JP6569566B2 - Method for producing CdSe colloidal particles - Google Patents
Method for producing CdSe colloidal particles Download PDFInfo
- Publication number
- JP6569566B2 JP6569566B2 JP2016045060A JP2016045060A JP6569566B2 JP 6569566 B2 JP6569566 B2 JP 6569566B2 JP 2016045060 A JP2016045060 A JP 2016045060A JP 2016045060 A JP2016045060 A JP 2016045060A JP 6569566 B2 JP6569566 B2 JP 6569566B2
- Authority
- JP
- Japan
- Prior art keywords
- liquid
- raw material
- cdse
- particles
- material liquid
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Active
Links
Images
Description
本発明は、光ルミネセンス材料の一種の可視発光コロイド粒子であるＣｄＳｅコロイド粒子を製造する方法に関する。 The present invention relates to a method for producing CdSe colloidal particles, which are a kind of visible light emitting colloidal particles of a photoluminescent material.
１９８０年代初期に量子サイズ効果の概念が導入されて以来、ＣｄＳｅ（セレン化カドミウム）コロイド粒子は無機半導体ナノ粒子の中で最も研究されてきたナノ結晶である。高品質のＣｄＳｅコロイド粒子を作るために、非常に成功した製造方法が確立している（例えば、非特許文献１参照。）。非特許文献１に示される方法は、Ｓｅ（セレン）とアルキルホスフィンとの間で前駆体を作るために、アルキルホスフィンとして、トリオクチルホスフィン（ＴＯＰ）又はトリブチルホスフィン（ＴＢＰ）を用いている。 Since the concept of quantum size effect was introduced in the early 1980s, CdSe (cadmium selenide) colloidal particles are the most studied nanocrystals among inorganic semiconductor nanoparticles. In order to produce high-quality CdSe colloidal particles, a very successful production method has been established (for example, see Non-Patent Document 1). The method shown in Non-Patent Document 1 uses trioctylphosphine (TOP) or tributylphosphine (TBP) as the alkylphosphine in order to make a precursor between Se (selenium) and alkylphosphine.
しかしながら、ＴＯＰとＴＢＰは有害で化学的に不安定な物質であり、しかも高価な材料であるため、商業化の大きな負荷となっていた。この点を改良するために、非特許文献１に示されたコロイドの品質を維持しつつ、環境負荷が低くかつ高価でない溶媒であるオクタデシルアミン（ＯＤＡ）とオクタデセン（ＯＤＥ）を用いたＣｄＳｅコロイド粒子の製造方法が開示されている（例えば、非特許文献２参照。）。 However, TOP and TBP are harmful and chemically unstable substances, and are expensive materials, which have been a heavy burden for commercialization. In order to improve this point, CdSe colloidal particles using octadecylamine (ODA) and octadecene (ODE), which are low environmental impact and inexpensive solvents, while maintaining the quality of the colloid shown in Non-Patent Document 1. Is disclosed (for example, see Non-Patent Document 2).
一般的に、可視発光コロイド粒子であるコロイド蛍光体では、発光波長を精密に制御することが重要であって、量子サイズ効果の原理に従うと、それはＣｄＳｅコロイド粒子の粒径を精密に制御することにある。非特許文献２の方法では、所定のＳｅ−ＯＤＡ錯体を形成したＳｅ原料液を利用して、反応時間を変えることにより、ＣｄＳｅコロイド粒子の粒径を制御していた。しかしながら、この方法では、安定したＳｅ原料液を用いているため、量子効率が高い微小な粒径のＣｄＳｅコロイド粒子を得るには反応時間を数秒間という極めて短い時間にする必要があった。このためこの方法では、Ｃｄ−Ｓｅ原料に対して、得られるＣｄＳｅコロイド粒子の収量が低い上、ＣｄＳｅ結晶の質が低くなり高い量子効率を得ることが難しい問題点があった。 In general, in the colloidal phosphor that is a visible light-emitting colloidal particle, it is important to precisely control the emission wavelength, and according to the principle of the quantum size effect, it can precisely control the particle size of the CdSe colloidal particle. It is in. In the method of Non-Patent Document 2, the particle size of CdSe colloidal particles is controlled by changing the reaction time using a Se raw material liquid in which a predetermined Se-ODA complex is formed. However, in this method, since a stable Se raw material solution is used, in order to obtain CdSe colloidal particles having a small particle size with high quantum efficiency, it was necessary to set the reaction time to an extremely short time of several seconds. For this reason, in this method, the yield of CdSe colloidal particles obtained is low with respect to the Cd—Se raw material, and the quality of the CdSe crystal is low, so that it is difficult to obtain high quantum efficiency.
本発明の目的は、粒径が１〜６ｎｍであってフォトルミネッセンス・スペクトル（以下、「ＰＬスペクトル」という。）のピークにおける半値幅が３０ｎｍ以下である、量子効率が高い高品質のＣｄＳｅコロイド粒子を高い収量で製造する方法を提供することにある。 An object of the present invention is a high-quality CdSe colloidal particle having a high quantum efficiency, having a particle size of 1 to 6 nm and a half-value width of 30 nm or less at the peak of a photoluminescence spectrum (hereinafter referred to as “PL spectrum”). Is to provide a method of producing a high yield.
本発明者らは、数時間かけてＳｅとＯＤＡが錯形態を変化させながら所定の平衡状態の錯形態に到達するＳｅ原料液を、平衡状態に達していないエネルギー的に不安定な段階で、Ｃｄ原料液と混合すると、合成初期で合成液中のＣｄ−Ｓｅの原料が多量に消費され、ＣｄＳｅコロイド核の生成数が多くなり、その後の粒子への成長過程で、微小粒径を維持したまま、結晶の品質向上のための時間を確保でき、結果として原料液中のＣｄとＳｅをほぼ全量消費できることに着目し、本発明に到達した。 The inventors of the present invention have prepared a Se raw material liquid that reaches a complex state of a predetermined equilibrium state while Se and ODA change the complex form over several hours, in an energetically unstable stage that has not reached the equilibrium state. When mixed with the Cd raw material liquid, a large amount of the Cd-Se raw material in the synthetic liquid is consumed at the initial stage of synthesis, the number of CdSe colloid nuclei generated is increased, and the fine particle size is maintained in the subsequent growth process to particles. Focusing on the fact that time for improving the quality of the crystals can be secured, and as a result, almost all Cd and Se in the raw material liquid can be consumed, the present invention has been achieved.
本発明の第１の観点は、Ｃｄ原料液にＳｅ原料液を注入して混合することによりＣｄＳｅコロイド粒子を製造する方法において、(a) 前記Ｓｅ原料液を、Ｓｅ源と配位性溶媒とを混合した後、２００〜２６０℃の温度に加熱して１０分〜２時間保持し、続いて９０〜１１０℃の温度に降温することにより調製する工程と、(b) ２７０〜２９０℃の温度に保持された前記Ｃｄ原料液に９０〜１１０℃の温度に保持された前記Ｓｅ原料液を注入して混合した後、注入開始時刻から１０分〜１５時間保持することにより、合成液を調製し、前記合成液中で生成したＣｄＳｅコロイド核を粒成長させる工程と、(c) 前記ＣｄＳｅコロイド核が粒成長した液に極性溶媒を添加混合して前記液中で分散しているＣｄＳｅコロイド粒子をＣｄＳｅコロイド凝集粒子にする工程と、(d) 前記液を固液分離して前記ＣｄＳｅコロイド凝集粒子を回収する工程と、(e) 前記回収したＣｄＳｅコロイド凝集粒子に非極性溶媒を添加混合してＣｄＳｅコロイド粒子が分散した液にする工程と、(f) 前記液に極性溶媒を添加混合して前記液中で分散しているＣｄＳｅコロイド粒子をＣｄＳｅコロイド凝集粒子にする工程と、(g) 前記液を固液分離して前記ＣｄＳｅコロイド凝集粒子を回収する工程と、(h) 前記回収したＣｄＳｅコロイド凝集粒子に非極性溶媒を添加混合してＣｄＳｅコロイド粒子が分散した液にする工程とを上記(a)〜(h)の工程順に含むことを特徴とするＣｄＳｅコロイド粒子の製造方法である。 According to a first aspect of the present invention, in a method for producing CdSe colloidal particles by injecting and mixing an Se raw material liquid into a Cd raw material liquid, (a) the Se raw material liquid is mixed with an Se source and a coordinating solvent. And a step of preparing by heating to a temperature of 200 to 260 ° C. and holding for 10 minutes to 2 hours, followed by lowering to a temperature of 90 to 110 ° C., and (b) a temperature of 270 to 290 ° C. After injecting and mixing the Se raw material liquid maintained at a temperature of 90 to 110 ° C. into the Cd raw material liquid held at 10 to 15 hours from the injection start time, a synthesis liquid was prepared. A step of growing CdSe colloidal nuclei generated in the synthetic liquid, and (c) adding a polar solvent to the liquid in which the CdSe colloidal nuclei have been grown and mixing them to disperse CdSe colloidal particles dispersed in the liquid. CdSe colloid aggregates And (d) collecting the CdSe colloidal aggregated particles by solid-liquid separation, and (e) adding a nonpolar solvent to the collected CdSe colloidal aggregated particles to mix CdSe colloidal particles. (F) a step of adding a polar solvent to the liquid and mixing the mixture to make CdSe colloidal particles dispersed in the liquid to be CdSe colloidal agglomerated particles; Separating the recovered CdSe colloidal particles and (h) adding a non-polar solvent to the recovered CdSe colloidal aggregated particles and mixing them to obtain a liquid in which the CdSe colloidal particles are dispersed. It is a manufacturing method of the CdSe colloidal particle characterized by including in order of the process of (h).
本発明の第２の観点は、第１の観点の発明に基づく発明であって、前記(h)工程の後で、前記(f)工程から前記(h)工程まで１回又は２回以上繰り返すＣｄＳｅコロイド粒子の製造方法である。 The second aspect of the present invention is the invention based on the invention of the first aspect, and is repeated once or twice or more after the step (h) from the step (f) to the step (h). This is a method for producing CdSe colloidal particles.
本発明の第３の観点は、Ｃｄ原料液にＳｅ原料液を注入して混合することによりＣｄＳｅコロイド粒子を製造する方法において、(m) 前記Ｓｅ原料液を、Ｓｅ源と配位性溶媒とを混合した後、２００〜２６０℃の温度に加熱して１０分〜２時間保持し、続いて１００〜２８０℃の温度に降温又は昇温することにより調製する工程と、(n) ２７０〜２９０℃の温度に保持された前記Ｃｄ原料液に前記Ｃｄ原料液の温度と同一又は前記温度より低い１００〜２８０℃の温度に保持された前記Ｓｅ原料液を注入して混合した後、注入開始時刻から7〜１３分保持することにより、合成液を調製し、前記合成液中で生成したＣｄＳｅコロイド核を粒成長させる工程と、(o) 前記ＣｄＳｅコロイド核が粒成長した液に極性溶媒を添加混合して前記液中で分散しているＣｄＳｅコロイド粒子をＣｄＳｅコロイド凝集粒子にする工程と、(p) 前記液を固液分離して前記ＣｄＳｅコロイド凝集粒子を回収する工程と、(q) 前記回収したＣｄＳｅコロイド凝集粒子に非極性溶媒を添加混合してＣｄＳｅコロイド粒子が分散した液にする工程と、(r) 前記液に極性溶媒を添加混合して前記液中で分散しているＣｄＳｅコロイド粒子をＣｄＳｅコロイド凝集粒子にする工程と、(s) 前記液を固液分離して前記ＣｄＳｅコロイド凝集粒子を回収する工程と、(t) 前記回収したＣｄＳｅコロイド凝集粒子に非極性溶媒を添加混合してＣｄＳｅコロイド粒子が分散した液にする工程とを上記(m)〜(t)の工程順に含むことを特徴とするＣｄＳｅコロイド粒子の製造方法である。
According to a third aspect of the present invention, in the method for producing CdSe colloidal particles by injecting and mixing an Se raw material liquid into a Cd raw material liquid, (m) the Se raw material liquid is mixed with an Se source and a coordinating solvent. After mixing, the step of heating to 200 to 260 ° C. and holding for 10 minutes to 2 hours, followed by lowering or raising the temperature to 100 to 280 ° C., (n) 270 to 290 Injection start time after injecting and mixing the Se raw material liquid maintained at a temperature of 100 to 280 ° C., which is the same as or lower than the temperature of the Cd raw material liquid, into the Cd raw material liquid maintained at a temperature of Holding for 7 to 13 minutes from the step of preparing a synthesis solution and growing CdSe colloid nuclei generated in the synthesis solution; and (o) adding a polar solvent to the solution in which the CdSe colloid nuclei are grown Mix and disperse in the liquid Converting the CdSe colloidal particles into CdSe colloidal aggregated particles, (p) collecting the CdSe colloidal aggregated particles by solid-liquid separation of the liquid, and (q) nonpolarizing the recovered CdSe colloidal aggregated particles. A step of adding and mixing a solvent to obtain a liquid in which CdSe colloidal particles are dispersed; and (r) a step of adding and mixing a polar solvent to the liquid to convert the CdSe colloidal particles dispersed in the liquid to CdSe colloidal agglomerated particles. And (s) a step of solid-liquid separation of the liquid to recover the CdSe colloidal aggregated particles, and (t) a liquid in which CdSe colloidal particles are dispersed by adding and mixing a nonpolar solvent to the recovered CdSe colloidal aggregated particles. A method for producing CdSe colloidal particles, comprising the steps of (m) to (t) in the order of the steps described above.
本発明の第４の観点は、第３の観点の発明に基づく発明であって、前記(t)工程の後で、前記(r)工程から前記(t)工程まで１回又は２回以上繰り返すＣｄＳｅコロイド粒子の製造方法である。 A fourth aspect of the present invention is an invention based on the invention of the third aspect, and is repeated one or more times from the step (r) to the step (t) after the step (t). This is a method for producing CdSe colloidal particles.
本発明の第５の観点は、第１ないし第４の観点のいずれかの観点の発明に基づく発明であって、前記Ｓｅ原料液が、金属セレンとオクタデシルアミンとオクタデセンとを混合した後、前記金属セレンと前記オクタデシルアミンとによる錯形態が平衡状態に達していない溶液であるＣｄＳｅコロイド粒子の製造方法である。 A fifth aspect of the present invention is the invention based on the invention according to any one of the first to fourth aspects, wherein the Se raw material liquid is a mixture of metal selenium, octadecylamine and octadecene, This is a method for producing CdSe colloidal particles, which is a solution in which the complex form of metal selenium and octadecylamine does not reach an equilibrium state.
本発明の第１の観点のＣｄＳｅコロイド粒子の製造方法では、Ｓｅ源と配位性溶媒とを混合した後、前記Ｓｅ源と前記配位性溶媒とによる錯形態が平衡状態に達していないエネルギー的に不安定な段階で、Ｓｅ原料液をＣｄ原料液と混合するため、合成初期で合成液中のＣｄ−Ｓｅの原料が多量に消費され、ＣｄＳｅコロイド核の生成数が多くなる。その後の粒子への成長過程で、微小粒径が維持されるとともに、結晶の品質向上のための時間を確保でき、結果として原料液中のＣｄとＳｅをほぼ全量消費でき、収量を高くすることができる。第１の観点の製造条件を満たすことにより、粒径が１〜６ｎｍの範囲内にあり、ＰＬスペクトルのピークにおける半値幅が３０ｎｍ以下であり、量子効率が４５％以上であり、収量が０．５５以上であるＣｄＳｅコロイド粒子を得ることができる。特に合成液を注入開始時刻から数分間で反応液を調製した場合には、比較的短時間で高品質のＣｄＳｅコロイド粒子が得られる。 In the method for producing CdSe colloidal particles according to the first aspect of the present invention, after mixing the Se source and the coordinating solvent, the energy at which the complex form of the Se source and the coordinating solvent does not reach an equilibrium state. Since the Se raw material liquid is mixed with the Cd raw material liquid at an unstable stage, a large amount of the Cd—Se raw material in the synthetic liquid is consumed at the initial stage of synthesis, and the number of CdSe colloid nuclei generated is increased. In the subsequent growth process to particles, the fine particle size is maintained and time for improving the quality of the crystal can be secured. As a result, almost all of Cd and Se in the raw material liquid can be consumed, and the yield is increased. Can do. By satisfying the manufacturing condition of the first aspect, the particle size is in the range of 1 to 6 nm, the half width at the peak of the PL spectrum is 30 nm or less, the quantum efficiency is 45% or more, and the yield is 0. CdSe colloidal particles having 55 or more can be obtained. In particular, when a reaction solution is prepared within a few minutes from the injection start time, a high-quality CdSe colloidal particle can be obtained in a relatively short time.
本発明の第２の観点及び第４の観点のＣｄＳｅコロイド粒子の製造方法では、極性溶媒の添加によりＣｄＳｅコロイド粒子をＣｄＳｅコロイド凝集粒子にする工程と、非極性溶媒の添加によりＣｄＳｅコロイド凝集粒子をＣｄＳｅコロイド粒子に再分散させる工程を繰り返すことにより、ＣｄＳｅコロイド粒子が洗浄され、より一層上記半値幅が狭まる。 In the method for producing CdSe colloidal particles according to the second aspect and the fourth aspect of the present invention, the step of converting the CdSe colloidal particles into CdSe colloidal aggregated particles by adding a polar solvent; By repeating the step of redispersing in the CdSe colloidal particles, the CdSe colloidal particles are washed, and the half width is further narrowed.
本発明の第３の観点のＣｄＳｅコロイド粒子の製造方法では、Ｓｅ源と配位性溶媒とを混合した後、前記Ｓｅ源と前記配位性溶媒とによる錯形態が平衡状態に達していないエネルギー的に不安定な段階で、Ｓｅ原料液をＣｄ原料液と混合するため、合成初期で合成液中のＣｄ−Ｓｅの原料が多量に消費され、ＣｄＳｅコロイド核の生成数が多くなる。その後の粒子への成長過程で、微小粒径が維持されるとともに、結晶の品質向上のための時間を確保でき、結果として原料液中のＣｄとＳｅをほぼ全量消費でき、収量を高くすることができる。第３の観点の製造条件を満たすことにより、粒径が１〜６ｎｍの範囲内にあり、ＰＬスペクトルのピークにおける半値幅が３０ｎｍ以下であり、量子効率が４５％以上であり、収量が０．５５以上であるＣｄＳｅコロイド粒子を得ることができる。特にＳｅ原料液を注入するときの液温を２８０℃にするか、又は２８０℃に近い温度にした場合には、Ｓｅ原料液の注入時に、両原料液の温度差がなくなるか、又は小さくなり、Ｓｅ原料液とＣｄ原料液とを混合した合成液中で温度ムラを生じにくく、大規模に高品質のＣｄＳｅコロイド粒子を製造することができる。 In the method for producing CdSe colloidal particles according to the third aspect of the present invention, after mixing the Se source and the coordinating solvent, the energy at which the complex form of the Se source and the coordinating solvent does not reach the equilibrium state. Since the Se raw material liquid is mixed with the Cd raw material liquid at an unstable stage, a large amount of the Cd—Se raw material in the synthetic liquid is consumed at the initial stage of synthesis, and the number of CdSe colloid nuclei generated is increased. In the subsequent growth process to particles, the fine particle size is maintained and time for improving the quality of the crystal can be secured. As a result, almost all of Cd and Se in the raw material liquid can be consumed, and the yield is increased. Can do. By satisfying the manufacturing condition of the third aspect, the particle diameter is in the range of 1 to 6 nm, the half width at the peak of the PL spectrum is 30 nm or less, the quantum efficiency is 45% or more, and the yield is 0. CdSe colloidal particles having 55 or more can be obtained. In particular, if the liquid temperature when injecting the Se raw material liquid is set to 280 ° C. or close to 280 ° C., the temperature difference between the two raw material liquids disappears or becomes smaller when the Se raw material liquid is injected. In the synthetic liquid obtained by mixing the Se raw material liquid and the Cd raw material liquid, temperature unevenness is unlikely to occur, and high-quality CdSe colloidal particles can be produced on a large scale.
本発明の第５の観点のＣｄＳｅコロイド粒子の製造方法では、Ｓｅ原料液を、金属セレンとオクタデシルアミンとオクタデセンとを混合した後、前記金属セレンと前記オクタデシルアミンとによる錯形態が平衡状態に達していない溶液にすることにより、金属セレンが溶解し易く、かつオクタデシルアミンが金属セレンと錯体を形成し易く、また合成時に熱解離し易いため、Ｃｄ−Ｓｅモノマーの過飽和度が増大し、この結果、核生成数を増加させることができる。 In the method for producing CdSe colloidal particles according to the fifth aspect of the present invention, after the Se raw material liquid is mixed with metal selenium, octadecylamine and octadecene, the complex form of the metal selenium and octadecylamine reaches an equilibrium state. As a result, since the metal selenium is easily dissolved and octadecylamine is easily complexed with the metal selenium and is easily thermally dissociated during the synthesis, the degree of supersaturation of the Cd-Se monomer is increased. The nucleation number can be increased.
次に本発明を実施するための形態を図面に基づいて説明する。 Next, an embodiment for carrying out the present invention will be described with reference to the drawings.
＜第１の実施形態＞
第１の実施形態のＣｄＳｅコロイド粒子は、図１に示す工程を経て作られる。図１に示す温度は本発明の実施例の温度である。各原料の秤量は各原料の雰囲気ガスとの反応を回避するため、窒素ガス等の不活性ガス雰囲気下で行われる。
<First Embodiment>
The CdSe colloidal particles of the first embodiment are made through the process shown in FIG. The temperature shown in FIG. 1 is the temperature of the embodiment of the present invention. Each raw material is weighed under an inert gas atmosphere such as nitrogen gas in order to avoid reaction with the atmospheric gas of each raw material.
〔Ｃｄ原料液の調製〕
第１の実施形態のＣｄ原料液は、不活性ガスで置換した容器内にＣｄ源としての粉末状の金属カドミウム（Ｃｄ）又は粉末状の酸化カドミウム（ＣｄＯ）等のカドミウムの酸化物を入れ、これにカルボン酸と非配位性溶媒を加えて混合した後、加熱することにより調製される。カルボン酸としては、ギ酸、酢酸、プロピオン酸等の飽和脂肪酸、オレイン酸、リノール酸、リノレン酸等の不飽和脂肪酸が挙げられる。非配位性溶媒としては、オクタデセン（ＯＤＥ：Ｃ１８Ｈ３６）、トリオクチルホスフィン（ＴＯＰ：Ｃ２４Ｈ５１Ｐ）、トリオクチルホスフィンオキシド（ＴＯＰＯ：Ｃ２４Ｈ５１ＯＰ）、オレイルアミン（ＯＬＡ：Ｃ１８Ｈ３７Ｎ）、ヘキサデシルアミン（ＨＤＡ：Ｃ１６Ｈ３５Ｎ）等が挙げられる。Ｃｄ源１ｍｏｌに対して、カルボン酸を２〜６ｍｏｌ、非配位性溶媒を５０〜３００ｍｏｌ加える。各原料の混合液が入った容器に不活性ガスを通気しながら この容器をオイルバスなどで加熱する。このオイルバスで各原料の混合液を加熱して到達する温度は２７０〜２９０℃である。この温度で混合液が透明になり、２７０〜２９０℃のＣｄ原料液が調製される。Ｃｄ原料液の温度が下限値未満では、後述するＳｅ原料液との反応が進みにくく、上限値を超えるとＣｄ原料液が蒸発し易くなる。
[Preparation of Cd raw material solution]
In the Cd raw material liquid of the first embodiment, a cadmium oxide such as powdered metal cadmium (Cd) or powdered cadmium oxide (CdO) as a Cd source is placed in a container substituted with an inert gas, This is prepared by adding a carboxylic acid and a non-coordinating solvent and mixing them, followed by heating. Examples of the carboxylic acid include saturated fatty acids such as formic acid, acetic acid, and propionic acid, and unsaturated fatty acids such as oleic acid, linoleic acid, and linolenic acid. Non-coordinating solvents include octadecene (ODE: C 18 H 36 ), trioctyl phosphine (TOP: C 24 H 51 P), trioctyl phosphine oxide (TOPO: C 24 H 51 OP), oleylamine (OLA: C 18 H 37 N), hexadecylamine (HDA: C 16 H 35 N), and the like. 2-6 mol of carboxylic acid and 50-300 mol of non-coordinating solvent are added to 1 mol of Cd source. This container is heated with an oil bath or the like while passing an inert gas through the container containing the mixture of raw materials. The temperature reached by heating the mixture of each raw material in this oil bath is 270 to 290 ° C. At this temperature, the liquid mixture becomes transparent, and a 270 to 290 ° C. Cd raw material liquid is prepared. When the temperature of the Cd raw material liquid is less than the lower limit value, the reaction with the Se raw material liquid described later hardly proceeds, and when the temperature exceeds the upper limit value, the Cd raw material liquid easily evaporates.
〔Ｓｅ原料液の調製〕
第１の実施形態のＳｅ原料液は、不活性ガスで置換した容器内にＳｅ源としての粉末状の金属セレン（Ｓｅ）又は粉末状の酸化セレン等のセレンの酸化物を入れ、これに配位性溶媒を混合して加熱することにより調製される。第１の実施形態の特徴ある第１の点は、Ｓｅ源と配位性溶媒とが錯形態を変化させながら所定の平衡状態の錯形態に到達する前のエネルギー的に不安定なＳｅ原料液を調製することにある。加熱温度が高くかつ加熱時間が長くなると、平衡状態の錯形態になり易い。配位性溶媒としては、オクタデセン（ＯＤＥ：Ｃ１８Ｈ３６）、トリオクチルホスフィン（ＴＯＰ：Ｃ２４Ｈ５１Ｐ）や、オクタデシルアミン（ＯＤＡ：Ｃ１８Ｈ３９Ｎ）、ヘキサデシルアミン（ＨＤＡ：Ｃ１６Ｈ３５Ｎ）等のアミン類、トリブチルホスホン酸（ＴＢＰＡ：Ｃ１８Ｈ１２Ｂｒ３Ｎ）等のホスホン酸類等が挙げられる。Ｓｅ源１ｍｏｌに対して、配位性溶媒を２〜１０ｍｏｌ加える。Ｃｄ原料液の調製と同様に、各原料の混合液が入った容器に不活性ガスを通気しながら この容器をオイルバスなどで加熱する。このオイルバスで各原料の混合液を加熱する温度は２００〜２６０℃であり、加熱した温度での保持時間は１０分〜２時間である。加熱温度が２００℃未満又は保持時間が１０分未満では、Ｓｅ源の配位性溶媒への溶解が十分でなく、Ｓｅ源の未溶解分が発生し易い。また加熱温度が２６０℃を超えるか又は保持時間が２時間を超えると、Ｓｅ源とＯＤＡとが平衡状態の錯形態になってしまい、収量を高くすることができない。第１の実施形態の特徴ある第２の点は、加熱した後、容器をオイルバスから取り出して空冷することにより降温して、最終のＳｅ原料液の温度を９０〜１１０℃の一定の温度にすることにある。Ｓｅ原料液の温度が下限値未満にまで降温すると、Ｓｅの有機塩が生成する等の不具合を生じる。Ｓｅ源としては、金属セレンが溶解し易いことから好ましく、配位性溶媒としては、オクタデシルアミンがＳｅと錯体を形成し易く、また合成時に熱解離し易いことから好ましい。なお、オクタデセン等を上述したＣｄ原料液では「非配位性溶媒」とし、上述したＳｅ原料液では「配位性溶媒」としたのは、同じ有機物（官能基）でも、金属種により、「配位性」を示したり、「非配位性」を示したりするからである。
[Preparation of Se raw material liquid]
In the Se raw material liquid of the first embodiment, selenium oxide such as powdered metal selenium (Se) or powdered selenium oxide as a Se source is placed in a container substituted with an inert gas, and distributed to this. It is prepared by mixing and heating a neutral solvent. The characteristic first point of the first embodiment is that the Se source solution is unstable in terms of energy before the Se source and the coordinating solvent reach a complex form in a predetermined equilibrium state while changing the complex form. Is to prepare. When the heating temperature is high and the heating time is long, an equilibrium complex form is likely to occur. As a coordinating solvent, octadecene (ODE: C 18 H 36 ), trioctyl phosphine (TOP: C 24 H 51 P), octadecylamine (ODA: C 18 H 39 N), hexadecylamine (HDA: C And amines such as 16 H 35 N) and phosphonic acids such as tributylphosphonic acid (TBPA: C 18 H 12 Br 3 N). 2-10 mol of coordinating solvent is added to 1 mol of Se source. Similar to the preparation of the Cd raw material liquid, the container is heated with an oil bath or the like while passing an inert gas through the container containing the mixed liquid of the respective raw materials. The temperature at which the mixed liquid of each raw material is heated in this oil bath is 200 to 260 ° C., and the holding time at the heated temperature is 10 minutes to 2 hours. When the heating temperature is less than 200 ° C. or the holding time is less than 10 minutes, the Se source is not sufficiently dissolved in the coordinating solvent, and the Se source is not easily dissolved. On the other hand, when the heating temperature exceeds 260 ° C. or the holding time exceeds 2 hours, the Se source and ODA are in a complex form in an equilibrium state, and the yield cannot be increased. The characteristic second point of the first embodiment is that after heating, the container is taken out from the oil bath and cooled by air cooling, so that the temperature of the final Se raw material liquid becomes a constant temperature of 90 to 110 ° C. There is to do. When the temperature of the Se raw material liquid falls below the lower limit, problems such as the generation of an organic salt of Se occur. The Se source is preferable because metal selenium is easily dissolved, and the coordinating solvent is preferable because octadecylamine is easy to form a complex with Se and is thermally dissociated during synthesis. It should be noted that octadecene or the like is designated as a “non-coordinating solvent” in the above-mentioned Cd raw material liquid and “coordinating solvent” in the above-described Se raw material liquid, even for the same organic substance (functional group), depending on the metal species. This is because it indicates “coordination” or “non-coordination”.
〔Ｃｄ原料液とＳｅ原料液の合成〕
Ｃｄ原料液とＳｅ原料液の合成は、ホットソープ法で行われる。即ち、Ｃｄ原料液が入った容器に不活性ガスを通気しながら この容器をオイルバスで加熱した状態で、２７０〜２９０℃のＣｄ原料液中に９０〜１１０℃のＳｅ原料液をシリンジを用いて一気に注入してＣｄ原料液とＳｅ原料液の合成を行う。具体的には内径１０ｍｍのシリンジを用いて１〜１０ｍＬ／秒の押し込み速度で注入する。下限値未満の速度でゆっくり注入すると、液中で形成した核の表面にまた核が形成され、核が微小になりにくく、ＰＬスペクトルのピークにおける半値幅も広がる。上限値を超えた高速度では注入操作がやりにくい。これにより、Ｃｄ原料液にＳｅ原料液を混合した合成液が調製される。Ｃｄ原料液にＳｅ原料液を混合する方法として、混合の規模によっては、不活性圧縮ガスを利用して、ノズル混合、エジェクター混合等の混合方法を採用してもよい。ここで所定の平衡状態の錯形態に到達する前のエネルギー的に不安定なＳｅ原料液の注入すると、注入直後から液温低下が始まり、ＣｄＳｅコロイド核が大量に生成し始める。ここで合成液を２４５〜２５５℃の温度で保持し、ＣｄＳｅコロイド核を粒成長させる。第１の実施形態の特徴ある第３の点は、注入開始時刻から起算される合成時間を１０分〜１５時間の範囲にすることにある。好ましくは、合成時間を１３分〜８時間の範囲にする。下限値の１０分未満では、Ｃｄ原料液とＳｅ原料液の合成が不十分で収量を高くすることができない。また上限値の１５時間を超えると、製造効率が悪化し易い。
[Synthesis of Cd raw material liquid and Se raw material liquid]
The synthesis of the Cd raw material liquid and the Se raw material liquid is performed by a hot soap method. That is, in a state where an inert gas is passed through a container containing Cd raw material liquid and this container is heated in an oil bath, Se raw material liquid at 90 to 110 ° C. is used in a Cd raw material liquid at 270 to 290 ° C. using a syringe. Then, the Cd raw material liquid and the Se raw material liquid are synthesized. Specifically, injection is performed at a pushing speed of 1 to 10 mL / second using a syringe having an inner diameter of 10 mm. When it is slowly injected at a rate lower than the lower limit, nuclei are formed again on the surface of the nuclei formed in the liquid, the nuclei are less likely to be minute, and the half-value width at the peak of the PL spectrum is widened. The injection operation is difficult at high speeds exceeding the upper limit. Thereby, a synthetic liquid is prepared by mixing the Se raw material liquid with the Cd raw material liquid. As a method of mixing the Se raw material liquid with the Cd raw material liquid, a mixing method such as nozzle mixing or ejector mixing may be employed using an inert compressed gas depending on the scale of mixing. Here, when an energy-unstable Se raw material liquid is injected before reaching a complex state of a predetermined equilibrium state, the liquid temperature starts decreasing immediately after the injection, and a large amount of CdSe colloid nuclei starts to be generated. Here, the synthesis solution is held at a temperature of 245 to 255 ° C. to grow CdSe colloid nuclei. A characteristic third point of the first embodiment is that the synthesis time calculated from the injection start time is in the range of 10 minutes to 15 hours. Preferably, the synthesis time is in the range of 13 minutes to 8 hours. If the lower limit is less than 10 minutes, the synthesis of the Cd raw material liquid and the Se raw material liquid is insufficient and the yield cannot be increased. If the upper limit of 15 hours is exceeded, the production efficiency tends to deteriorate.
〔ＣｄＳｅコロイド粒子の分散液の作製〕
上記合成時間が経過した後、オイルバスから容器を取り出し、そこに極性溶媒を加えて合成液の温度を下げ、粒成長したＣｄＳｅコロイドの凝集粒子を得る。極性溶媒としては、ブタノール（Ｃ４Ｈ１０Ｏ）、メタノール（ＣＨ４Ｏ）、エタノール（Ｃ２Ｈ６Ｏ）、１（又は２）−プロパノール（Ｃ３Ｈ８Ｏ）等が挙げられる。ＣｄＳｅコロイド凝集粒子が液をミキサー等で十分に撹拌した後、遠心分離等により固液分離して、固形分であるＣｄＳｅコロイド凝集粒子を回収する。回収したＣｄＳｅコロイド凝集粒子に非極性溶媒を加えて、ミキサー等で十分に撹拌して、コロイド凝集粒子を分散させてコロイド粒子の分散液を得る。非極性溶媒としては、ヘキサン（Ｃ６Ｈ１４）、トルエン（Ｃ７Ｈ８）、ジエチルエーテル（Ｃ４Ｈ１０Ｏ）、クロロホルム（ＣＨＣｌ３）等が挙げられる。
[Preparation of CdSe colloidal particle dispersion]
After the synthesis time has elapsed, the container is taken out from the oil bath, and a polar solvent is added thereto to lower the temperature of the synthesis solution to obtain aggregated particles of CdSe colloids that have grown. Examples of the polar solvent include butanol (C 4 H 10 O), methanol (CH 4 O), ethanol (C 2 H 6 O), 1 (or 2) -propanol (C 3 H 8 O), and the like. After the CdSe colloid aggregated particles are sufficiently agitated with a mixer or the like, the liquid is separated into solid and liquid by centrifugation or the like, and the CdSe colloid aggregated particles as a solid content are recovered. A nonpolar solvent is added to the collected CdSe colloidal aggregated particles, and the mixture is sufficiently stirred with a mixer or the like to disperse the colloidal aggregated particles to obtain a dispersion of colloidal particles. Examples of the nonpolar solvent include hexane (C 6 H 14 ), toluene (C 7 H 8 ), diethyl ether (C 4 H 10 O), chloroform (CHCl 3 ), and the like.
次いで、コロイド粒子の分散液に極性溶媒を加え、ミキサー等で十分に撹拌することにより、コロイド粒子を凝集粒子にする。この液に対して、例えば６０００ｒｐｍで５分間の遠心分離を行うことにより、ＣｄＳｅコロイド凝集粒子を回収する。更にＣｄＳｅコロイド凝集粒子に非極性溶媒を所定量添加し、ミキサーで十分に撹拌しコロイド凝集粒子をほぐしてコロイド粒子の分散液にする。これにより、粒径が１〜６ｎｍの範囲内にあり、ＰＬスペクトルのピークにおける半値幅が３０ｎｍ以下であり、量子効率が４５％以上であり、収量が０．５５以上である高品質のＣｄＳｅコロイド粒子を得ることができる。極性溶媒によりコロイド粒子を凝集させ、コロイド凝集粒子を遠心分離により回収し、非極性溶媒によりコロイド粒子を分散させる操作は、更に１回又は２回以上行うことが望ましい。 Next, a polar solvent is added to the dispersion liquid of the colloid particles, and the colloid particles are agglomerated by sufficiently stirring with a mixer or the like. For example, CdSe colloid aggregated particles are collected by centrifuging the liquid at 6000 rpm for 5 minutes. Further, a predetermined amount of a nonpolar solvent is added to the CdSe colloidal aggregated particles, and the mixture is sufficiently stirred to loosen the colloidal aggregated particles to form a colloidal particle dispersion. As a result, a high-quality CdSe colloid having a particle size in the range of 1 to 6 nm, a half width at the PL spectrum peak of 30 nm or less, a quantum efficiency of 45% or more, and a yield of 0.55 or more. Particles can be obtained. The operations of aggregating colloidal particles with a polar solvent, collecting the colloidal agglomerated particles by centrifugation, and dispersing the colloidal particles with a nonpolar solvent are preferably performed once or twice or more.
＜第２の実施形態＞
第２の実施形態のＣｄＳｅコロイド粒子は、図２に示す工程を経て作られる。図２に示す温度は本発明の実施例の温度である。各原料の秤量は各原料の雰囲気ガスとの反応を回避するため、窒素ガス等の不活性ガス雰囲気下で行われる。
<Second Embodiment>
The CdSe colloidal particles of the second embodiment are made through the process shown in FIG. The temperature shown in FIG. 2 is the temperature of the embodiment of the present invention. Each raw material is weighed under an inert gas atmosphere such as nitrogen gas in order to avoid reaction with the atmospheric gas of each raw material.
〔Ｃｄ原料液の調製〕
第２の実施形態のＣｄ原料液は、第１の実施形態のＣｄ原料液と同様に調製される。
[Preparation of Cd raw material solution]
The Cd raw material liquid of the second embodiment is prepared in the same manner as the Cd raw material liquid of the first embodiment.
〔Ｓｅ原料液の調製〕
第２の実施形態のＳｅ原料液は、不活性ガスで置換した容器内にＳｅ源としての粉末状の金属セレン（Ｓｅ）又は粉末状の酸化セレン等のセレンの酸化物を入れ、これに配位性溶媒を混合して加熱することにより調製される。第２の実施形態の特徴ある第１の点は、Ｓｅ源と配位性溶媒とが錯形態を変化させながら所定の平衡状態の錯形態に到達する前のエネルギー的に不安定なＳｅ原料液を調製することにある。加熱温度が高くかつ加熱時間が長くなると、平衡状態の錯形態になり易い。配位性溶媒としては、オクタデセン（ＯＤＥ：Ｃ１８Ｈ３６）、トリオクチルホスフィン（ＴＯＰ：Ｃ２４Ｈ５１Ｐ）や、オクタデシルアミン（ＯＤＡ：Ｃ１８Ｈ３９Ｎ）、ヘキサデシルアミン（ＨＤＡ：Ｃ１６Ｈ３５Ｎ）等のアミン類、トリブチルホスホン酸（ＴＢＰＡ：Ｃ１８Ｈ１２Ｂｒ３Ｎ）等のホスホン酸類等が挙げられる。Ｓｅ源１ｍｏｌに対して、配位性溶媒を２〜１０ｍｏｌ加える。Ｃｄ原料液の調製と同様に、各原料の混合液が入った容器に不活性ガスを通気しながら この容器をオイルバスなどで加熱する。このオイルバスで各原料の混合液を加熱する温度は２００〜２６０℃であり、加熱した温度での保持時間は１０分〜２時間である。加熱温度が２００℃未満又は保持時間が１０分未満では、Ｓｅ源の配位性溶媒への溶解が十分でなく、Ｓｅ源の未溶解分が発生し易い。また加熱温度が２６０℃を超えるか又は保持時間が３時間を超えると、Ｓｅ源とＯＤＡとが平衡状態の錯形態になってしまい、収量を高くすることができない。第２の実施形態の特徴ある第２の点は、加熱した後、容器をオイルバスから取り出して空冷して降温するか、又は容器をオイルバスに入れた状態でオイルバスを加熱して昇温することにより、最終のＳｅ原料液の温度を１００〜２８０℃の温度にすることにある。Ｓｅ原料液の温度が１００℃未満にすると、Ｓｅの有機塩が生成する等の不具合を生じ、２８０℃を超えると、Ｓｅ原料液が蒸発し易くなる。Ｓｅ源としては、金属セレンが溶解し易いことから好ましく、配位性溶媒としては、オクタデシルアミンがＳｅと錯体を形成し易く、また合成時に熱解離し易いことから好ましい。
[Preparation of Se raw material liquid]
In the Se raw material liquid of the second embodiment, selenium oxide such as powdered metal selenium (Se) or powdered selenium oxide as a Se source is placed in a container substituted with an inert gas, and distributed to this. It is prepared by mixing and heating a neutral solvent. The characteristic first point of the second embodiment is that the Se source solution is energetically unstable before the Se source and the coordinating solvent reach the complex form in a predetermined equilibrium state while changing the complex form. Is to prepare. When the heating temperature is high and the heating time is long, an equilibrium complex form is likely to occur. As a coordinating solvent, octadecene (ODE: C 18 H 36 ), trioctyl phosphine (TOP: C 24 H 51 P), octadecylamine (ODA: C 18 H 39 N), hexadecylamine (HDA: C And amines such as 16 H 35 N) and phosphonic acids such as tributylphosphonic acid (TBPA: C 18 H 12 Br 3 N). 2-10 mol of coordinating solvent is added to 1 mol of Se source. Similar to the preparation of the Cd raw material liquid, the container is heated with an oil bath or the like while passing an inert gas through the container containing the mixed liquid of the respective raw materials. The temperature at which the mixed liquid of each raw material is heated in this oil bath is 200 to 260 ° C., and the holding time at the heated temperature is 10 minutes to 2 hours. When the heating temperature is less than 200 ° C. or the holding time is less than 10 minutes, the Se source is not sufficiently dissolved in the coordinating solvent, and the Se source is not easily dissolved. On the other hand, when the heating temperature exceeds 260 ° C. or the holding time exceeds 3 hours, the Se source and ODA are in an equilibrium state and the yield cannot be increased. The second characteristic point of the second embodiment is that, after heating, the container is taken out from the oil bath and cooled by air, or the temperature is raised by heating the oil bath while the container is placed in the oil bath. By doing this, the temperature of the final Se raw material liquid is set to a temperature of 100 to 280 ° C. If the temperature of the Se raw material liquid is less than 100 ° C., problems such as the formation of an organic salt of Se occur. If the temperature exceeds 280 ° C., the Se raw material liquid is easily evaporated. The Se source is preferable because metal selenium is easily dissolved, and the coordinating solvent is preferable because octadecylamine is easy to form a complex with Se and is thermally dissociated during synthesis.
〔Ｃｄ原料液とＳｅ原料液の合成〕
Ｃｄ原料液とＳｅ原料液の合成は、ホットソープ法で行われる。即ち、Ｃｄ原料液が入った容器に不活性ガスを通気しながら この容器をオイルバスで加熱した状態で、２７０〜２９０℃のＣｄ原料液中に１００〜２８０℃の範囲に温度調整された複数種類のＳｅ原料液を各別にシリンジを用いて一気に注入してＣｄ原料液とＳｅ原料液の合成を行う。注入速度は第１の実施形態と同じである。またそれ以外の操作は、第１の実施形態と同様に行われる。これにより、Ｃｄ原料液にＳｅ原料液を混合した合成液が調製される。所定の平衡状態の錯形態に到達する前のエネルギー的に不安定なＳｅ原料液の注入すると、注入直後から液温低下が始まり、ＣｄＳｅコロイド核が大量に生成し始める。ここで合成液を２４５〜２８０℃の温度で保持し、ＣｄＳｅコロイド核を粒成長させる。第２の実施形態の特徴ある第３の点は、注入開始時刻から起算される合成時間を一定にすることにある。具体的には、注入開始時刻から７〜１３分間経過した後、オイルバスから容器を取り出し、そこに極性溶媒を加えて合成液の温度を下げ、粒成長したＣｄＳｅコロイドの凝集粒子を得る。
[Synthesis of Cd raw material liquid and Se raw material liquid]
The synthesis of the Cd raw material liquid and the Se raw material liquid is performed by a hot soap method. In other words, while the inert gas is passed through the container containing the Cd raw material liquid and the container is heated in an oil bath, the temperature is adjusted in the range of 100 to 280 ° C. in the Cd raw material liquid at 270 to 290 ° C. Each type of Se raw material liquid is injected at once using a syringe to synthesize the Cd raw material liquid and the Se raw material liquid. The injection rate is the same as in the first embodiment. Other operations are performed in the same manner as in the first embodiment. Thereby, a synthetic liquid is prepared by mixing the Se raw material liquid with the Cd raw material liquid. When an Se raw material liquid that is unstable in energy before reaching a complex state of a predetermined equilibrium state is injected, the liquid temperature starts decreasing immediately after the injection, and a large amount of CdSe colloid nuclei starts to be generated. Here, the synthesis solution is held at a temperature of 245 to 280 ° C. to grow CdSe colloidal nuclei. A characteristic third point of the second embodiment is to make the synthesis time calculated from the injection start time constant. Specifically, after 7 to 13 minutes have elapsed from the injection start time, the container is taken out from the oil bath, and a polar solvent is added thereto to lower the temperature of the synthesis solution to obtain agglomerated CdSe colloidal particles.
〔ＣｄＳｅコロイド粒子の分散液の作製〕
上記合成時間が経過した後、オイルバスから容器を取り出し、そこに極性溶媒を加えて合成液の温度を下げ、粒成長したＣｄＳｅコロイドの凝集粒子を得る。それ以降の操作は、第１の実施形態と同様に行われる。極性溶媒としては、ブタノール（Ｃ４Ｈ１０Ｏ）、メタノール（ＣＨ４Ｏ）、エタノール（Ｃ２Ｈ６Ｏ）、１（又は、２）−プロパノール（Ｃ３Ｈ８Ｏ）等が挙げられる。ＣｄＳｅコロイド凝集粒子が液をミキサー等で十分に撹拌した後、遠心分離等により固液分離して、固形分であるＣｄＳｅコロイド凝集粒子を回収する。更にＣｄＳｅコロイド凝集粒子に非極性溶媒を所定量添加し、ミキサーで十分に撹拌しコロイド凝集粒子をほぐしてコロイド粒子の分散液にする。
[Preparation of CdSe colloidal particle dispersion]
After the synthesis time has elapsed, the container is taken out from the oil bath, and a polar solvent is added thereto to lower the temperature of the synthesis solution to obtain aggregated particles of CdSe colloids that have grown. Subsequent operations are performed in the same manner as in the first embodiment. Examples of the polar solvent include butanol (C 4 H 10 O), methanol (CH 4 O), ethanol (C 2 H 6 O), 1 (or 2) -propanol (C 3 H 8 O), and the like. After the CdSe colloid aggregated particles are sufficiently agitated with a mixer or the like, the liquid is separated into solid and liquid by centrifugation or the like, and the CdSe colloid aggregated particles as a solid content are recovered. Further, a predetermined amount of a nonpolar solvent is added to the CdSe colloidal aggregated particles, and the mixture is sufficiently stirred to loosen the colloidal aggregated particles to form a colloidal particle dispersion.
コロイド粒子の分散液は、第１の実施形態と同様に、極性溶媒でコロイド粒子を凝集させ、遠心分離でコロイド粒子を回収し、非極性溶媒でコロイド粒子を分散させる。これにより、粒径が１〜６ｎｍの範囲内にあり、ＰＬスペクトルのピークにおける半値幅が３０ｎｍ以下であり、量子効率が４５％以上であり、収量が０．５５以上である高品質のＣｄＳｅコロイド粒子を得ることができる。極性溶媒によるコロイド粒子を凝集させ、コロイド凝集粒子を遠心分離により回収し、非極性溶媒によるコロイド粒子の分散させる操作は、更に１回又は２回以上行うことが望ましい。 As in the first embodiment, the colloidal particle dispersion is obtained by aggregating colloidal particles with a polar solvent, collecting the colloidal particles by centrifugation, and dispersing the colloidal particles with a nonpolar solvent. As a result, a high-quality CdSe colloid having a particle size in the range of 1 to 6 nm, a half width at the PL spectrum peak of 30 nm or less, a quantum efficiency of 45% or more, and a yield of 0.55 or more. Particles can be obtained. The operation of aggregating colloidal particles with a polar solvent, collecting the colloidal aggregated particles by centrifugation, and dispersing the colloidal particles with a nonpolar solvent is preferably performed once or twice or more.
次に本発明の実施例を比較例とともに詳しく説明する。 Next, examples of the present invention will be described in detail together with comparative examples.
＜実施例１＞
図１に示す工程順に以下の方法により、II−VI半導体であるＣｄＳｅコロイドをホットソープ法で作製した。
<Example 1>
A CdSe colloid, which is an II-VI semiconductor, was prepared by a hot soap method in the order of steps shown in FIG.
秤量作業は全てグローブボックス内（Ｎ２ガス雰囲気）で実施した。５０ｍＬフラスコ内に酸化カドミウム（ＣｄＯ）０．０１５４ｇ（０．１２ｍｍｏｌ）を入れ、これにオレイン酸（ＯＡ：Ｃ１８Ｈ３４Ｏ２）０．１１６７ｍＬ（０．３６ｍｍｏｌ）とオクタデセン（ＯＤＥ：Ｃ１８Ｈ３６）４．９１ｍＬ（１３．８３ｍｍｏｌ）を加えて混合した後、このフラスコをグローブボックス内から取り出した。このフラスコを２４０℃のシリコーンオイルに浸し、フラスコ内の混合液を撹拌しながら昇温した。混合液の温度が２４０℃に達した後、この温度で１０分間保持し、その後２８０℃まで昇温した。２８０℃に達した後、フラスコ内の液は完全な透明液となった。これをＣｄ原料液とした。図１では「Ｃｄ−ＯＡ溶液」として示している。 All weighing operations were performed in a glove box (N 2 gas atmosphere). Into a 50 mL flask was placed 0.0154 g (0.12 mmol) of cadmium oxide (CdO), 0.1167 mL (0.36 mmol) of oleic acid (OA: C 18 H 34 O 2 ) and octadecene (ODE: C 18 H). 36 ) After adding and mixing 4.91 mL (13.83 mmol), the flask was removed from the glove box. The flask was immersed in 240 ° C. silicone oil, and the temperature of the mixture was increased while stirring. After the temperature of the mixed solution reached 240 ° C., the temperature was maintained at this temperature for 10 minutes, and then the temperature was raised to 280 ° C. After reaching 280 ° C., the liquid in the flask became a completely transparent liquid. This was used as a Cd raw material liquid. In FIG. 1, it is shown as “Cd-OA solution”.
５０ｍＬフラスコ内に金属セレン（Ｓｅ）０．１８８ｇ（２．３８ｍｍｏｌ）を入れ、これにオクタデシルアミン（ＯＤＡ：Ｃ１８Ｈ３９Ｎ）１．９４ｇ（６．９８ｍｍｏｌ）とオクタデセン（ＯＤＥ：Ｃ１８Ｈ３６）１８．００ｍＬ（５０．６２ｍｍｏｌ）を加えて混合した後、このフラスコをグローブボックス内から取り出した。このフラスコを１００℃のシリコ−ンオイルに浸し，フラスコ内の混合液を撹拌しながら昇温した。混合液の温度が１００℃に達した後、この温度で２０分間保持し，その後２２０℃まで昇温した。２２０℃に達した状態でセレンがＯＤＡに溶解した液を１時間保持した後，シリコーンオイルからフラスコを取り出し，空冷を開始した。１００℃まで降温した最終液をＳｅ原料液とした。図１では「Ｓｅ−ＯＤＡ溶液」として示している。 Into a 50 mL flask was placed 0.188 g (2.38 mmol) of metal selenium (Se), and 1.94 g (6.98 mmol) of octadecylamine (ODA: C 18 H 39 N) and octadecene (ODE: C 18 H 36). ) After adding 18.00 mL (50.62 mmol) and mixing, the flask was taken out of the glove box. The flask was immersed in 100 ° C. silicone oil, and the temperature of the mixture was increased while stirring. After the temperature of the mixed solution reached 100 ° C., the temperature was maintained at this temperature for 20 minutes, and then the temperature was raised to 220 ° C. The liquid in which selenium was dissolved in ODA was held for 1 hour in a state where the temperature reached 220 ° C., and then the flask was taken out from the silicone oil and air cooling was started. The final liquid cooled to 100 ° C. was used as the Se raw material liquid. In FIG. 1, it is shown as “Se-ODA solution”.
１００℃まで空冷したＳｅ原料液（Ｓｅ−ＯＤＡ溶液）を内径１０ｍｍのシリンジで２ｍＬ採取し、これを一気に２ｍＬ／秒の押し込み速度でＣｄ原料液へ注入して混合することにより、Ｃｄ原料液にＳｅ原料液を混合した合成液を調製した。この注入タイミングを注入開始時刻とした。注入直後に液温低下が始まり、ＣｄＳｅコロイド核が生成し始めた。２５０℃に達した後、その２５０℃で保持し、ＣｄＳｅコロイド核を粒成長させた。注入開始時刻から１０分間保持してＣｄ原料液にＳｅ原料液を合成させた後にシリコ−ンオイルからフラスコを取り出し、そこにブタノール（Ｃ４Ｈ１０Ｏ）１４．０ｍＬとメタノール（ＣＨ４Ｏ）１４．０ｍＬを加え冷却することにより、粒成長したＣｄＳｅコロイド粒子が凝集した反応液を調製した。冷却した反応液をミキサーで十分に撹拌した後、この液に対して６０００ｒｐｍで５分間の遠心分離を行い、ＣｄＳｅコロイド凝集粒子を回収した。 2 mL of Se raw material liquid (Se-ODA solution) air-cooled to 100 ° C. is collected with a syringe with an inner diameter of 10 mm, and this is poured into the Cd raw material liquid at a pushing speed of 2 mL / second at a stroke to be mixed. A synthesis solution was prepared by mixing the Se raw material solution. This injection timing was set as the injection start time. Immediately after injection, the liquid temperature began to drop, and CdSe colloid nuclei began to form. After reaching 250 ° C., the temperature was maintained at 250 ° C. to grow CdSe colloidal nuclei. The mixture was held for 10 minutes from the injection start time to synthesize the Se raw material liquid into the Cd raw material liquid, and then the flask was taken out from the silicone oil, and then 14.0 mL of butanol (C 4 H 10 O) and methanol (CH 4 O) 14 By adding 0.0 mL and cooling, a reaction solution in which the CdSe colloidal particles grown were aggregated was prepared. After the cooled reaction liquid was sufficiently stirred with a mixer, the liquid was centrifuged at 6000 rpm for 5 minutes to collect CdSe colloidal aggregated particles.
回収したＣｄＳｅコロイド凝集粒子にヘキサン（Ｃ６Ｈ１４）２．０ｍＬを加え、ミキサーで十分に撹拌しコロイド凝集粒子をほぐしてコロイド粒子の分散液を得た。そこにブタノール（Ｃ４Ｈ１０Ｏ）４．０ｍＬとメタノール（ＣＨ４Ｏ）４．０ｍＬを加え、ミキサーで十分に撹拌してコロイド粒子を再び凝集粒子にした後、この液に対して６０００ｒｐｍで５分間の遠心分離を行い、ＣｄＳｅコロイド凝集粒子を回収した。最後にＣｄＳｅコロイド凝集粒子にヘキサン（Ｃ６Ｈ１４）２．０ｍＬを加え、ミキサーで十分に撹拌しコロイド凝集粒子をほぐしてコロイド粒子の分散液を得た。 To the collected CdSe colloid aggregated particles, 2.0 mL of hexane (C 6 H 14 ) was added, and the mixture was sufficiently stirred to loosen the colloid aggregated particles to obtain a dispersion of colloidal particles. Thereto was added 4.0 mL of butanol (C 4 H 10 O) and 4.0 mL of methanol (CH 4 O), and the mixture was sufficiently stirred to make the colloidal particles agglomerated again. Centrifugation for 5 minutes was performed to collect CdSe colloid aggregated particles. Finally, 2.0 mL of hexane (C 6 H 14 ) was added to the CdSe colloidal aggregated particles, and the mixture was sufficiently stirred to loosen the colloidal aggregated particles to obtain a dispersion of colloidal particles.
＜実施例２〜１０、比較例１〜１０＞
実施例２〜１０及び比較例１〜１０では、セレンがＯＤＡに溶解したＳｅ原料液（Ｓｅ−ＯＤＡ溶液）を次のように調製した。即ち、調製後の保持温度を２２０℃に設定して、表１に示すように、保持時間を１０分、１時間、２時間又は３時間に変えて保持し、その後実施例１と同様に空冷して９０℃〜１１０℃に降温することにより、最終のＳｅ原料液（Ｓｅ−ＯＤＡ溶液）を得た。これらのＳｅ原料液を実施例１と同様に各別にＣｄ原料液に注入して混合し、合成液を調製した。このとき注入開始時刻から起算される合成時間を表１に示すように、１秒から１５時間の間に設定した。以下、実施例１と同様の操作で、ＣｄＳｅコロイド粒子の分散液を得た。
<Examples 2 to 10, Comparative Examples 1 to 10>
In Examples 2 to 10 and Comparative Examples 1 to 10, a Se raw material liquid (Se-ODA solution) in which selenium was dissolved in ODA was prepared as follows. That is, the holding temperature after preparation was set to 220 ° C., and the holding time was changed to 10 minutes, 1 hour, 2 hours, or 3 hours as shown in Table 1, and then air-cooled in the same manner as in Example 1. Then, the final Se raw material liquid (Se-ODA solution) was obtained by lowering the temperature to 90 ° C to 110 ° C. In the same manner as in Example 1, these Se raw material liquids were poured into Cd raw material liquids and mixed to prepare a synthetic liquid. At this time, the synthesis time calculated from the injection start time was set between 1 second and 15 hours as shown in Table 1. Thereafter, a CdSe colloidal particle dispersion was obtained in the same manner as in Example 1.
＜実施例１１〜１９、比較例１１〜１６＞
実施例１１〜１９及び比較例１１〜１６では、セレンがＯＤＡに溶解したＳｅ原料液を実施例１と次のように調製した。即ち、調製後の保持温度を２２０℃に設定して、表２に示すように、保持時間を１０分、１時間、２時間、３時間又は１０時間に変えて保持し、その後実施例１と同様に空冷するか、又は実施例１と異なって昇温して、表２に示すように、９０℃から２８０℃の間に温度に変えて、最終のＳｅ原料液を得た。これらのＳｅ原料液を実施例１と同様に各別にＣｄ原料液に注入して混合し、合成液を調製した。このとき注入開始時刻から起算される時間を表２に示すように、７分から１３分の間に設定した。以下、実施例１と同様の操作で、ＣｄＳｅコロイド粒子の分散液を得た。なお、表２には、上記合成液の合成時間が１０分、１０分、１３分、９分である実施例１、実施例３、実施例８及び比較例８も一緒に示している。
<Examples 11 to 19 and Comparative Examples 11 to 16>
In Examples 11 to 19 and Comparative Examples 11 to 16, a Se raw material solution in which selenium was dissolved in ODA was prepared as in Example 1 as follows. That is, the holding temperature after preparation was set to 220 ° C., and as shown in Table 2, the holding time was changed to 10 minutes, 1 hour, 2 hours, 3 hours, or 10 hours and then held as in Example 1. Similarly, air cooling was performed, or the temperature was raised differently from Example 1, and the temperature was changed between 90 ° C. and 280 ° C. as shown in Table 2 to obtain the final Se raw material liquid. In the same manner as in Example 1, these Se raw material liquids were poured into Cd raw material liquids and mixed to prepare a synthetic liquid. At this time, as shown in Table 2, the time calculated from the injection start time was set between 7 minutes and 13 minutes. Thereafter, a CdSe colloidal particle dispersion was obtained in the same manner as in Example 1. Table 2 also shows Example 1, Example 3, Example 8, and Comparative Example 8 in which the synthesis time of the synthesis solution is 10 minutes, 10 minutes, 13 minutes, and 9 minutes.
＜比較評価＞
実施例１〜１９及び比較例１〜１６で得られた分散液中のＣｄＳｅコロイド粒子について、次に述べる方法により、粒径、ＰＬスペクトルのピークにおける半値幅、量子効率及び収量を調べた。これらの結果を製造条件とともに以下の表１及び表２に示す。
<Comparison evaluation>
For the CdSe colloidal particles in the dispersions obtained in Examples 1 to 19 and Comparative Examples 1 to 16, the particle diameter, the half width at the peak of the PL spectrum, the quantum efficiency, and the yield were examined by the methods described below. These results are shown in Table 1 and Table 2 below together with the production conditions.
(1) ＣｄＳｅコロイド粒子の粒径
分散液中のＣｄＳｅコロイドを極性溶媒を用いて凝集させ遠心分離にて回収したものをテトラクロロエチレン（Ｃ２Ｃｌ４）１．５ｍＬに再分散させ、紫外可視近赤外分光光度計（日立ハイテクサイエンス社製）にて吸光光度を測定した。ピーク波長よりコロイド粒子の粒径を算出した。
(1) Particle size of CdSe colloidal particles The CdSe colloid in the dispersion was agglomerated using a polar solvent and collected by centrifugation, and then redispersed in 1.5 mL of tetrachloroethylene (C 2 Cl 4 ), and UV-visible near red Absorbance was measured with an external spectrophotometer (manufactured by Hitachi High-Tech Science Co., Ltd.). The particle size of the colloidal particles was calculated from the peak wavelength.
(2) ＣｄＳｅコロイド粒子のＰＬスペクトルのピークにおける半値幅
上記吸光光度測定に用いた分散液を利用して、ＰＬ測定システム（大塚電子社製）にてＰＬスペクトルを測定した。ＰＬスペクトルのピーク値で規格化されたＰＬスペクトルにおける半値幅をコロイド粒子の均一性の指標として求めた。この半値幅が小さければ、粒径が均一であることを示している。
(2) Half-width at the peak of the PL spectrum of CdSe colloidal particles The PL spectrum was measured with a PL measurement system (manufactured by Otsuka Electronics Co., Ltd.) using the dispersion used for the above-mentioned absorption photometry. The full width at half maximum in the PL spectrum normalized by the peak value of the PL spectrum was determined as an index of colloid particle uniformity. A small half width indicates that the particle size is uniform.
(3) ＣｄＳｅコロイド粒子の量子効率
上記吸光光度測定に用いた分散液を利用して、量子効率測定システム（大塚電子社製）にて量子効率を測定した。この量子効率が高いほど、コロイド粒子の結晶の質が優れていることを示している。
(3) Quantum efficiency of CdSe colloidal particles Quantum efficiency was measured with a quantum efficiency measurement system (manufactured by Otsuka Electronics Co., Ltd.) using the dispersion liquid used for the above-mentioned absorption photometry. The higher the quantum efficiency, the better the crystal quality of the colloidal particles.
(4) ＣｄＳｅコロイド粒子の収量
分散液中のＣｄＳｅコロイド粒子を極性溶媒を用いて凝集させ遠心分離にて回収したものを真空乾燥して得られた乾燥物の質量から消費されたカドミウム質量を算出し、仕込みカドミウム質量を１としたときの消費割合を収量と定義した。この収量が高いほど、Ｃｄ源が無駄なく消費されたことを示している。
(4) Yield of CdSe colloidal particles Calculate the mass of cadmium consumed from the mass of the dried product obtained by aggregating the CdSe colloidal particles in the dispersion using a polar solvent and collecting them by centrifugation. The consumption ratio when the charged cadmium mass was 1 was defined as the yield. A higher yield indicates that the Cd source was consumed without waste.
表１から明らかなように、Ｃｄ原料液とＳｅ原料液の合成時間が１秒間である比較例１、３、４、６では、Ｃｄ原料液とＳｅ原料液の合成が不十分であるため、収量が０．０１〜０．２０と極めて低く、また量子効率が２９〜３３％と低かった。またＣｄ原料液とＳｅ原料液の合成時間が１分間である比較例２、５では、収量は０．６１及び０．４１と低くなかったが、Ｃｄ原料液とＳｅ原料液の合成時間が不十分であるため、量子効率が４２〜４３％に留まり、高い量子効率が得られなかった。比較例２で収量が０．６１と低くなかったのは、比較例２におけるＳｅ−ＯＤＡ液の保持時間が１０分であるので、Ｓｅ前駆錯体の大部分が平衡状態に達しておらず、Ｃｄ−Ｓｅモノマーが非常に熱解離し易かったためと考えられる。 As is clear from Table 1, in Comparative Examples 1, 3, 4, and 6 in which the synthesis time of the Cd raw material liquid and the Se raw material liquid is 1 second, the synthesis of the Cd raw material liquid and the Se raw material liquid is insufficient. The yield was as extremely low as 0.01-0.20, and the quantum efficiency was as low as 29-33%. In Comparative Examples 2 and 5 where the synthesis time of the Cd raw material liquid and the Se raw material liquid was 1 minute, the yields were not as low as 0.61 and 0.41, but the synthesis time of the Cd raw material liquid and the Se raw material liquid was not sufficient. Since it was sufficient, the quantum efficiency remained at 42 to 43%, and high quantum efficiency was not obtained. The reason why the yield in Comparative Example 2 was not as low as 0.61 was that the Se-ODA liquid retention time in Comparative Example 2 was 10 minutes, so that most of the Se precursor complex did not reach the equilibrium state, and Cd This is probably because the Se monomer was very easily thermally dissociated.
またＳｅ−ＯＤＡ液を調製した後の保持時間を３時間にした比較例７〜１０では、Ｓｅ源とＯＤＡとが平衡状態の錯形態になってしまい、収量が０．０８〜０．３０と極めて低かった。特に比較例８及び９では、Ｓｅ−ＯＤＡ液の保持時間が３時間以上で、Ｓｅ前駆錯体の大部分が平衡状態に達しているので、Ｃｄ−Ｓｅモノマーがゆっくりと熱解離する、即ち、コロイド粒子がゆっくりと成長すると考えられ、ゆっくり成長することで、原子の再配置運動が起こり易くなり、その結果、結晶の品質が向上し、量子効率が高くなると考えられる。 In Comparative Examples 7 to 10 in which the retention time after preparing the Se-ODA liquid was 3 hours, the Se source and ODA were in a complex state of equilibrium, and the yield was 0.08 to 0.30. It was very low. Particularly, in Comparative Examples 8 and 9, since the retention time of the Se-ODA liquid is 3 hours or more and most of the Se precursor complex has reached an equilibrium state, the Cd-Se monomer is slowly thermally dissociated, that is, colloid. It is thought that the particles grow slowly, and the slow growth facilitates the rearrangement movement of atoms. As a result, the quality of the crystal is improved and the quantum efficiency is considered to be increased.
更に合成時間が１秒〜９分という短い比較例１〜８では、粒子成長に伴うＰＬスペクトルの縮小の原理からＰＬスペクトルが広がったままであるため、また合成時間が２時間又は１５時間と長い比較例９〜１０では、オストワルド成長も同時に進行しＰＬスペクトルの広がりが生じたため、ＰＬスペクトルのピークにおける半値幅が３０ｎｍを超えていた。 Furthermore, in Comparative Examples 1 to 8, which have a short synthesis time of 1 second to 9 minutes, the PL spectrum is still broadened due to the principle of shrinking the PL spectrum accompanying particle growth, so that the synthesis time is long as 2 hours or 15 hours. In Examples 9 to 10, the Ostwald growth also progressed simultaneously, and the PL spectrum broadened, so the half width at the peak of the PL spectrum exceeded 30 nm.
これに対して、Ｓｅ−ＯＤＡ液を調製した後の保持時間を１０分〜２時間にし、Ｓｅ−ＯＤＡ液の最終液温を９０〜１１０℃にし、Ｃｄ原料液とＳｅ原料液の合成時間を１０分〜１５時間にした実施例１〜１０では、粒径が１．８〜５．７ｎｍであり、ＰＬスペクトルのピークにおける半値幅が３０ｎｍ以下であり、量子効率が５８以上であり、収量が０．５５〜１．００と高かった。 In contrast, the retention time after preparing the Se-ODA liquid is 10 minutes to 2 hours, the final liquid temperature of the Se-ODA liquid is 90 to 110 ° C., and the synthesis time of the Cd raw material liquid and the Se raw material liquid is In Examples 1 to 10 in which the time is 10 minutes to 15 hours, the particle size is 1.8 to 5.7 nm, the half width at the peak of the PL spectrum is 30 nm or less, the quantum efficiency is 58 or more, and the yield is It was as high as 0.55 to 1.00.
表２から明らかなように、Ｓｅ−ＯＤＡ液を調製するときの加熱保持時間を３時間又は１０時間にした比較例８、１１〜１５では、ＰＬスペクトルのピークにおける半値幅が３１〜３６ｎｍと広くなり、かつ収量が０．２０〜０．２８と低かった。これは、Ｓｅ−ＯＤＡ液の保持時間が３時間以上で、Ｓｅ前駆錯体の大部分が平衡状態に達しているので、Ｃｄ−Ｓｅモノマーがゆっくりと熱解離し、その結果、Ｓｅ原料液をＣｄ原料液に注入した直後に消費されるＣｄ−Ｓｅモノマー量が少なくなり、核生成と成長の分離が悪化する（ＬａＭｅｒモデル）ことによる。この核生成と成長の分離が悪化すると、粒度分布は広がり、それを反映して、ＰＬスペクトルのピークにおける半値幅が広くなるものと考えられる。 As is clear from Table 2, in Comparative Examples 8 and 11-15 in which the heating and holding time when preparing the Se-ODA liquid was 3 hours or 10 hours, the half width at the peak of the PL spectrum was as wide as 31 to 36 nm. And the yield was as low as 0.20 to 0.28. This is because the retention time of the Se-ODA liquid is 3 hours or more and most of the Se precursor complex has reached an equilibrium state, so that the Cd-Se monomer slowly thermally dissociates, and as a result, the Se raw material liquid is converted into Cd. This is because the amount of Cd—Se monomer consumed immediately after injection into the raw material liquid decreases, and the separation between nucleation and growth deteriorates (LaMer model). When the separation between nucleation and growth is deteriorated, the particle size distribution is broadened, and it is considered that the half width at the peak of the PL spectrum is widened.
Ｓｅ−ＯＤＡ液を調製するときの加熱保持時間を１０時間にした比較例１６では、Ｓｅ−ＯＤＡ液が平衡状態に達しているが、合成液温が２８０℃と高いため、その温度効果でＣｄ−Ｓｅの原料錯体からの熱解離が速くなり、Ｃｄ−Ｓｅ消費量が大きく収量が０．８７と高くなった。また温度効果でＣｄ−Ｓｅの原料錯体からの熱解離が速くなるので、成長に寄与するＣｄ−Ｓｅ量も増え、粒径が６．１ｎｍと大きくなった。 In Comparative Example 16 in which the heating and holding time when preparing the Se-ODA liquid was 10 hours, the Se-ODA liquid reached an equilibrium state, but the synthesis liquid temperature was as high as 280 ° C. Thermal dissociation from the raw material complex of -Se was accelerated, the consumption of Cd-Se was large, and the yield was as high as 0.87. In addition, since the thermal dissociation from the Cd—Se raw material complex is accelerated due to the temperature effect, the amount of Cd—Se contributing to the growth is increased, and the particle size is increased to 6.1 nm.
比較例１１〜１６は、Ｓｅ−ＯＤＡ液の最終温度とＣｄ原料液温度（２８０℃）の差が小さくなっており、混合後の合成液の液温低下が小さくなり、核生成と粒成長の分離ができないので、合成途中で核生成が起こる。途中で生成した核の成長はその分合成時間が短い。従って、結晶化に必要な時間を掛けられていないコロイド粒子も存在する。そのようなコロイド粒子が存在する分、トータルの量子効率は低下する。 In Comparative Examples 11 to 16, the difference between the final temperature of the Se-ODA liquid and the Cd raw material liquid temperature (280 ° C.) is small, the liquid temperature drop of the synthetic liquid after mixing is small, and nucleation and grain growth Nucleation occurs during synthesis because it cannot be separated. The growth of nuclei generated along the way has a shorter synthesis time. Therefore, there are colloidal particles that do not take the time necessary for crystallization. The total quantum efficiency is reduced by the presence of such colloidal particles.
これに対して、Ｓｅ−ＯＤＡ液を調製した後の保持時間を１０分〜２時間にし、Ｓｅ−ＯＤＡ液の最終液温を１００〜２８０℃にし、Ｃｄ原料液とＳｅ原料液の合成時間を９〜１３分にした実施例１、３、８、１１〜１９では、粒径が１．８〜６．０ｎｍであり、ＰＬスペクトルのピークにおける半値幅が３０ｎｍ以下であり、量子効率が４５以上であり、収量が０．５５〜１．００と高かった。 In contrast, the retention time after preparing the Se-ODA liquid is 10 minutes to 2 hours, the final liquid temperature of the Se-ODA liquid is 100 to 280 ° C., and the synthesis time of the Cd raw material liquid and the Se raw material liquid is In Examples 1, 3, 8, and 11 to 19 that are 9 to 13 minutes, the particle size is 1.8 to 6.0 nm, the half width at the peak of the PL spectrum is 30 nm or less, and the quantum efficiency is 45 or more. The yield was as high as 0.55 to 1.00.
本発明の方法で製造されたＣｄＳｅコロイド粒子は、ディスプレイ、照明、医療用画像、バイオセンサー、ＬＥＤ、レーザーの分野で利用することができる。 The CdSe colloidal particles produced by the method of the present invention can be used in the fields of displays, illumination, medical images, biosensors, LEDs, and lasers.
Claims (5)
(a) 前記Ｓｅ原料液を、Ｓｅ源と配位性溶媒とを混合した後、２００〜２６０℃の温度に加熱して１０分〜２時間保持し、続いて９０〜１１０℃の温度に降温することにより調製する工程と、
(b) ２７０〜２９０℃の温度に保持された前記Ｃｄ原料液に９０〜１１０℃の温度に保持された前記Ｓｅ原料液を注入して混合した後、注入開始時刻から１０分〜１５時間保持することにより、合成液を調製し、前記合成液中で生成したＣｄＳｅコロイド核を粒成長させる工程と、
(c) 前記ＣｄＳｅコロイド核が粒成長した液に極性溶媒を添加混合して前記液中で分散しているＣｄＳｅコロイド粒子をＣｄＳｅコロイド凝集粒子にする工程と、
(d) 前記液を固液分離して前記ＣｄＳｅコロイド凝集粒子を回収する工程と、
(e) 前記回収したＣｄＳｅコロイド凝集粒子に非極性溶媒を添加混合してＣｄＳｅコロイド粒子が分散した液にする工程と、
(f) 前記液に極性溶媒を添加混合して前記液中で分散しているＣｄＳｅコロイド粒子をＣｄＳｅコロイド凝集粒子にする工程と、
(g) 前記液を固液分離して前記ＣｄＳｅコロイド凝集粒子を回収する工程と、
(h) 前記回収したＣｄＳｅコロイド凝集粒子に非極性溶媒を添加混合してＣｄＳｅコロイド粒子が分散した液にする工程と
を上記(a)〜(h)の工程順に含むことを特徴とするＣｄＳｅコロイド粒子の製造方法。 In the method of producing CdSe colloidal particles by injecting and mixing the Se raw material liquid into the Cd raw material liquid,
(a) After mixing the Se raw material liquid with the Se source and the coordinating solvent, the Se raw material liquid is heated to a temperature of 200 to 260 ° C. and held for 10 minutes to 2 hours, and then cooled to a temperature of 90 to 110 ° C. A step of preparing by:
(b) After injecting and mixing the Se raw material liquid maintained at a temperature of 90 to 110 ° C. into the Cd raw material liquid maintained at a temperature of 270 to 290 ° C., the mixture is maintained for 10 minutes to 15 hours from the injection start time. A step of preparing a synthesis solution and growing grains of CdSe colloid nuclei generated in the synthesis solution;
(c) adding a polar solvent to the liquid in which the CdSe colloid nuclei are grown and mixing the mixture to make CdSe colloidal particles dispersed in the liquid into CdSe colloidal aggregated particles;
(d) recovering the CdSe colloidal agglomerated particles by solid-liquid separation of the liquid;
(e) adding a non-polar solvent to the collected CdSe colloidal aggregated particles and mixing them to obtain a liquid in which CdSe colloidal particles are dispersed;
(f) adding a polar solvent to the liquid and mixing the CdSe colloidal particles dispersed in the liquid into CdSe colloidal agglomerated particles;
(g) recovering the CdSe colloidal agglomerated particles by solid-liquid separation of the liquid;
(h) including a step of adding a nonpolar solvent to the collected CdSe colloidal aggregated particles and mixing them to form a liquid in which the CdSe colloidal particles are dispersed, in the order of the steps (a) to (h) above. Particle production method.
(m) 前記Ｓｅ原料液を、Ｓｅ源と配位性溶媒とを混合した後、２００〜２６０℃の温度に加熱して１０分〜２時間保持し、続いて１００〜２８０℃の温度に降温又は昇温することにより調製する工程と、
(n) ２７０〜２９０℃の温度に保持された前記Ｃｄ原料液に前記Ｃｄ原料液の温度と同一又は前記温度より低い１００〜２８０℃の温度に保持された前記Ｓｅ原料液を注入して混合した後、注入開始時刻から7〜１３分保持することにより、合成液を調製し、前記合成液中で生成したＣｄＳｅコロイド核を粒成長させる工程と、
(o) 前記ＣｄＳｅコロイド核が粒成長した液に極性溶媒を添加混合して前記液中で分散しているＣｄＳｅコロイド粒子をＣｄＳｅコロイド凝集粒子にする工程と、
(p) 前記液を固液分離して前記ＣｄＳｅコロイド凝集粒子を回収する工程と、
(q) 前記回収したＣｄＳｅコロイド凝集粒子に非極性溶媒を添加混合してＣｄＳｅコロイド粒子が分散した液にする工程と、
(r) 前記液に極性溶媒を添加混合して前記液中で分散しているＣｄＳｅコロイド粒子をＣｄＳｅコロイド凝集粒子にする工程と、
(s) 前記液を固液分離して前記ＣｄＳｅコロイド凝集粒子を回収する工程と、
(t) 前記回収したＣｄＳｅコロイド凝集粒子に非極性溶媒を添加混合してＣｄＳｅコロイド粒子が分散した液にする工程と
を上記(m)〜(t)の工程順に含むことを特徴とするＣｄＳｅコロイド粒子の製造方法。 In the method of producing CdSe colloidal particles by injecting and mixing the Se raw material liquid into the Cd raw material liquid,
(m) After mixing the Se raw material liquid with the Se source and the coordinating solvent, the Se raw material liquid is heated to a temperature of 200 to 260 ° C. and held for 10 minutes to 2 hours, and then the temperature is lowered to a temperature of 100 to 280 ° C. Or a step of preparing by raising the temperature;
(n) Injecting and mixing the Se raw material liquid maintained at a temperature of 100 to 280 ° C., which is the same as or lower than the temperature of the Cd raw material liquid, into the Cd raw material liquid maintained at a temperature of 270 to 290 ° C. Then, by holding for 7 to 13 minutes from the injection start time, a step of preparing a synthesis solution and growing CdSe colloid nuclei generated in the synthesis solution,
(o) adding a polar solvent to the liquid in which the CdSe colloid nuclei have grown and mixing the mixture to make CdSe colloidal particles dispersed in the liquid to be CdSe colloidal aggregated particles;
(p) solid-liquid separation of the liquid to recover the CdSe colloidal aggregated particles;
(q) adding a nonpolar solvent to the recovered CdSe colloidal aggregated particles and mixing them to obtain a liquid in which CdSe colloidal particles are dispersed;
(r) adding CdSe colloidal particles dispersed in the liquid by adding a polar solvent to the liquid to make CdSe colloidal aggregated particles;
(s) recovering the CdSe colloid aggregated particles by solid-liquid separation of the liquid;
(t) adding a non-polar solvent to the recovered CdSe colloidal aggregated particles and mixing them to obtain a liquid in which CdSe colloidal particles are dispersed, in the order of the steps (m) to (t) above. Particle production method.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2016045060A JP6569566B2 (en) | 2016-03-09 | 2016-03-09 | Method for producing CdSe colloidal particles |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2016045060A JP6569566B2 (en) | 2016-03-09 | 2016-03-09 | Method for producing CdSe colloidal particles |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JP2017160072A JP2017160072A (en) | 2017-09-14 |
| JP6569566B2 true JP6569566B2 (en) | 2019-09-04 |
Family
ID=59853866
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP2016045060A Active JP6569566B2 (en) | 2016-03-09 | 2016-03-09 | Method for producing CdSe colloidal particles |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP6569566B2 (en) |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108373919A (en) * | 2018-01-16 | 2018-08-07 | 湖北新纵科病毒疾病工程技术有限公司 | A kind of preparation method of CdSe quantum dot |
Family Cites Families (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP4772105B2 (en) * | 2008-12-10 | 2011-09-14 | シャープ株式会社 | Semiconductor light emitting device and image display device using the same |
| JP5709188B2 (en) * | 2011-05-23 | 2015-04-30 | 独立行政法人産業技術総合研究所 | Fluorescent fine particles comprising thin film silica glass coated quantum dots and method for producing the same |
| US9493351B2 (en) * | 2011-12-07 | 2016-11-15 | East China University Of Science And Technology | Methods of producing cadmium selenide multi-pod nanocrystals |
-
2016
- 2016-03-09 JP JP2016045060A patent/JP6569566B2/en active Active
Also Published As
| Publication number | Publication date |
|---|---|
| JP2017160072A (en) | 2017-09-14 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| JP6114369B2 (en) | Nanoparticles | |
| TWI547540B (en) | Group iii-v/zinc chalcogenide alloyed semiconductor quantum dots | |
| CN109312228A (en) | Improve the method for the core shell quantum dots form of the nanostructure of highly luminescent | |
| KR20190015516A (en) | Synthesis of core-shell nanocrystals at high temperature | |
| US10865109B2 (en) | Method for preparation of magic-sized nano-crystalline substance | |
| JP5698679B2 (en) | Low temperature synthesis of colloidal nanocrystals | |
| JP2018115315A (en) | Cd-FREE COLLOIDAL QUANTUM DOT EMITTING VISIBLE FLORESCENCE AND METHOD FOR PRODUCING THE SAME | |
| JP2020521707A (en) | Method for synthesizing semiconducting materials | |
| JP5019052B2 (en) | CdSe quantum dot and method for producing the same | |
| TW201523874A (en) | Colloidal semiconductor metal chalcogenide nanostructures | |
| JP2007224233A (en) | Method and apparatus for producing semiconductor nanoparticles | |
| Chakrabarty et al. | Cadmium deoxycholate: a new and efficient precursor for highly luminescent CdSe nanocrystals | |
| JP4714859B2 (en) | Method for synthesizing copper sulfide nanoparticles | |
| Li et al. | One-pot self-assembly of flower-like Cu 2 S structures with near-infrared photoluminescent properties | |
| JP6569566B2 (en) | Method for producing CdSe colloidal particles | |
| US11859117B2 (en) | Preparation method for quantum dots | |
| JP5212588B2 (en) | Method for producing nanoparticles | |
| JP6531681B2 (en) | Method of producing CdSe colloidal particles | |
| JP2013060593A (en) | Preparation of nanoparticle with narrow luminescence spectrum | |
| JP6561879B2 (en) | Method for producing InAs colloidal particles | |
| CN113845897B (en) | Synthetic method of colloidal semiconductor flaky nanocrystal | |
| Nikolenko et al. | Nonisothermal high-temperature colloidal synthesis of CdSe nanocrystals | |
| KR100963538B1 (en) | Process for preparing nano-sized cadmium and cadmium chalcogenide colloid in organic solvents | |
| JP6947017B2 (en) | Method for synthesizing InAs colloidal particles | |
| WO2018135434A1 (en) | Cd-free colloidal quantum dot capable of emitting visible fluorescence, and method for producing same |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| A621 | Written request for application examination |
Free format text: JAPANESE INTERMEDIATE CODE: A621 Effective date: 20180926 |
|
| A131 | Notification of reasons for refusal |
Free format text: JAPANESE INTERMEDIATE CODE: A131 Effective date: 20190423 |
|
| A977 | Report on retrieval |
Free format text: JAPANESE INTERMEDIATE CODE: A971007 Effective date: 20190426 |
|
| A521 | Written amendment |
Free format text: JAPANESE INTERMEDIATE CODE: A523 Effective date: 20190509 |
|
| TRDD | Decision of grant or rejection written | ||
| A01 | Written decision to grant a patent or to grant a registration (utility model) |
Free format text: JAPANESE INTERMEDIATE CODE: A01 Effective date: 20190709 |
|
| A61 | First payment of annual fees (during grant procedure) |
Free format text: JAPANESE INTERMEDIATE CODE: A61 Effective date: 20190722 |
|
| R150 | Certificate of patent or registration of utility model |
Ref document number: 6569566 Country of ref document: JP Free format text: JAPANESE INTERMEDIATE CODE: R150 |