adding S to the wavelength conversion nanoparticles (ZnSe: Mn), the emission intensity in the vicinity of 400 nm is obtained. It was found that the peak decreased and the peak of the emission intensity near 600 nm became stronger.
つまり、例えばＸ＝０．６の場合、波長変換ナノ粒子の発光強度（具体的には５８２ｎｍにおける発光ピーク強度）は、５２０００であった。
ｂ）次に、上述の様にして製造された波長変換ナノ粒子の輝度調整方法について説明する。
That is, for example, when X = 0.6, the emission intensity of the wavelength conversion nanoparticles (specifically, the emission peak intensity at 582 nm) was 52,000.
b) Next, a method for adjusting the luminance of the wavelength conversion nanoparticles produced as described above will be described.
本実施例における輝度調整方法は、前記実施例１と同様である。
具体的には、前記図３に示す様に、波長変換ナノ粒子が分散したｐＨ１０．５の水溶液を５ｍｌとり、容積１０ｍｌのガラス容器１に入れた後に、ガラス容器１をゴム栓７で封止する。
The brightness adjustment method in this embodiment is the same as that in the first embodiment.
Specifically, as shown in FIG. 3, 5 ml of a pH 10.5 aqueous solution in which wavelength conversion nanoparticles are dispersed is taken and placed in a glass container 1 having a volume of 10 ml, and then the glass container 1 is sealed with a rubber stopper 7. To do.
その後、ゴム栓７に第２注射針１７を刺した後に、第１注射針１５を刺し、窒素ガスボンベ１３から第１注射針１５を介してガラス容器１内に窒素ガスを供給した。
次に、ガラス容器１のゴム栓７にマイクロシリングを差し込み、純酸素１００μｌ供給した。これにより、空間３内の酸素濃度を２％とした。
Thereafter, after the second injection needle 17 was inserted into the rubber stopper 7, the first injection needle 15 was inserted, and nitrogen gas was supplied into the glass container 1 from the nitrogen gas cylinder 13 through the first injection needle 15.
Next, microshilling was inserted into the rubber stopper 7 of the glass container 1, and 100 μl of pure oxygen was supplied. Thereby, the oxygen concentration in the space 3 was set to 2%.
その結果、酸素を供給してから２１日後の溶液中の波長変換ナノ粒子の発光強度（具体的には５８７ｎｍにおける発光ピーク強度）は、ｐＨ１０．５の水溶液中の製造直後の波長変換ナノ粒子に比べて大きく（１０倍以上）向上していた。 As a result, the emission intensity of the wavelength conversion nanoparticles in the solution 21 days after supplying oxygen (specifically, the emission peak intensity at 587 nm) is the same as that of the wavelength conversion nanoparticles immediately after production in the aqueous solution at pH 10.5. Compared with that, it was greatly improved (10 times or more).
この様に、ＳｅとＳとの両者を用いた波長変換ナノ粒子（ＺｎＳｅＳ：Ｍｎ）では、実施例１より一層良好な発光強度が得られ、太陽電池等に応用すればその効率を一層向上させられることが分かった。 Thus, wavelength conversion nanoparticles (ZnSeS: Mn) using both Se and S can provide better emission intensity than Example 1, and further improve the efficiency when applied to solar cells and the like. I found out that
ｃ）次に、上述した酸素を供給する処理によって発光輝度を高めることができる原理について説明する。
図５（Ａ）に示す様に、本実施例の製造方法の場合は、Ｚｎ、Ｓｅ、Ｓ、Ｍｎを含む前駆体の水溶液を、ｐＨ１０．５に調整して、６気圧にて、２００℃で加熱すると、波長変換ナノ粒子（ＺｎＳｅＳ：Ｍｎ）が生成される。
c) Next, the principle that the emission luminance can be increased by the above-described process of supplying oxygen will be described.
As shown in FIG. 5 (A), in the case of the production method of this example, an aqueous solution of a precursor containing Zn, Se, S, and Mn was adjusted to pH 10.5 and 200 ° C. at 6 atmospheres. When heated at, wavelength converted nanoparticles (ZnSeS: Mn) are produced.
この状態では、図５（Ｂ）に示すように、ＺｎＳｅＳ中に多くのＭｎが含まれるので、多数のＭｎが影響し合って発光が低減するいわゆる濃度消光によって、発光輝度が低下する。なお、濃度消光については、例えば”N.Pradhan,J.A.M.CHEM.SOC.129,11,2007,3339”に開示されている。 In this state, as shown in FIG. 5B, since a large amount of Mn is contained in ZnSeS, the emission luminance is lowered by so-called concentration quenching in which light emission is reduced by the influence of a large number of Mn. Concentration quenching is disclosed in, for example, “N. Pradhan, J. A. M. CHEM. SOC. 129, 11, 2007, 3339”.
その後、図５（Ｃ）に示すように、水溶液を酸素に晒すことにより、波長変換ナノ粒子（ＺｎＳｅＳ：Ｍｎ）中の過剰のＭｎが酸化して水溶液中に析出する。これによって、ＺｎＳｅＳ中のＭｎが少なくなるので、濃度消光の影響が低下し、よって、発光輝度が向上すると推定される。 Thereafter, as shown in FIG. 5C, by exposing the aqueous solution to oxygen, excess Mn in the wavelength conversion nanoparticles (ZnSeS: Mn) is oxidized and deposited in the aqueous solution. As a result, the amount of Mn in ZnSeS is reduced, so that the influence of concentration quenching is reduced, and it is estimated that the light emission luminance is improved.
次に、実施例３について説明するが、前記実施例２と同様な内容の説明は省略又は簡易化する。
本実施例では、波長変換ナノ粒子の製造方法は、前記実施例２と同様であるが、その後の輝度調整方法において、酸素を供給した後に炭酸ガスを供給した点が異なるので、異なる輝度調整方法について説明する。
Next, the third embodiment will be described, but the description of the same contents as the second embodiment will be omitted or simplified.
In this example, the method for producing wavelength-converting nanoparticles is the same as in Example 2. However, in the subsequent luminance adjustment method, the difference is that carbon dioxide gas is supplied after oxygen is supplied. Will be described.
具体的には、前記図３に示す様に、波長変換ナノ粒子が分散したｐＨ１０．５の水溶液を５ｍｌとり、容積１０ｍｌのガラス容器１に入れた後に、ガラス容器１をゴム栓７で封止する。 Specifically, as shown in FIG. 3, 5 ml of a pH 10.5 aqueous solution in which wavelength conversion nanoparticles are dispersed is taken and placed in a glass container 1 having a volume of 10 ml, and then the glass container 1 is sealed with a rubber stopper 7. To do.
その後、ゴム栓７に第２注射針１７を刺した後に、第１注射針１５を刺し、窒素ガスボンベ１３から第１注射針１５を介してガラス容器１内に窒素ガスを供給した。
次に、ガラス容器１のゴム栓７にマイクロシリングを差し込み、純酸素１００μｌ供給した。これにより、空間３内の酸素濃度を２％とした。
Thereafter, after the second injection needle 17 was inserted into the rubber stopper 7, the first injection needle 15 was inserted, and nitrogen gas was supplied into the glass container 1 from the nitrogen gas cylinder 13 through the first injection needle 15.
Next, microshilling was inserted into the rubber stopper 7 of the glass container 1, and 100 μl of pure oxygen was supplied. Thereby, the oxygen concentration in the space 3 was set to 2%.
そして、酸素を供給した後に、例えば１６日後に、空間３内に炭酸ガスを５分間供給した。これによって、水溶液のｐＨが（例えば７．０に）低下する。
このｐＨが低下すると、波長変換ナノ粒子中のＭｎが水溶液中に溶出するので、上述した濃度消光の影響が一層低減する。その結果、波長変換ナノ粒子の発光強度が向上する。
［実験例１］
次に、本発明の効果を確認するために行った実験例について説明する。
Then, after supplying oxygen, for example, 16 days later, carbon dioxide was supplied into the space 3 for 5 minutes. This reduces the pH of the aqueous solution (eg, to 7.0).
When this pH is lowered, Mn in the wavelength conversion nanoparticles elutes in the aqueous solution, so that the influence of the concentration quenching described above is further reduced. As a result, the emission intensity of the wavelength conversion nanoparticles is improved.
[Experiment 1]
Next, experimental examples conducted for confirming the effects of the present invention will be described.
本実験例１は、前記実施例２の輝度調整方法を用いて、酸素濃度と発光輝度（発光強度）の径時変化との関係を調べたものである。
具体的には、実施例２の方法で製造された波長変換ナノ粒子が分散した水溶液に対して、濃度が異なる酸素を加えた試料を作製した。
In this Experimental Example 1, the relationship between the oxygen concentration and the time-dependent change in emission luminance (emission intensity) was examined using the luminance adjustment method of Example 2.
Specifically, a sample was prepared by adding oxygen having different concentrations to the aqueous solution in which the wavelength conversion nanoparticles produced by the method of Example 2 were dispersed.
そして、各試料における発光強度（Ｍｎ発光ピーク強度：５８２ｎｍ）の径時変化を調べた。その結果を、図６に示す。
図６に示すように、酸素濃度２０％の試料は、酸素を供給してから４日後に発光強度のピークに達し、その後白濁した。
And the change with time of the emission intensity (Mn emission peak intensity: 582 nm) in each sample was examined. The result is shown in FIG.
As shown in FIG. 6, the sample having an oxygen concentration of 20% reached the peak of emission intensity after 4 days from the supply of oxygen, and then became cloudy.
また、酸素濃度１０％の試料は、酸素を供給してから８日後に発光強度のピークに達し、その後白濁した。なお、この試料の強度ピークは、酸素濃度２０％の試料の強度ピークよりも大きかった。 In addition, the sample having an oxygen concentration of 10% reached the peak of emission intensity 8 days after supplying oxygen, and then became cloudy. The intensity peak of this sample was larger than the intensity peak of the sample having an oxygen concentration of 20%.
更に、酸素濃度２％の試料は、酸素を供給してから２０日後に発光強度のピークに達し、その後白濁した。なお、この試料の強度ピークは、酸素濃度２０％、１０％の試料の強度ピークよりも大きかった。 Furthermore, the sample with an oxygen concentration of 2% reached the peak of the emission intensity 20 days after supplying oxygen, and then became cloudy. The intensity peak of this sample was larger than the intensity peak of the sample having an oxygen concentration of 20% and 10%.
この実験例から、酸素濃度の低いものは、発光強度の上昇率は小さいものの、最も大きな発光強度が得られることが分かる。
従って、最も高い発光強度の状態で、水溶液にプルランやポリ水酸化ビニル系等のバインダを加えて固化させることにより、その発光強度を維持することができる。
From this experimental example, it can be seen that the one having a low oxygen concentration has the highest emission intensity although the rate of increase in the emission intensity is small.
Therefore, the emission intensity can be maintained by adding a binder such as pullulan or polyvinyl hydroxide to the aqueous solution and solidifying it in the state of the highest emission intensity.
なお、各試料を入れた容器の底部に僅かに茶色の沈殿が見えられた。この沈殿を分析したところＭｎの酸化物であった。
［実験例２］
次に、他の実験例２について説明する。
A slightly brown precipitate was seen at the bottom of the container containing each sample. When this precipitate was analyzed, it was an oxide of Mn.
[Experiment 2]
Next, another experimental example 2 will be described.
本実験例は、水溶液に酸素を供給するだけでなく、酸素供給後に水溶液のｐＨを低下させ、その場合の発光強度の変化を調べたものである。
具体的には、実施例２の方法で製造された波長変換ナノ粒子が分散した水溶液に対して、酸素濃度２％となる試料を作製し、酸素の供給後１６日目に、水溶液に炭酸ガス（ＣＯ２）を５分間供給して封入した。これによって、水溶液のｐＨを低下させた。その結果を、図７に示すが、炭酸ガスの供給直後に発光強度が急上昇した。
In this experimental example, not only oxygen was supplied to the aqueous solution, but also the pH of the aqueous solution was lowered after the supply of oxygen, and the change in emission intensity in that case was examined.
Specifically, a sample having an oxygen concentration of 2% was prepared for the aqueous solution in which the wavelength conversion nanoparticles produced by the method of Example 2 were dispersed, and carbon dioxide gas was added to the aqueous solution on the 16th day after the supply of oxygen. (CO2) was supplied for 5 minutes and sealed. This lowered the pH of the aqueous solution. The result is shown in FIG. 7, and the emission intensity rapidly increased immediately after the supply of carbon dioxide gas.
これにより、酸素の供給に加えて、炭酸ガスを供給してｐＨを低下させることによって、発光強度を大きく向上できることが分かった。
なお、本実験例では、炭酸ガスを供給して水溶液のｐＨを低回させたが、これとは別に、水溶液に、例えばＨＣｌ等の酸性溶液を加えたり、純水を加えて希釈することにより、ｐＨを低下させてもよい。
Thus, it has been found that the emission intensity can be greatly improved by lowering the pH by supplying carbon dioxide in addition to supplying oxygen.
In this experimental example, carbon dioxide gas was supplied to lower the pH of the aqueous solution, but separately from this, by adding an acidic solution such as HCl or diluting pure water to the aqueous solution. The pH may be lowered.
尚、本発明は前記実施例になんら限定されるものではなく、本発明を逸脱しない範囲において種々の態様で実施しうることはいうまでもない。
（１）例えば、上記各実施例では、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。また、ＳまたはＳｅと、Ｍｎと、Ｚｎとは、どういう順番で混ぜてもよい。
Needless to say, the present invention is not limited to the above-described embodiments, and can be implemented in various modes without departing from the scope of the present invention.
(1) For example, in each of the above embodiments, Zn and Mn are used as cations, but the type of cation can be variously changed, such as using Cd instead of Mn. Further, S or Se, Mn, and Zn may be mixed in any order.
（２）また、本発明の輝度調整方法は、例えば上述した非特許文献１に記載の製造方法で製造された波長変換ナノ粒子の輝度調整にも利用することができる。 (2) Moreover, the brightness | luminance adjustment method of this invention can be utilized also for the brightness | luminance adjustment of the wavelength conversion nanoparticle manufactured with the manufacturing method of the nonpatent literature 1 mentioned above, for example.
１…ガラス容器
３…空間
５…開口
７…ゴム栓
９…ｐＨ測定器
DESCRIPTION OF SYMBOLS 1 ... Glass container 3 ... Space 5 ... Opening 7 ... Rubber stopper 9 ... pH meter
Claims (8)
Ｎ−アセチル−Ｌ−システインと発光中心となるＭｎイオンとを１：１のモル比で含む溶液と、Ｎ−アセチル−Ｌ−システインと無機ナノ粒子を構成するＺｎ原子とを１：４．８のモル比で含む溶液とを、水系溶媒で混合し、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高圧下で１５０℃〜２５０℃に加熱して、前記溶液中にて波長変換ナノ粒子を生成する加熱工程と、
を有し、
前記加熱工程の後に、前記波長変換ナノ粒子が分散した溶液に、酸素を含むガスを供給することを特徴とする波長変換ナノ粒子の輝度調整方法。 As a manufacturing process to manufacture wavelength conversion nanoparticles,
A solution containing N-acetyl-L-cysteine and Mn ions serving as a luminescent center in a molar ratio of 1: 1, and N-acetyl-L-cysteine and Zn atoms constituting the inorganic nanoparticles are 1: 4.8. A mixing step of adjusting the pH of the solution obtained by mixing the solution containing the molar ratio of
Heating the pH-adjusted solution to 150 ° C. to 250 ° C. under high pressure to produce wavelength conversion nanoparticles in the solution; and
Have
After the said heating process, the gas containing oxygen is supplied to the solution in which the said wavelength conversion nanoparticle was disperse | distributed, The brightness | luminance adjustment method of the wavelength conversion nanoparticle characterized by the above-mentioned.
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Ｎ−アセチル−Ｌ−システインと、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Ｎ−アセチル−Ｌ−システインと、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、
前記発光中心となるＭｎイオン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１〜７のいずれか１項に記載の波長変換ナノ粒子の輝度調整方法。 As atoms constituting the inorganic nanoparticles, S and Se are included,
The mixing step includes
The ion source that provides each atom other than Se constituting the inorganic nanoparticles and the N-acetyl-L-cysteine are mixed in an aqueous solvent, and the pH of the resulting solution is adjusted. One mixing step,
The ion source that provides each atom other than S constituting the inorganic nanoparticles and the N-acetyl-L-cysteine are mixed in an aqueous solvent, and the pH of the resulting solution is adjusted. Two mixing steps;
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
Ion source to provide a Mn ions of the luminescent center, according to any one of claims 1 to 7, characterized in that it is mixed with the said solution in the first mixing step or the second mixing step Brightness adjustment method of wavelength conversion nanoparticle.
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