JP2014019759A - Brightness control method of wavelength conversion nano-particle, and wavelength conversion nano-particle - Google Patents
Brightness control method of wavelength conversion nano-particle, and wavelength conversion nano-particle Download PDFInfo
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Abstract
Description
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、及び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に関する。 The present invention relates to a method for adjusting the brightness of wavelength-converting nanoparticles capable of improving the brightness (light-emitting brightness) of wavelength-converting nanoparticles that generate light having a wavelength different from that of absorbed light, and the brightness-adjusting brightness of the wavelength-converting nanoparticles by this brightness-adjusting method. It relates to tuned wavelength conversion nanoparticles.
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及び波長変換ナノ粒子を提供することにある。 The present invention has been made to solve the above-mentioned problems, and the object thereof is to provide a method for adjusting the brightness of wavelength-converted nanoparticles and the wavelength capable of further increasing the light-emission brightness of the wavelength-converted nanoparticles in the produced solution. It is to provide conversion nanoparticles.
本発明の波長変換ナノ粒子の輝度調整方法では、特定の波長の光を発生する発光中心となる金属イオンを無機ナノ粒子にドープした波長変換ナノ粒子を、所定のｐＨに調整した溶液中にて製造した後に、その波長変換ナノ粒子が分散した溶液のｐＨを、製造時の所定のｐＨよりも低下させるｐＨ低下処理を行う。 In the method of adjusting the brightness of the wavelength conversion nanoparticle of the present invention, the wavelength conversion nanoparticle doped with a metal ion serving as a light emission center for generating light of a specific wavelength in an inorganic nanoparticle is adjusted in a solution adjusted to a predetermined pH. After the production, a pH lowering treatment is performed to lower the pH of the solution in which the wavelength conversion nanoparticles are dispersed to a predetermined pH at the time of production.
このｐＨ低下処理を行うことによって、後述する実験例からも明かな様に、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、ｐＨを低下させ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ｐＨ低下処理を行うことによって、波長変換ナノ粒子から溶液中に金属イオンを析出させ、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。
By performing this pH reduction treatment, the emission luminance of the wavelength conversion nanoparticles can be improved from the emission luminance at the time of manufacture, as is apparent from the experimental examples described later.
As described above, the reason why the emission luminance is improved by lowering the pH is that the wavelength conversion nanoparticles dispersed in the solution have a low emission luminance due to concentration quenching, as will be described in detail later. It is presumed that by performing a pH lowering treatment on this solution, metal ions are precipitated in the solution from the wavelength conversion nanoparticles, thereby reducing the influence of concentration quenching.
従って、この様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 in this way and whose emission luminance is increased are applied to, for example, a solar cell, the efficiency of the solar cell can be improved by converting ultraviolet rays into visible light. 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、製造時におけるｐＨが例えば９〜１１の溶液に対して、ｐＨ低下処理によって、溶液のｐＨを例えば６〜８の範囲に低下させることができる。これにより、後述する実験例から明かな様に、製造時における波長変換ナノ粒子の発光輝度を大きく向上することができる。
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 this invention, pH of a solution can be reduced to the range of 6-8, for example with the pH reduction process with respect to the solution of pH 9-9 at the time of manufacture, for example. Thereby, as will be apparent from the experimental examples described later, the emission luminance of the wavelength conversion nanoparticles during production can be greatly improved.
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 (for example, 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.
更に、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。 Furthermore, Mn ions can be employed as the metal ions that serve as the emission center, and Zn can be included 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.
・また、波長変換ナノ粒子を製造した後に、溶液中又はその周囲に、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。 In addition, after the wavelength conversion nanoparticles are manufactured, an inert gas such as argon (Ar) gas or nitrogen (N 2 ) gas is supplied in or around the solution, and then pH reduction treatment is performed. Good. Since the luminance fluctuation can be suppressed by supplying the inert gas, the luminance can be maintained until the pH lowering process is performed.
・更に、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、ガラスをバインダー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。 Furthermore, when the above-described luminance variation of the wavelength conversion nanoparticles is completely stopped and the luminance is maintained, the solution in which the wavelength conversion nanoparticles are dispersed may be solidified. Examples of the solidification method include a sol-gel method using glass as a binder and a method of mixing and solidifying in polyvinyl hydroxide.
・また、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。 In addition, 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）に示す様に、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）に示す様に、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）に示す様に、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、図１（Ｄ）に示す様に、前記水溶液に更にＮａＯＨを添加することによって、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, as shown in FIG. 1 (D), the pH is adjusted to 10.5 by further adding NaOH to the aqueous solution, and then heated to 200 ° C. under high pressure (for example, 6 atmospheres) to convert the wavelength. 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.
このように、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, extremely strong emission luminance (emission intensity) was obtained compared to the wavelength conversion nanoparticle produced in the conventional aqueous solvent. 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、炭酸ガス（ＣＯ2）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 carbon dioxide gas (CO 2 ).
まず、図３（Ａ）に示す様に、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. 3 (A), 5 ml of an aqueous solution containing the wavelength conversion nanoparticles produced by the production method described above, that is, an aqueous solution having a pH of 10.5 in which the wavelength conversion nanoparticles are dispersed, is taken and 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）に示す様に、炭酸ガスボンベ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）に示す様に、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 carbon dioxide cylinder 11, and the first injection needle 15 was attached to the tip of the pipe 13.
Then, as shown in FIG. 3C, the second injection needle 17 was inserted into the rubber stopper 7 of the glass container 1 so that the gas in the glass container 3 was discharged out of the glass container 1.
次に、図３（Ｄ）に示す様に、ガラス容器１のゴム栓７に第１注射針１５を刺し、炭酸ガスボンベ１３から第１注射針１５を介してガラス容器１内に炭酸ガスを供給した。詳しくは、炭酸ガスを毎分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）を炭酸ガスに入れ替えた。 Next, as shown in FIG. 3 (D), the first injection needle 15 is inserted into the rubber stopper 7 of the glass container 1, and carbon dioxide gas is supplied from the carbon dioxide gas cylinder 13 into the glass container 1 through the first injection needle 15. did. Specifically, carbon dioxide 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 carbon dioxide.
この状態で、水溶液のｐＨの変化を測定したところ、炭酸ガスを注入してから徐々にｐＨが低下し、炭酸ガスの注入から５分後に、溶液のｐＨが７．０となった。
そこで、このｐＨ７．０となった水溶液に対して、前記と同様にして、蛍光分光測定器を用いて、波長変換ナノ粒子の発光スペクトルを調べた。
When the change in pH of the aqueous solution was measured in this state, the pH gradually decreased after the carbon dioxide gas was injected, and the pH of the solution became 7.0 5 minutes after the carbon dioxide gas was injected.
Therefore, the emission spectrum of the wavelength-converted nanoparticles was examined with respect to this aqueous solution having a pH of 7.0 using a fluorescence spectrometer in the same manner as described above.
その結果、ｐＨを７．０に低下させ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、約1．４倍であり（図６参照）、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向上していた。なお、図６は、ｐＨ７．５に調整した例であるが、同様に大きく発光強度が向上する。 As a result, the emission intensity (specifically, the emission peak intensity at 582 nm) of the wavelength conversion nanoparticles in the solution whose pH was lowered to 7.0 was about 1.4 times (see FIG. 6). Compared with the wavelength-converted nanoparticles immediately after production in the aqueous solution No. 5 were greatly improved. FIG. 6 shows an example in which the pH is adjusted to 7.5. Similarly, the emission intensity is greatly improved.
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、上述した様に、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 this example, as described above, in the wavelength conversion nanoparticle production process, the pH is adjusted to pH 10.5, which is higher than the conventional one, and then treated at high pressure (for example, 6 atm) and high temperature (for example, 200 ° C.). As a result, the emission luminance can be increased as compared with the prior art.
特に本実施例では、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炭酸ガスを供給することにより、水溶液のｐＨを（例えばｐＨ７．０に）低下させるので、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。 In particular, in this embodiment, after the wavelength conversion nanoparticles are produced, the pH of the aqueous solution is lowered (for example, to pH 7.0) by supplying carbon dioxide gas to the aqueous solution in which the wavelength conversion nanoparticles are dispersed. As is clear from the experimental examples, the emission luminance of the wavelength conversion nanoparticles immediately after production 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。
前述の様に、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 when Se is used as the anion constituting the inorganic nanoparticles and when S is used.
そこで、本実施例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 a so-called mixed crystal semiconductor 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様に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 steps of FIGS. 1A and 1B described above, and in place of Se as described above in the steps 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５８７ｎｍ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 587 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、炭酸ガスボンベ１３から第１注射針１５を介してガラス容器１内に炭酸ガスを供給した。
この状態で、ｐＨの変化を測定したところ、炭酸ガスの注入から５分後に、溶液のｐＨが７．０となった。
Thereafter, after the second injection needle 17 was inserted into the rubber stopper 7, the first injection needle 15 was inserted, and carbon dioxide gas was supplied from the carbon dioxide gas cylinder 13 into the glass container 1 through the first injection needle 15.
When the change in pH was measured in this state, the pH of the solution became 7.0 after 5 minutes from the injection of carbon dioxide gas.
そこで、このｐＨ７．０となった水溶液に対して、前記と同様にして、蛍光分光測定器を用いて、波長変換ナノ粒子の発光スペクトルを調べた。
その結果、ｐＨを７．０に低下させた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、約８００００（図７参照）であり、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向上していた。
Therefore, the emission spectrum of the wavelength-converted nanoparticles was examined with respect to this aqueous solution having a pH of 7.0 using a fluorescence spectrometer in the same manner as described above.
As a result, the emission intensity (specifically, the emission peak intensity at 587 nm) of the wavelength conversion nanoparticles in the solution whose pH was lowered to 7.0 was about 80000 (see FIG. 7), and the aqueous solution with pH 10.5. It was greatly improved compared to the wavelength-converted nanoparticles immediately after production.
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）ここで、上述したｐＨ低下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) Here, the principle by which the light emission luminance can be increased by the above-described pH lowering process 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）に示す様に、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 reduced 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）に示す様に、水溶液を例えば炭酸ガスに晒すことによりｐＨを低下させると、ＺｎＳｅＳから過剰のＭｎが水溶液中に溶け出す。なお、Ｍｎが水溶液中に溶け出す理由は、Ｍｎは、酸（希酸）や中性など、（高アルカリに比べて）酸性に近い方が溶出し易い特性があると考えられるからである。 Thereafter, as shown in FIG. 5C, when the pH is lowered by exposing the aqueous solution to, for example, carbon dioxide gas, excess Mn is dissolved from the ZnSeS into the aqueous solution. The reason why Mn is dissolved in the aqueous solution is that Mn is considered to have a characteristic that it is more likely to be eluted when it is close to acidity (compared to high alkali) such as acid (dilute acid) or neutrality.
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。 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、炭酸ガスではなく塩酸（ＨＣｌ）を用いる点が異なるので、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.
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 hydrochloric acid (HCl) is used instead of carbon dioxide gas. Will be described.
まず、前記実施例２と同様な製造方法で波長変換ナノ粒子（ＺｎＳｅＳ：Ｍｎ）を作製し、その波長変換ナノ粒子が分散した水溶液を、５ｍｌ容器に投入した。
そして、その水溶液をスターラーバーで回転させながら、１ＮのＨＣｌを１０μｌ投入して混合した。
First, wavelength conversion nanoparticles (ZnSeS: Mn) were produced by the same production method as in Example 2, and an aqueous solution in which the wavelength conversion nanoparticles were dispersed was put into a 5 ml container.
Then, 10 μl of 1N HCl was added and mixed while rotating the aqueous solution with a stirrer bar.
次に、混合した水溶液のｐＨを測定した。
そして、前記ＨＣｌの投入とｐＨの測定とを繰り返し、目標のｐＨ（例えばｐＨ７．０）に達した時点で、その処理を終了した。
Next, the pH of the mixed aqueous solution was measured.
Then, the introduction of HCl and the measurement of pH were repeated, and when the target pH (for example, pH 7.0) was reached, the treatment was terminated.
このｐＨ低下処理の後に、ｐＨ７．０の水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）を調べたところ、約１．４倍であり（図６参照）、ｐＨが１０．５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向上していた。 After this pH lowering treatment, when the emission intensity of the wavelength conversion nanoparticles in the aqueous solution of pH 7.0 (specifically, the emission peak intensity at 582 nm) was examined, it was about 1.4 times (see FIG. 6). Compared with the wavelength-converted nanoparticles immediately after production in an aqueous solution having a pH of 10.5, it was greatly improved.
なお、この方法では、ＨＣｌの濃度を希釈することにより、ｐＨを微調整することができる。しかし、そうすると、投入量が多くなり、最初の波長変換ナノ粒子（ＺｎＳｅＳ：Ｍｎ）濃度が希釈されてしまうので、高濃度に保つには、高濃度のＨＣｌを用いた方が有利である。 In this method, the pH can be finely adjusted by diluting the concentration of HCl. However, if it does so, since the input amount will increase and the initial wavelength conversion nanoparticle (ZnSeS: Mn) density | concentration will be diluted, in order to keep high concentration, it is more advantageous to use high concentration HCl.
本実施例においては、塩酸によるｐＨ低下処理によって輝度調整された波長変換ナノ粒子は、実施例１より一層良好な発光輝度を有しているので、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。 In the present example, the wavelength-converted nanoparticles whose brightness is adjusted by the pH lowering treatment with hydrochloric acid have a light emission brightness that is better than that of Example 1, so that the efficiency can be further improved if applied to solar cells and the like. Be made.
次に、実施例４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、炭酸ガスではなく純水（Ｈ2Ｏ）を用いて希釈する点が異なるので、異なる輝度調整方法について説明する。
Next, the fourth embodiment will be described, but the description of the same contents as the second embodiment will be omitted.
In this example, the method for producing wavelength-converting nanoparticles is the same as that in Example 2, except that in the subsequent luminance adjustment method, dilution is performed using pure water (H 2 O) instead of carbon dioxide. Therefore, different brightness adjustment methods will be described.
まず、前記実施例２と同様な製造方法で波長変換ナノ粒子（ＺｎＳｅＳ：Ｍｎ）を作製し、その波長変換ナノ粒子が分散した水溶液を、５ｍｌ容器に投入した。
そして、その水溶液をスターラーバーで回転させながら、純水を１０μｌ投入して混合し希釈した。
First, wavelength conversion nanoparticles (ZnSeS: Mn) were produced by the same production method as in Example 2, and an aqueous solution in which the wavelength conversion nanoparticles were dispersed was put into a 5 ml container.
Then, while rotating the aqueous solution with a stirrer bar, 10 μl of pure water was added, mixed and diluted.
次に、希釈した水溶液のｐＨを測定した。
そして、前記純水の投入とｐＨの測定とを繰り返し、目標のｐＨ（例えばｐＨ７．０）に達した時点で、その処理を終了した。
Next, the pH of the diluted aqueous solution was measured.
Then, the introduction of the pure water and the measurement of the pH were repeated, and when the target pH (for example, pH 7.0) was reached, the treatment was terminated.
このｐＨ低下処理の後に、ｐＨ７．０の水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）を調べたところ、約３倍（図８の１００倍希釈）であり、ｐＨが１０．５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向上していた。 After this pH lowering treatment, the emission intensity (specifically, the emission peak intensity at 582 nm) of the wavelength conversion nanoparticles in an aqueous solution of pH 7.0 was examined, and was about 3 times (100 times dilution in FIG. 8). As compared with the wavelength conversion nanoparticles immediately after the production in an aqueous solution having a pH of 10.5, it was greatly improved.
本実施例においては、希釈によるｐＨ低下処理によって輝度調整された波長変換ナノ粒子は、実施例１より一層良好な発光輝度を有しているので、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。
［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１について説明する。
In this example, the wavelength-converted nanoparticles whose brightness is adjusted by the pH reduction treatment by dilution have a better light emission brightness than that of Example 1, so that the efficiency can be further improved if applied to solar cells and the like. Be made.
[Experimental Example 1]
Next, Experimental Example 1 performed for confirming the effect of the present invention will be described.
本実験例は、前記実施例２の輝度調整方法を用いて、ｐＨ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（Ｚｎ：Ｓｅ：Ｓ：Ｍｎ＝１：０．３：ｘ：０．０５、ｘ＝０．３）が分散した水溶液（ｐＨ１０．５）に対して、最初に窒素ガスを封入し、１日後に窒素ガスとアルゴンガスとを入れ換えた。
In this experimental example, the relationship between pH and time-dependent change in emission luminance (emission intensity) was examined using the luminance adjustment method of Example 2.
Specifically, an aqueous solution in which wavelength conversion nanoparticles (Zn: Se: S: Mn = 1: 0.3: x: 0.05, x = 0.3) produced by the method of Example 2 are dispersed ( With respect to pH 10.5), nitrogen gas was first sealed, and nitrogen gas and argon gas were replaced after one day.
次に、製造から６日後に、アルゴンガスに換えて炭酸ガスを封入し、水溶液のｐＨ１０．５を、ｐＨ７．５に低下させた。
そして、上述した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。
Next, 6 days after the production, carbon dioxide gas was sealed instead of argon gas, and the pH of the aqueous solution was lowered to pH 7.5.
Then, the change with time in the emission intensity (Mn emission peak intensity: 582 nm) in the above-described sample was examined. The result is shown in FIG.
図６に示す様に、ｐＨ７．５に調整した試料の発光強度は、ｐＨを低下させた直後に大きく上昇し、その後徐々に大きくなった。なお、白濁は生じなかった。
この実験から、製造直後に窒素ガス（又はアルゴンガス）を充填した場合は、発光強度が維持され殆ど低下しないことが分かった。
As shown in FIG. 6, the emission intensity of the sample adjusted to pH 7.5 increased greatly immediately after the pH was lowered, and then gradually increased. In addition, white turbidity did not arise.
From this experiment, it was found that when nitrogen gas (or argon gas) was filled immediately after production, the emission intensity was maintained and hardly decreased.
また、その後、アルゴンガスを炭酸ガスに入れ換えてｐＨをｐＨ７．５に低下させると、発光強度が大きく上昇することが分かった。
［実験例２］
次に、本発明の効果を確認するために行った実験例２について説明する。
Further, it was found that when the argon gas was replaced with carbon dioxide gas and the pH was lowered to pH 7.5, the emission intensity increased greatly.
[Experiment 2]
Next, Experimental Example 2 performed to confirm the effect of the present invention will be described.
本実験例は、前記実施例３の輝度調整方法を用いて、ｐＨ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３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、塩酸を加えることによって、その水溶液のｐＨ１０．５を、ｐＨ８、ｐＨ７、ｐＨ６に低下させた試料を作製した。また、比較例として、塩酸を加えない試料も作製した。
In this experimental example, the relationship between the pH and the time-dependent change in emission luminance (emission intensity) was examined using the luminance adjustment method of Example 3.
Specifically, a sample in which pH 10.5 of the aqueous solution was lowered to pH 8, pH 7, and pH 6 by adding hydrochloric acid to the aqueous solution in which the wavelength conversion nanoparticles produced by the method of Example 3 were dispersed. Was made. Moreover, the sample which does not add hydrochloric acid as a comparative example was also produced.
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７に示す。
図７に示す様に、ｐＨ８、ｐＨ７、ｐＨ６の試料の発光強度は、ｐＨを低下させた直後に大きく上昇し、その後徐々に大きくなり、約３０日後にほぼ上限に達した。
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. 7, the luminescence intensity of the samples of pH 8, pH 7, and pH 6 increased greatly immediately after the pH was lowered, then gradually increased, and reached the almost upper limit after about 30 days.
このうち、特にｐＨ６の試料は、最初に発光強度が最も大きく上昇し、その後もｐＨ８、ｐＨ７の試料に比べて発光強度が大きかった。
それに対して、ｐＨ１０、５の比較例の試料は、６日〜１０日は、急激に発光強度が上昇するが、１０日を過ぎると発光強度が低下し、白濁した。
Among these samples, particularly, the pH 6 sample showed the largest increase in emission intensity at first, and thereafter, the emission intensity was higher than that of the pH 8 and pH 7 samples.
On the other hand, in the samples of Comparative Examples having pH of 10 and 5, the emission intensity rapidly increased from 6 to 10 days, but after 10 days, the emission intensity decreased and became cloudy.
この実験から、製造直後のｐＨよりもｐＨをｐＨ６〜８に低下させたものは、発光強度の上昇が大きく、しかも、長時間（２ヶ月以上）経過した場合でも、発光強度の低下が見られず、好適であった。 From this experiment, when the pH was lowered to pH 6-8 from the pH immediately after production, the emission intensity increased greatly, and the emission intensity decreased even after a long time (two months or more). It was suitable.
なお、本実験例では、製造時のｐＨを１０．５としたが、本発明者等の研究によれば、製造時のｐＨを９〜１１とした場合でも、同様な効果が得られることが分かっている。
［実験例３］
次に、他の実験例３について説明する。
In this experimental example, the pH at the time of production was set to 10.5. However, according to the study by the present inventors, the same effect can be obtained even when the pH at the time of production is set to 9 to 11. I know.
[Experiment 3]
Next, another experimental example 3 will be described.
本実験例は、前記実施例４の輝度調整方法を用いて、ｐＨと輝度の径時変化との関係を調べたものである。
具体的には、実験に用いる原液として、前記実施例３の製造方法によって、波長変換ナノ粒子（Ｚｎ：Ｓｅ：Ｓ：Ｍｎ＝１：０．３：０．３：０．０５）が分散した水溶液を作製するとともに、前記実施例３と同様にして、１ＮＨＣｌを加えることによってｐＨ７．０の水溶液とした。
In this experimental example, the relationship between pH and luminance change with time was examined using the luminance adjustment method of Example 4.
Specifically, wavelength conversion nanoparticles (Zn: Se: S: Mn = 1: 0.3: 0.3: 0.05) were dispersed by the manufacturing method of Example 3 as a stock solution used in the experiment. An aqueous solution was prepared, and an aqueous solution having a pH of 7.0 was obtained by adding 1N HCl in the same manner as in Example 3.
そして、この水溶液に対して、ｐＨ７．０のＨＣｌ溶液を用いて、１倍、２倍、５倍、１０倍、１００倍、２００倍に希釈した。
そして、各希釈溶液を、超純水を用いて薄めて、原液の２００倍となるように調整し（即ち波長変換ナノ粒子の濃度が揃うように調整し）、前記と同様に発光強度（Ｍｎ発光ピーク強度：５８２ｎｍ）を調べた。その結果を、図８に示す。なお、図８は、超純水を加えて調整してからの発光強度の経時変化を示す。
And this aqueous solution was diluted 1 time, 2 times, 5 times, 10 times, 100 times, and 200 times using a pH 7.0 HCl solution.
Then, each diluted solution is diluted with ultrapure water and adjusted to be 200 times that of the stock solution (that is, adjusted so that the concentrations of the wavelength conversion nanoparticles are uniform). Emission peak intensity: 582 nm). The result is shown in FIG. In addition, FIG. 8 shows the time-dependent change of the emitted light intensity after adjusting by adding ultrapure water.
この図８から、希釈の程度が大きいほど、発光強度が上昇しているのが分かる。
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。
It can be seen from FIG. 8 that the emission intensity increases as the degree of dilution increases.
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）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。 (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などの輝度調整にも利用することができる。
つまり、所定のｐＨ値の溶液中で製造された波長変換ナノ粒子に対して、上述したｐＨ低下処理を行うことにより、発光輝度を向上させることができる。
(2) Moreover, the brightness | luminance adjustment method of this invention can be utilized also for brightness | luminance adjustment of the wavelength conversion nanoparticle etc. which were manufactured with the manufacturing method of the nonpatent literature 1 mentioned above, for example.
That is, the emission luminance can be improved by performing the above-described pH reduction treatment on the wavelength conversion nanoparticles produced in a solution having a predetermined pH value.
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 (13)
前記波長変換ナノ粒子が分散した溶液のｐＨを、前記製造時の所定のｐＨよりも低下させるｐＨ低下処理を行うことを特徴とする波長変換ナノ粒子の輝度調整方法。 After producing wavelength-converting nanoparticles in which inorganic nanoparticles are doped with metal ions that are emission centers that generate light of a specific wavelength, in a solution adjusted to a predetermined pH,
A method for adjusting the brightness of wavelength-converted nanoparticles, comprising performing a pH lowering process for lowering the pH of the solution in which the wavelength-converted nanoparticles are dispersed to a predetermined pH at the time of production.
前記発光中心となる金属イオンを提供するイオン源と、前記無機ナノ粒子を構成する原子を提供するイオン源と、前記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、
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、
を有することを特徴とする請求項１〜８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 a manufacturing process for manufacturing the wavelength conversion nanoparticles,
In an aqueous solvent, an ion source that provides a metal ion serving as the emission center, an ion source that provides an atom constituting the inorganic nanoparticle, and a hydrophilic ligand that coordinates to the inorganic nanoparticle. A mixing step of mixing and adjusting the pH of the resulting solution;
Heating the pH-adjusted solution to 150 ° C. to 250 ° C. under high pressure to produce wavelength conversion nanoparticles in the solution; and
The method for adjusting the luminance of wavelength-converted nanoparticles according to any one of claims 1 to 8, wherein:
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、
前記発光中心となる金属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９〜１１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
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
12. The ion source that provides the metal ion serving as the light emission center is mixed into the solution in the first mixing step or the second mixing step. 12. Brightness adjustment method of wavelength conversion nanoparticle.
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Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2004285233A (en) * | 2003-03-24 | 2004-10-14 | Sumitomo Chem Co Ltd | Process for producing fluorescent substance |
| JP2004352594A (en) * | 2003-05-30 | 2004-12-16 | Hitachi Software Eng Co Ltd | Nanoparticle production method, and nanoparticle produced by the method |
| JP2005306713A (en) * | 2003-10-22 | 2005-11-04 | Fuji Photo Film Co Ltd | Method of producing inorganic semiconductor- or phosphor-primary particle and inorganic semiconductor- or phosphor-primary particle |
| US20080102201A1 (en) * | 2006-10-30 | 2008-05-01 | Samsung Electronics Co., Ltd. | Method For Dispersing Nanoparticles and Methods for Producing Nanoparticle Thin Films By Using The Same |
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Patent Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2004285233A (en) * | 2003-03-24 | 2004-10-14 | Sumitomo Chem Co Ltd | Process for producing fluorescent substance |
| JP2004352594A (en) * | 2003-05-30 | 2004-12-16 | Hitachi Software Eng Co Ltd | Nanoparticle production method, and nanoparticle produced by the method |
| EP1491502A2 (en) * | 2003-05-30 | 2004-12-29 | Hitachi Software Engineering Co., Ltd. | A method for producing nanoparticles through size-selective photoetching |
| US20070065665A1 (en) * | 2003-05-30 | 2007-03-22 | Hitachi Software Engineering Co., Ltd. | Nanoparticles and production thereof |
| JP2005306713A (en) * | 2003-10-22 | 2005-11-04 | Fuji Photo Film Co Ltd | Method of producing inorganic semiconductor- or phosphor-primary particle and inorganic semiconductor- or phosphor-primary particle |
| US20080102201A1 (en) * | 2006-10-30 | 2008-05-01 | Samsung Electronics Co., Ltd. | Method For Dispersing Nanoparticles and Methods for Producing Nanoparticle Thin Films By Using The Same |
| JP2008111187A (en) * | 2006-10-30 | 2008-05-15 | Samsung Electronics Co Ltd | Method for dispersing nanoparticle, and method for producing nanoparticle thin film using the same |
Non-Patent Citations (2)
| Title |
|---|
| JPN6014044092; Ｊｏｕｒｎａｌ ｏｆ Ｐｈｙｓｉｃａｌ Ｃｈｅｍｉｓｔｒｙ Ｃ Ｖｏｌ．１１３（２００９）， ｐｐ．１２９３-１３００, 2009 * |
| JPN6015044946; 門毅、神原満彦: '無公害高効率半導体ナノ発光体の開発' １１月度ＮＢＭＦの概要 , 20051116, ＮＢＣＩ イノベーションエンジン（株）、（株）シナジッ * |
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