TW202113037A - Quantum dots and production method therefor - Google Patents

Quantum dots and production method therefor Download PDF

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TW202113037A
TW202113037A TW109127723A TW109127723A TW202113037A TW 202113037 A TW202113037 A TW 202113037A TW 109127723 A TW109127723 A TW 109127723A TW 109127723 A TW109127723 A TW 109127723A TW 202113037 A TW202113037 A TW 202113037A
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quantum dots
silver
quantum dot
quantum
infrared region
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TWI838568B (en
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島崎俊明
荷方惣一朗
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日商Ｎｓ材料股份有限公司
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    • B—PERFORMING OPERATIONS; TRANSPORTING
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    • B82Y20/00—Nanooptics, e.g. quantum optics or photonic crystals
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B82—NANOTECHNOLOGY
    • B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
    • B82Y40/00—Manufacture or treatment of nanostructures
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    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
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    • C09K11/00—Luminescent, e.g. electroluminescent, chemiluminescent materials
    • C09K11/08—Luminescent, e.g. electroluminescent, chemiluminescent materials containing inorganic luminescent materials
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    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
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    • C09K11/88—Luminescent, e.g. electroluminescent, chemiluminescent materials containing inorganic luminescent materials containing selenium, tellurium or unspecified chalcogen elements
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Abstract

The purpose of the present invention is to provide: Ag2E (E is at least one of tellurium, selenium, and sulfur) quantum dots which exhibit a distinct absorption peak in the near-infrared region and with which it is possible to control the absorption wavelength in the near-infrared region according to purpose; and a highly safe quantum dot production method with which mass production is possible and the absorption wavelength can be freely controlled within the near-infrared region according to purpose. A quantum dot according to the present invention is characterized by being a nanocrystal represented by Ag2E (E is at least one of Te, Se, and S) that contains silver and a chalcogen, and by having an average particle size of 1-15 nm, inclusive. In the present invention, it is preferable for the absorption wavelength to be in the range of the near-infrared region from 800-1700 nm.

Description

量子點及其製造方法Quantum dot and its manufacturing method

本發明係關於一種於近紅外區域進行吸收或者發光之量子點、及其製造方法。The present invention relates to a quantum dot that absorbs or emits light in the near-infrared region, and a manufacturing method thereof.

量子點係包含幾百～幾千個左右之原子之奈米粒子。量子點亦被稱為螢光奈米粒子、半導體奈米粒子或奈米晶體。Quantum dots are nano-particles containing hundreds to thousands of atoms. Quantum dots are also called fluorescent nanoparticles, semiconductor nanoparticles or nanocrystals.

對於量子點，可藉由奈米粒子之粒徑或組成對發光波長進行各種變更。又，作為表示量子點之性能或特性者，可列舉：螢光量子產率(Quantum Yield：QY)、螢光半高寬(Full Width at Half Maximum：FWHM)、吸收波長或螢光波長。For quantum dots, the emission wavelength can be changed in various ways by the particle size or composition of the nanoparticle. In addition, examples of the performance or characteristics of quantum dots include: fluorescence quantum yield (Quantum Yield: QY), fluorescence half-width at half maximum (FWHM), absorption wavelength, or fluorescence wavelength.

例如，於下述非專利文獻1及非專利文獻2中，有關於銀硫屬化物量子點之記載。For example, in the following Non-Patent Document 1 and Non-Patent Document 2, there are descriptions of silver chalcogenide quantum dots.

於非專利文獻1中，報告了藉由使用CdTe之陽離子交換法進行之Ag2 Te量子點之合成法。又，於非專利文獻2中，報告了經由矽烷基醯胺化銀之Ag2 Te量子點之合成法。In Non-Patent Document 1, a method of synthesizing Ag 2 Te quantum dots by a cation exchange method using CdTe is reported. In addition, in Non-Patent Document 2, a method for synthesizing Ag 2 Te quantum dots via silver silylamide is reported.

然而，非專利文獻1係經由作為有毒規制對象重金屬之鎘中間物之合成法，缺乏實用化。又，非專利文獻2中所使用之矽烷基醯胺化銀係於大氣下使用時具有較高之反應性之反應劑，其操作需要注意。 先前技術文獻 非專利文獻However, Non-Patent Document 1 is a method for synthesizing cadmium intermediates, which is a heavy metal that is a target of toxic regulation, and lacks practical application. In addition, the silver silyl amide used in Non-Patent Document 2 is a reactant that has high reactivity when used in the atmosphere, and care must be taken in its operation. Prior art literature Non-patent literature

非專利文獻1：ACS Appl. Mater. Interfaces 2013, VOL. 5, pp 1149-1155 Cation Exchange-Based Facile Aqueous Synthesis of Small, Stable, and Nontoxic Near-Infrared Ag2 Te/ZnS Core/Shell Quantum DotsEmitting in the Second Biological Window 非專利文獻2：ACS NANO 2011, VOL. 5, NO. 5, pp 3758-3765 Infrared Emitting and Photoconducting Colloidal SilverChalcogenide Nanocrystal Quantum Dots from a Silylamide-Promoted SynthesisNon-Patent Document 1: ACS Appl. Mater. Interfaces 2013, VOL. 5, pp 1149-1155 Cation Exchange-Based Facile Aqueous Synthesis of Small, Stable, and Nontoxic Near-Infrared Ag 2 Te/ZnS Core/Shell Quantum DotsEmitting in the Second Biological Window Non-Patent Document 2: ACS NANO 2011, VOL. 5, NO. 5, pp 3758-3765 Infrared Emitting and Photoconducting Colloidal SilverChalcogenide Nanocrystal Quantum Dots from a Silylamide-Promoted Synthesis

[發明所欲解決之問題][The problem to be solved by the invention]

因此，要求開發Ag2 E(E為Te、Se、S中之至少任一種)量子點之實用化及安全性較高之製造法。此外，存在如下課題。Therefore, it is required to develop a practical and safe manufacturing method for Ag 2 E (E is at least one of Te, Se, and S) quantum dots. In addition, there are the following problems.

即，重要的是於使用量子點作為近紅外區域之吸收材料之情形時，於近紅外區域存在明確之吸收峰，又，能夠根據目的而控制自如地調整吸收波長。然而，尚未確立如下銀硫屬化物量子點、及其製造方法，該銀硫屬化物量子點係吸收峰明確地存在於近紅外區域，進而能夠適當地獲得基於目的之吸收波長。That is, it is important that when quantum dots are used as the absorption material in the near-infrared region, there is a clear absorption peak in the near-infrared region, and the absorption wavelength can be adjusted freely according to the purpose. However, silver chalcogenide quantum dots have not yet been established, and a method of manufacturing the silver chalcogenide quantum dots whose absorption peaks are clearly present in the near-infrared region, and which can appropriately obtain the absorption wavelengths for the purpose.

又，認為對於非專利文獻1及非專利文獻2中所記載之銀硫屬化物量子點之近紅外螢光光譜，當根據雖未明確記載但已揭示之光譜進行判斷時，螢光半高寬(Full Width at Half Maximum：FWHM)超過200 nm。In addition, it is considered that for the near-infrared fluorescence spectra of silver chalcogenide quantum dots described in Non-Patent Document 1 and Non-Patent Document 2, when judged based on the unspecified but disclosed spectra, the fluorescence half-width (Full Width at Half Maximum: FWHM) exceeds 200 nm.

根據以上內容，而強烈要求開發銀硫屬化物量子點之實用化及安全性較高之製造方法，以及解析藉由此種方法所製造之銀硫屬化物量子點之物性。Based on the above, it is strongly requested to develop practical and safe manufacturing methods of silver chalcogenide quantum dots, and to analyze the physical properties of silver chalcogenide quantum dots manufactured by this method.

本發明係鑒於上述方面而完成者，其目的在於提供一種如下Ag2 E(E為Te、Se、S中之至少任一種)量子點、及量子點之製造方法，上述Ag2 E(E為Te、Se、S中之至少任一種)量子點能夠於近紅外區域顯示明確之吸收峰，並且獲得基於目的之吸收波長，上述量子點之製造方法可進行量產，進而於近紅外區域可根據目的而自由地控制吸收波長，且安全性高。The present invention was completed in view of the above aspects, and its purpose is to provide the following Ag 2 E (E is at least any one of Te, Se, S) quantum dots and a method for manufacturing quantum dots, the Ag 2 E (E is At least any one of Te, Se, S) quantum dots can show clear absorption peaks in the near-infrared region and obtain the absorption wavelength based on the purpose. The manufacturing method of the above-mentioned quantum dots can be mass-produced, and in the near-infrared region, it can be based on The purpose is to freely control the absorption wavelength, and the safety is high.

又，本發明係鑒於上述方面而完成者，其目的在於提供一種顯示高亮度之近紅外螢光之Ag2 E(E為Te、Se、S中之至少任一種)量子點、及可進行量產且安全性高之量子點之製造方法。 [解決問題之技術手段]In addition, the present invention was completed in view of the above-mentioned aspects, and its purpose is to provide an Ag 2 E (E is at least any one of Te, Se, and S) quantum dots displaying high-brightness near-infrared fluorescence, and a processable quantity A method for manufacturing quantum dots with high safety and production. [Technical means to solve the problem]

本發明中之量子點之特徵在於：其係含有銀與硫屬元素之Ag2 E(E為碲、硒或硫中之至少任一種)所表示之奈米晶體，且平均粒徑為1 nm以上15 nm以下。The quantum dots of the present invention are characterized in that they are nanocrystals represented by Ag 2 E (E is at least one of tellurium, selenium or sulfur) containing silver and chalcogen elements, and have an average particle size of 1 nm Above 15 nm.

本發明中之量子點之製造方法之特徵在於：藉由銀原料與含硫屬元素之三辛基膦來合成表示為Ag2 E(E為碲、硒或者硫中之至少任一種)之量子點。The method of manufacturing quantum dots in the present invention is characterized in that: a quantum dot represented by Ag 2 E (E is at least one of tellurium, selenium, or sulfur) is synthesized from silver raw material and trioctyl phosphine containing chalcogen elements. point.

又，本發明中之量子點之製造方法之特徵在於：藉由銀原料與二硫屬元素化合物來合成表示為Ag2 E(E為碲、硒或者硫中之至少任一種)之量子點。 [發明之效果]In addition, the method for manufacturing quantum dots in the present invention is characterized by synthesizing quantum dots represented by Ag 2 E (E is at least any one of tellurium, selenium, or sulfur) from a silver raw material and a dichalcogen compound. [Effects of Invention]

根據本發明之量子點，能夠於近紅外區域顯示明確之吸收峰，並且具有基於目的之吸收波長。According to the quantum dots of the present invention, it is possible to show a clear absorption peak in the near-infrared region and have an absorption wavelength based on the purpose.

或者，根據本發明之量子點，能夠使近紅外區域中之螢光半高寬變窄，能夠顯示高亮度之近紅外螢光。Or, according to the quantum dots of the present invention, the half-height width of the fluorescence in the near-infrared region can be narrowed, and high-brightness near-infrared fluorescence can be displayed.

又，根據本發明之量子點之製造方法，可於大氣下進行操作時，不使用顯示較高反應性之反應劑或有毒規制對象重金屬而藉由可進行量產之方法來合成。In addition, the method for manufacturing quantum dots according to the present invention can be synthesized by a method that can be mass-produced without using reactants showing high reactivity or heavy metals that are toxic regulatory targets when operating in the atmosphere.

於本發明中，作為量子點之合成法，可使用將銀原料與含硫屬元素之三辛基膦進行混合、或將銀原料與二硫屬元素化合物進行混合之方法。前者合成法適於可於近紅外區域顯示明確之吸收峰，並且根據目的而自由地控制吸收波長的量子點之製法。又，後者合成法適於可使近紅外區域中之螢光半高寬變窄，可顯示高亮度之近紅外螢光的量子點之製法。In the present invention, as a method for synthesizing quantum dots, a method of mixing a silver raw material with chalcogen-containing trioctyl phosphine, or mixing a silver raw material with a dichalcogen compound can be used. The former synthesis method is suitable for the production method of quantum dots that can show a clear absorption peak in the near-infrared region and freely control the absorption wavelength according to the purpose. In addition, the latter synthesis method is suitable for the production method of quantum dots that can narrow the fluorescence half-height width in the near-infrared region and display high-brightness near-infrared fluorescence.

以下，詳細地說明本發明之一實施方式(以下簡稱「實施方式」)。再者，本發明並不限於以下實施方式，可於其主旨之範圍內進行各種變形後實施。於本說明書中，「～」之記法包含下限值及上限值。Hereinafter, one embodiment of the present invention (hereinafter referred to as "embodiment") will be described in detail. In addition, the present invention is not limited to the following embodiments, and can be implemented with various modifications within the scope of the gist. In this manual, the notation of "~" includes the lower limit and the upper limit.

圖1A及圖1B係本實施方式中之量子點之模式圖。圖1A所示之量子點1係含有銀(Ag)、與硫屬元素(係指碲(Te)、硒(Se)及硫(S)中之至少任一種)之奈米晶體。以下，以Ag2 E(E為Te、Se、S中之至少任一種)表示本實施方式之量子點之化學式。1A and 1B are schematic diagrams of quantum dots in this embodiment. The quantum dot 1 shown in FIG. 1A is a nanocrystal containing silver (Ag) and a chalcogen element (referring to at least one of tellurium (Te), selenium (Se), and sulfur (S)). Hereinafter, Ag 2 E (E is at least any one of Te, Se, and S) represents the chemical formula of the quantum dot of this embodiment.

本實施方式中之量子點具有基於帶邊發光之螢光特性，並且根據其粒子之大小表現量子尺寸效果。The quantum dots in this embodiment have fluorescent characteristics based on band-edge emission, and exhibit quantum size effects according to the size of their particles.

本實施方式之量子點之平均粒徑之特徵在於為1 nm以上15 nm以下。又，於本實施方式中，可滿足上述平均粒徑，並且以均勻之粒徑生成多個量子點。所謂「均勻」係指90%以上之粒子包含於平均粒徑±30%以內之狀態。如此，於本實施方式中，可量產微細且均勻之優質量子點。The average particle diameter of the quantum dots of this embodiment is characterized by being 1 nm or more and 15 nm or less. In addition, in this embodiment, the above-mentioned average particle size can be satisfied, and a plurality of quantum dots can be generated with a uniform particle size. The so-called "uniform" refers to the state where more than 90% of the particles are contained within ±30% of the average particle size. In this way, in this embodiment, fine and uniform high-quality quantum dots can be mass-produced.

本實施方式之量子點中所含之Ag與Te、Ag與Se、或Ag與S為主成分，亦可包含除該等元素以外之元素。然而，如下所述，於本實施方式之量子點之製法中，不使用於大氣下進行操作時顯示較高之反應性之金屬醯胺或有機鋰化合物等反應劑，且反應中間物不包含以Cd或Pb為代表之規制對象重金屬。含鎘/含鉛化合物為有毒規制對象重金屬，容易導致成本上升、操作受限、或製造步驟變得繁雜。本實施方式之量子點不包含源自高反應性反應劑之物質或規制對象重金屬。又，於本實施方式中，亦可包含Te、Se及S中之兩種以上。The main components of Ag and Te, Ag and Se, or Ag and S contained in the quantum dots of this embodiment may also include elements other than these elements. However, as described below, in the method for producing quantum dots in this embodiment, reactants such as metal amides or organolithium compounds that exhibit high reactivity when operated in the atmosphere are not used, and the reaction intermediates do not contain Cd or Pb is the representative heavy metal that is regulated. Cadmium-containing/lead-containing compounds are toxic heavy metals that are subject to regulation, which can easily lead to increased costs, restricted operations, or complicated manufacturing steps. The quantum dots of this embodiment do not contain substances derived from highly reactive reactants or heavy metals to be regulated. In addition, in this embodiment, two or more of Te, Se, and S may also be included.

如圖1A所示，較佳為於量子點之表面配位有多個有機配位基2。藉此，可抑制量子點彼此之凝集，表現目標光學特性。可用於反應之配位基並無特別限定，例如可列舉以下配位基作為具有代表性者。As shown in FIG. 1A, it is preferable that a plurality of organic ligands 2 are coordinated on the surface of the quantum dot. Thereby, the aggregation of quantum dots can be suppressed, and the target optical characteristics can be expressed. The ligands that can be used in the reaction are not particularly limited, and for example, the following ligands can be cited as representative ones.

(1)脂肪族一級胺系 油胺：C18 H35 NH2 ；硬脂基(十八烷基)胺：C18 H37 NH2 ；十二烷基(月桂基)胺：C12 H25 NH2 ；癸基胺：C10 H21 NH2 ；辛基胺：C8 H17 NH2 (2)脂肪酸系 油酸：C17 H33 COOH；硬脂酸：C17 H35 COOH；棕櫚酸：C15 H31 COOH；肉豆蔻酸：C13 H27 COOH；月桂酸：C11 H23 COOH；癸酸：C9 H19 COOH；辛酸：C7 H15 COOH (3)硫醇系 十八烷硫醇：C18 H37 SH；十六烷硫醇：C16 H33 SH；十四烷硫醇：C14 H29 SH；十二烷硫醇：C12 H25 SH；癸硫醇：C10 H21 SH；辛硫醇：C8 H17 SH (4)膦系 三辛基膦：(C8 H17 )3 P；三苯基膦：(C6 H5 )3 P；三丁基膦：(C4 H9 )3 P (5)氧化膦系 三辛基氧化膦：(C8 H17 )3 P=O；三苯基氧化膦：(C6 H5 )3 P=O；三丁基氧化膦：(C4 H9 )3 P=O(1) Aliphatic primary amine oleylamine: C 18 H 35 NH 2 ; Stearyl (octadecyl) amine: C 18 H 37 NH 2 ; Dodecyl (lauryl) amine: C 12 H 25 NH 2 ; Decylamine: C 10 H 21 NH 2 ; Octylamine: C 8 H 17 NH 2 (2) Fatty acid series Oleic acid: C 17 H 33 COOH; Stearic acid: C 17 H 35 COOH; Palmitic acid : C 15 H 31 COOH; Myristic acid: C 13 H 27 COOH; Lauric acid: C 11 H 23 COOH; Capric acid: C 9 H 19 COOH; Caprylic acid: C 7 H 15 COOH Alkyl mercaptan: C 18 H 37 SH; hexadecyl mercaptan: C 16 H 33 SH; tetradecyl mercaptan: C 14 H 29 SH; dodecyl mercaptan: C 12 H 25 SH; decane mercaptan: C 10 H 21 SH; octyl mercaptan: C 8 H 17 SH (4) phosphine trioctyl phosphine: (C 8 H 17 ) 3 P; triphenylphosphine: (C 6 H 5 ) 3 P; tributyl Phosphine: (C 4 H 9 ) 3 P (5) Phosphine oxide series Trioctyl phosphine oxide: (C 8 H 17 ) 3 P=O; Triphenyl phosphine oxide: (C 6 H 5 ) 3 P=O ; Tributyl phosphine oxide: (C 4 H 9 ) 3 P=O

於本實施方式中，如圖1B所示，量子點1可為具有核1a、及被覆於核1a之表面之殼1b的核殼結構。如圖1B所示，較佳為於量子點1之表面配位有多個有機配位基2。In this embodiment, as shown in FIG. 1B, the quantum dot 1 may have a core-shell structure having a core 1a and a shell 1b covering the surface of the core 1a. As shown in FIG. 1B, it is preferable that a plurality of organic ligands 2 are coordinated on the surface of the quantum dot 1.

圖1B所示之核1a為Ag2 E。殼1b與核1a同樣地不包含Cd、Hg或Pd等規制對象重金屬、或以金屬醯胺或有機鋰化合物為代表之源自高反應性反應劑之物質。The core 1a shown in Fig. 1B is Ag 2 E. Like the core 1a, the shell 1b does not contain heavy metals to be regulated such as Cd, Hg, or Pd, or substances derived from highly reactive reactants represented by metal amides or organolithium compounds.

再者，殼1b可為固溶化於核1a之表面之狀態。於圖1B中，以虛線示出了核1a與殼1b之邊界，但該情況係指可藉由分析確認核1a與殼1b之邊界、或無法藉由分析確認核1a與殼1b之邊界中之任一者。Furthermore, the shell 1b may be in a state of being dissolved on the surface of the core 1a. In Figure 1B, the boundary between the core 1a and the shell 1b is shown by a dashed line, but this situation means that the boundary between the core 1a and the shell 1b can be confirmed by analysis, or the boundary between the core 1a and the shell 1b cannot be confirmed by analysis Any of them.

然而，於本實施方式中，關於不使用殼1b而僅為核1a、即圖1A之核單一成分之量子點1，可具有下述所示之吸收波長，或者可具有下述所示之螢光波長及螢光半高寬。However, in this embodiment, regarding the quantum dot 1 that does not use the shell 1b but only the core 1a, that is, the single component of the core of FIG. 1A, the quantum dot 1 may have the absorption wavelength shown below, or may have the fluorescence shown below. Light wavelength and fluorescence half-height width.

[第1量子點] ＜吸收特性＞ 本發明人等藉由可進行量產且安全性優異之新穎之製造方法來合成含有銀與硫屬元素之Ag2 E(E為碲、硒或者硫中之至少任一種)所表示之奈米晶體，並進行物性解析，結果可知於800 nm～1700 nm之近紅外區域具有吸收波長。 [First quantum dot] <Absorption characteristics> The inventors synthesized Ag 2 E containing silver and chalcogen elements by a novel manufacturing method that can be mass-produced and is excellent in safety (E is in tellurium, selenium, or sulfur). At least any one of the nanocrystals represented by), and the physical properties are analyzed. As a result, it is found that the near-infrared region from 800 nm to 1700 nm has an absorption wavelength.

所謂「吸收波長」係指吸收光譜之波峰之波長、即吸收峰出現在近紅外區域之狀態。本發明人等主要進行了如下研究：(1)近紅外區域中觀察到之吸收峰之根據目的進行之自由控制；(2)使近紅外區域中觀察到之吸收峰之峰頂與波谷(valley)之對比度明確化。關於上述(1)，係為了響應欲根據目的於近紅外區域中調節吸收峰波長之要求。又，關於上述(2)，係為了於用作近紅外線吸收材料時，使吸收之導通/截止變得明確。The so-called "absorption wavelength" refers to the wavelength of the peak of the absorption spectrum, that is, the state where the absorption peak appears in the near-infrared region. The inventors of the present invention mainly conducted the following studies: (1) Free control of absorption peaks observed in the near-infrared region according to the purpose; (2) Make the peak tops and valleys of the absorption peaks observed in the near-infrared region The contrast is clarified. Regarding the above (1), it is in response to a request to adjust the wavelength of the absorption peak in the near-infrared region according to the purpose. In addition, regarding the above (2), when it is used as a near-infrared absorbing material, the on/off of absorption becomes clear.

根據本實施方式之量子點，於800 nm～1700 nm之近紅外區域具有吸收波長，又，能夠根據目的而自由地控制該吸收波長。關於控制方法，如下述製造方法所示，作為一例，可示出對溶劑之量(亦可說是銀與硫屬元素之濃度)、用作溶劑之十八烯(ODE)、及三辛基膦(TOP)之比率進行調節。According to the quantum dot of this embodiment, it has an absorption wavelength in the near-infrared region of 800 nm to 1700 nm, and the absorption wavelength can be freely controlled according to the purpose. Regarding the control method, as shown in the following manufacturing method, as an example, the amount of the solvent (the concentration of silver and chalcogen), the octadecene (ODE) used as the solvent, and trioctyl can be shown as an example. The ratio of phosphine (TOP) is adjusted.

於本實施方式中，可將吸收峰之峰頂與波谷(valley)之吸光度比設為1.0以上。吸光度比較佳為設為1.5以上，更佳為設為2.0以上。藉此，於用作近紅外線吸收材料時，可使吸收之導通/截止變得明確。In this embodiment, the absorbance ratio between the peak top of the absorption peak and the valley can be set to 1.0 or more. The absorbance is preferably 1.5 or more, and more preferably 2.0 or more. Thereby, when it is used as a near-infrared absorbing material, the on/off of absorption can be made clear.

於本實施方式中，較佳為具有上述吸光度比之最長吸收波長波峰存在於1000～1500 nm之近紅外區域內。藉此，可進一步使與所需目的對應之吸收之導通/截止變得明確。In this embodiment, it is preferable that the longest absorption wavelength peak having the aforementioned absorbance ratio exists in the near-infrared region of 1000 to 1500 nm. By this, it is possible to further clarify the on/off of absorption corresponding to the desired purpose.

於本實施方式中，較佳為於1100 nm～1600 nm之近紅外區域具有最長吸收波長。又，於本實施方式中，更佳為於1300 nm～1500 nm之近紅外區域具有最長吸收波長。In this embodiment, it is preferable that the near-infrared region of 1100 nm to 1600 nm has the longest absorption wavelength. Moreover, in this embodiment, it is more preferable to have the longest absorption wavelength in the near infrared region of 1300 nm to 1500 nm.

又，本實施方式之量子點之平均粒徑為1 nm以上15 nm以下，且均一化，但就於近紅外區域獲得吸收波長之方面而言，設為較小之粒徑亦為一個因素。In addition, the average particle diameter of the quantum dots of this embodiment is 1 nm or more and 15 nm or less, and is uniform. However, in terms of obtaining absorption wavelengths in the near-infrared region, a smaller particle diameter is also a factor.

＜配位基交換＞ 於本實施方式中，對於有機配位基2，較佳為使用較短之配位基(ligand)。上述情況並無限定，對於有機配位基2，可使用3-巰基丙酸(MPA)。＜Land Exchange＞ In this embodiment, for the organic ligand 2, it is preferable to use a shorter ligand. The above situation is not limited. For the organic ligand 2, 3-mercaptopropionic acid (MPA) can be used.

量子點例如大量分散於紅外線感測器之光吸收層(或者量子點層)而配置。此時，光吸收層中所含之量子點之配位基較佳為較藉由合成法而形成量子點時之配位基短。For example, a large number of quantum dots are dispersed in the light absorption layer (or quantum dot layer) of the infrared sensor. At this time, the ligand of the quantum dot contained in the light absorbing layer is preferably shorter than the ligand when the quantum dot is formed by a synthesis method.

如此，藉由對光吸收層中所含之量子點之配位基使用較短者，可使光吸收層之粗糙度變小，可提高電子、電洞之提取效率。另一方面，對藉由液相合成法而形成量子點時之配位基使用較長者，藉此可提高分散成膜性。In this way, by using a shorter ligand for the quantum dot contained in the light absorbing layer, the roughness of the light absorbing layer can be reduced, and the extraction efficiency of electrons and holes can be improved. On the other hand, using a longer ligand for the formation of quantum dots by the liquid phase synthesis method can improve the dispersion and film-forming properties.

於本實施方式中，可於藉由液相合成法而合成配位基較長之量子點後，在塗佈包含量子點之組成物之前或之後交換為較短之配位基(例如3-巰基丙酸)。In this embodiment, after synthesizing quantum dots with longer ligands by a liquid phase synthesis method, they can be exchanged for shorter ligands (such as 3- Mercaptopropionic acid).

雖無特別限定，但於本實施方式中，較佳為於合成階段之最終步驟中添加十二烷硫醇(DDT)。藉此，可迅速進行配位基交換。Although not particularly limited, in this embodiment, it is preferable to add dodecyl mercaptan (DDT) in the final step of the synthesis stage. In this way, ligand exchange can be performed quickly.

[第2量子點] ＜螢光特性＞ 本實施方式之量子點之螢光波長為800 m～1700 nm之近紅外區域之範圍，且螢光半高寬為200 nm以下。此處，所謂「螢光波長」係指螢光光譜之波峰之波長。本實施方式之量子點可於800 nm以上1700 nm以下之範圍內控制螢光波長，較佳為1000 nm以上1700 nm以下，更佳為1200 nm以上1700 nm以下。又，所謂「螢光半高寬」係指表示螢光光譜中之螢光強度之峰值的一半強度下之螢光波長之擴寬的半峰全幅值(Full Width at Half Maximum)。又，螢光半高寬較佳為150 nm以下，更佳為100 nm以下。[Second Quantum Dot] ＜Fluorescence characteristics＞ The fluorescence wavelength of the quantum dots of this embodiment is in the near-infrared region from 800 m to 1700 nm, and the fluorescence half-height width is less than 200 nm. Here, the so-called "fluorescence wavelength" refers to the wavelength of the peak of the fluorescence spectrum. The quantum dot of this embodiment can control the fluorescence wavelength in the range of 800 nm to 1700 nm, preferably 1000 nm to 1700 nm, and more preferably 1200 nm to 1700 nm. In addition, the so-called "fluorescence half-width at half maximum" refers to the full width at half maximum (Full Width at Half Maximum) that represents the widening of the fluorescence wavelength at half the intensity of the fluorescence intensity peak in the fluorescence spectrum. In addition, the fluorescence half-height width is preferably 150 nm or less, and more preferably 100 nm or less.

於本實施方式中，如下所述，作為合成量子點之反應系統，將二硫屬元素化合物作為前驅物，對前驅物進行導入Ag。藉由基於此種直接且簡易之合成反應來製造量子點，可使螢光半高寬變窄。如下述實驗結果所示，具體而言，可獲得150 nm以下之螢光半高寬。In this embodiment, as described below, as a reaction system for synthesizing quantum dots, a dichalcogen compound is used as a precursor, and Ag is introduced into the precursor. By manufacturing quantum dots based on such a direct and simple synthesis reaction, the fluorescence half-height width can be narrowed. As shown in the following experimental results, specifically, a fluorescent half-height width of less than 150 nm can be obtained.

本實施方式中之量子點之螢光量子產率(Quantum Yield)為5%以上。又，螢光量子產率更佳為10%以上，進而較佳為20%以上，進而更佳為30%以上。如此，於本實施方式中，可提高量子點之螢光量子產率。The fluorescence quantum yield (Quantum Yield) of the quantum dots in this embodiment is more than 5%. In addition, the fluorescence quantum yield is more preferably 10% or more, still more preferably 20% or more, and still more preferably 30% or more. In this way, in this embodiment, the fluorescence quantum yield of the quantum dots can be improved.

於本實施方式中，可於800 nm以上1700 nm以下之範圍內自由地控制螢光波長。本實施方式中之量子點係以除銀以外使用硫屬元素之Ag2 E作為基礎之固溶體。於本實施方式中，藉由調整量子點之平均粒徑及量子點之組成，能夠適當地控制螢光波長。螢光波長較佳為1000 nm以上，更佳為1200 nm以上。In this embodiment, the fluorescence wavelength can be freely controlled within the range of 800 nm to 1700 nm. The quantum dots in this embodiment are solid solutions based on Ag 2 E using chalcogen elements in addition to silver. In this embodiment, by adjusting the average particle diameter of the quantum dots and the composition of the quantum dots, the fluorescence wavelength can be appropriately controlled. The fluorescence wavelength is preferably 1000 nm or more, more preferably 1200 nm or more.

本實施方式之量子點亦能夠滿足上述第1量子點中所示之吸收特性、及上述第2量子點中所示之螢光特性兩者。The quantum dots of this embodiment can also satisfy both the absorption characteristics shown in the above-mentioned first quantum dots and the fluorescence characteristics shown in the above-mentioned second quantum dots.

[第1量子點之製造方法] 其次，對本實施方式之第1量子點之製造方法進行說明。於本實施方式中，藉由銀原料與含硫屬元素之三辛基膦而合成表示為Ag2 E(E為碲、硒或硫中之至少任一種)之量子點。[Method of Manufacturing the First Quantum Dot] Next, a method of manufacturing the first quantum dot of this embodiment will be described. In this embodiment, a quantum dot represented by Ag 2 E (E is at least any one of tellurium, selenium, or sulfur) is synthesized from silver raw material and trioctyl phosphine containing chalcogen.

於本實施方式中，Ag原料並無特別限定，例如可使用下述有機銀化合物或無機銀化合物。即，作為乙酸鹽，可使用乙酸銀(I)：Ag(OAc)；作為脂肪酸鹽，可使用硬脂酸銀：Ag(OC(=O)C17 H35 )；油酸銀：Ag(OC(=O)C17 H33 )；肉豆蔻酸銀：Ag(OC(=O)C13 H27 )；十二酸銀：Ag(OC(=O)C11 H23 )；乙醯丙酮酸銀：Ag(acac)；作為鹵化物，可使用一價化合物；且可使用氯化銀(I)：AgCl；溴化銀(I)：AgBr；碘化銀(I)：AgI等。In this embodiment, the Ag raw material is not particularly limited. For example, the following organic silver compounds or inorganic silver compounds can be used. That is, as the acetate salt, silver acetate (I): Ag(OAc) can be used; as the fatty acid salt, silver stearate: Ag(OC(=O)C 17 H 35 ); silver oleate: Ag(OC (=O)C 17 H 33 ); Silver myristate: Ag(OC(=O)C 13 H 27 ); Silver dodecanoate: Ag(OC(=O)C 11 H 23 ); Acetylpyruvate Silver: Ag (acac); as the halide, a monovalent compound may be used; and silver chloride (I): AgCl; silver bromide (I): AgBr; silver iodide (I): AgI, etc. may be used.

於本實施方式中，較佳為使銀原料溶解於作為溶劑之十八烯(ODE)、與三辛基膦(TOP)中。再者，亦能夠使用油胺代替TOP進行合成，但為了獲得優異之P/V比(波峰/波谷比)，較佳為使用TOP。於本實施方式中，藉由調節ODE與TOP之量(溶劑量)、及ODE/TOP之比率，能夠於近紅外區域內根據目的自由地控制吸收峰波長。雖無限定，較佳為於5 mL～30 mL之範圍內調整溶劑量(亦可說是銀與硫屬元素之濃度)。又，更佳為於10 mL～25 mL之範圍內調整溶劑量。又，雖無限定，較佳為將ODE/TOP之比率設為0.5～1.5之範圍。又，更佳為將ODE/TOP之比率設為0.8～1.0之範圍。In this embodiment, it is preferable to dissolve the silver raw material in octadecene (ODE) and trioctylphosphine (TOP) as a solvent. Furthermore, it is possible to use oleylamine instead of TOP for synthesis, but in order to obtain an excellent P/V ratio (peak/trough ratio), it is preferable to use TOP. In this embodiment, by adjusting the amount of ODE and TOP (amount of solvent) and the ratio of ODE/TOP, it is possible to freely control the absorption peak wavelength in the near-infrared region according to the purpose. Although there is no limitation, it is better to adjust the amount of solvent (it can also be said that the concentration of silver and chalcogen) within the range of 5 mL-30 mL. Furthermore, it is more preferable to adjust the amount of solvent within the range of 10 mL to 25 mL. Moreover, although it is not limited, it is preferable to set the ratio of ODE/TOP to the range of 0.5 to 1.5. Furthermore, it is more preferable to set the ratio of ODE/TOP to the range of 0.8 to 1.0.

關於含硫屬元素之三辛基膦，可列舉三辛基碲化膦(Te-TOP)、三辛基硒化膦(Se-TOP)及三辛基硫化膦(S-TOP)。As for the chalcogen-containing trioctyl phosphine, trioctyl phosphine telluride (Te-TOP), trioctyl phosphine selenide (Se-TOP), and trioctyl phosphine sulfide (S-TOP) can be cited.

於本實施方式中，於使銀原料溶解於溶劑中所獲得之溶液中混合含硫屬元素之三辛基膦，進而進行加熱而合成。於本實施方式中，可將加熱溫度低溫化。具體而言，可將加熱溫度設定為200℃以下。較佳為可設定為150℃以下。再者，加熱溫度之下限值為70℃左右。In this embodiment, chalcogen-containing trioctylphosphine is mixed with a solution obtained by dissolving a silver raw material in a solvent, and then heated to synthesize. In this embodiment, the heating temperature can be lowered. Specifically, the heating temperature can be set to 200°C or less. Preferably, it can be set to 150°C or less. Furthermore, the lower limit of the heating temperature is about 70°C.

藉由上述製造方法，可獲得如下量子點，該量子點係含有銀及硫屬元素之Ag2 E(E為碲、硒或硫中之至少任一種)所表示之奈米晶體，且平均粒徑為1 nm以上15 nm以下，進而吸收波長為800 nm～1700 nm之近紅外區域之範圍。又，根據本實施方式之量子點之製造方法，可於大氣下進行操作時，不使用顯示較高之反應性之反應劑或有毒規制對象重金屬而藉由可進行量產之方法來合成。By the above-mentioned manufacturing method, the following quantum dots can be obtained. The quantum dots are nanocrystals represented by Ag 2 E (E is at least one of tellurium, selenium, or sulfur) containing silver and chalcogen elements, and the average grain size is The diameter is 1 nm or more and 15 nm or less, and the absorption wavelength ranges from 800 nm to 1700 nm in the near-infrared region. In addition, according to the method of manufacturing quantum dots of the present embodiment, it is possible to synthesize by a method capable of mass production without using reagents showing high reactivity or heavy metals to be toxic and regulated when operating in the atmosphere.

又，於本實施方式中，可於合成階段之最終步驟中添加十二烷硫醇(DDT)。藉由添加DDT，能夠迅速進行量子點之配位基交換。Furthermore, in this embodiment, dodecyl mercaptan (DDT) may be added in the final step of the synthesis stage. By adding DDT, the ligand exchange of quantum dots can be carried out quickly.

[第2量子點之製造方法] 其次，對本實施方式之第2量子點之製造方法進行說明。於本實施方式中，藉由銀原料與二硫屬元素化合物而合成表示為Ag2 E(E為Te、Se或S中之至少任一種)之量子點。[Method of Manufacturing Second Quantum Dot] Next, a method of manufacturing the second quantum dot of this embodiment will be described. In this embodiment, a quantum dot represented by Ag 2 E (E is at least any one of Te, Se, or S) is synthesized from a silver raw material and a dichalcogen compound.

於本實施方式中，Ag原料並無特別限定，例如可使用下述有機銀化合物或無機銀化合物。即，作為乙酸鹽，可使用乙酸銀(I)：Ag(OAc)；作為脂肪酸鹽，可使用硬脂酸銀：Ag(OC(=O)C17 H35 )；油酸銀：Ag(OC(=O)C17 H33 )；肉豆蔻酸銀：Ag(OC(=O)C13 H27 )；十二酸銀：Ag(OC(=O)C11 H23 )、乙醯丙酮酸銀：Ag(acac)；作為鹵化物，可使用一價化合物；且可使用氯化銀(I)：AgCl；溴化銀(I)：AgBr；碘化銀(I)：AgI等。In this embodiment, the Ag raw material is not particularly limited. For example, the following organic silver compounds or inorganic silver compounds can be used. That is, as the acetate salt, silver acetate (I): Ag(OAc) can be used; as the fatty acid salt, silver stearate: Ag(OC(=O)C 17 H 35 ); silver oleate: Ag(OC (=O)C 17 H 33 ); Silver myristate: Ag(OC(=O)C 13 H 27 ); Silver dodecanoate: Ag(OC(=O)C 11 H 23 ), acetylpyruvate Silver: Ag (acac); as the halide, a monovalent compound may be used; and silver chloride (I): AgCl; silver bromide (I): AgBr; silver iodide (I): AgI, etc. may be used.

於本實施方式中，作為二硫屬元素化合物，可使用R1 -E1 -E2 -R2 所表示之二有機二硫屬元素化合物。此處，R1 及R2 可為烴基，E1 及E2 可為Te、Se或S中之至少任一種。R1 與R2 可相同，亦可不同。E1 與E2 可相同，亦可不同。In this embodiment, as the dichalcogen compound, a diorgano dichalcogen compound represented by R 1 -E 1 -E 2 -R 2 can be used. Here, R 1 and R 2 may be a hydrocarbon group, and E 1 and E 2 may be at least any one of Te, Se, or S. R 1 and R 2 may be the same or different. E 1 and E 2 may be the same or different.

於本實施方式中，於使碲固溶之情形時，可使用使有機碲化合物(有機硫屬元素化合物)或無機碲化合物溶解於高沸點溶劑所得者作為原料。化合物之結構並無特別限定，例如可使用二苯基二碲化物：(C6 H5 )2 Te2 等二烷基二碲化物：R2 Te2 。In this embodiment, when tellurium is dissolved in a solid solution, an organic tellurium compound (organic chalcogen compound) or an inorganic tellurium compound dissolved in a high boiling point solvent can be used as a raw material. The structure of the compound is not particularly limited. For example, diphenyl ditelluride: (C 6 H 5 ) 2 Te 2 or other dialkyl ditelluride: R 2 Te 2 can be used .

又，於本實施方式中，於使硒固溶之情形時，可使用使有機硒化合物(有機硫屬元素化合物)或無機硒化合物溶解於高沸點溶劑所得者作為原料。其結構並無特別限定，例如可使用如下溶液等，該溶液係於高溫下使硒溶解於二苯基二硒化物：(C6 H5 )2 Se2 等二烷基二硒化物：R2 Se2 、或作為如十八烯之長鏈烴之高沸點溶劑所得者。In addition, in this embodiment, when selenium is dissolved in a solid solution, an organic selenium compound (organic chalcogen compound) or an inorganic selenium compound can be used as a raw material by dissolving an organic selenium compound (organic chalcogen compound) in a high boiling point solvent. The structure is not particularly limited. For example, the following solution can be used, which dissolves selenium in diphenyl diselenide at high temperature: (C 6 H 5 ) 2 Se 2 and other dialkyl diselenide: R 2 Se 2 , or obtained as a high boiling point solvent for long-chain hydrocarbons such as octadecene.

又，於本實施方式中，於使硫固溶之情形時，使用使有機硫化合物(有機硫屬元素化合物)或無機硫化合物溶解於高沸點溶劑所得者作為原料。其結構並無特別限定，例如可使用如下溶液等，該溶液係於高溫下使硫溶解於二苯基二硫化物：(C6 H5 )2 S2 等二烷基二硫化物：R2 S2 、或作為如十八烯之長鏈烴之高沸點溶劑所得者。In addition, in the present embodiment, when sulfur is dissolved in a solid solution, an organic sulfur compound (organic chalcogen compound) or an inorganic sulfur compound dissolved in a high boiling point solvent is used as a raw material. The structure is not particularly limited. For example, the following solution can be used, which dissolves sulfur in diphenyl disulfide at high temperature: (C 6 H 5 ) 2 S 2 and other dialkyl disulfides: R 2 S 2 , or obtained as a high boiling point solvent for long-chain hydrocarbons such as octadecene.

於本實施方式中，由上述有機硫屬元素或無機硫屬元素獲得作為前驅物之二硫屬元素化合物。於本實施方式中，較佳為於120℃以上250℃以下之範圍內合成作為前驅物之二硫屬元素化合物。又，較佳為將反應溫度設為更低溫之100℃以上220℃以下，更佳為設為進而低溫之80℃以上200℃以下，進而較佳為設為進而低溫之60℃以上200℃以下。In this embodiment, a dichalcogen compound as a precursor is obtained from the organic chalcogen element or the inorganic chalcogen element. In this embodiment, it is preferable to synthesize the dichalcogen compound as a precursor within the range of 120°C or more and 250°C or less. Furthermore, the reaction temperature is preferably set to a lower temperature of 100°C or higher and 220°C or lower, more preferably set to a lower temperature of 80°C or higher and 200°C or lower, and still more preferably set to a lower temperature of 60°C or higher and 200°C or lower .

然後，混合銀原料與二硫屬元素化合物，使其溶解。關於溶劑，作為高沸點之飽和烴或不飽和烴，可使用十八烯。除此以外，作為芳香族系高沸點溶劑，可使用十二烷基苯(dodecylbenzene)，作為高沸點之酯系溶劑，可使用丁酸丁酯：C4 H9 COOC4 H9 ；丁酸苄酯：C3 H7 COOCH2 C6 H5 等；亦可使用脂肪族硫醇系、脂肪族胺系、或者脂肪酸系化合物或脂肪族磷系化合物作為溶劑。Then, the silver raw material and the dichalcogen compound are mixed and dissolved. Regarding the solvent, as a high-boiling saturated or unsaturated hydrocarbon, octadecene can be used. In addition, as an aromatic high boiling point solvent, dodecylbenzene can be used, and as a high boiling point ester solvent, butyl butyrate can be used: C 4 H 9 COOC 4 H 9 ; benzyl butyrate Ester: C 3 H 7 COOCH 2 C 6 H 5, etc.; aliphatic thiol-based, aliphatic amine-based, or fatty acid-based compound or aliphatic phosphorus-based compound may also be used as a solvent.

尤其為了獲得螢光強度較高之Ag2 E，較佳為於作為前驅物之二硫屬元素化合物與銀原料之反應中將硫醇相對於Te、Se或者S添加1～200當量，為了獲得螢光強度較高之量子點，更佳為添加5～1000當量，進而更佳為添加50～10000當量。硫醇並無特別限定，例如為十八烷硫醇：C18 H37 SH；十六烷硫醇：C16 H33 SH；十四烷硫醇：C14 H29 SH；十二烷硫醇：C12 H25 SH；癸硫醇：C10 H21 SH；辛硫醇：C8 H17 SH等。Especially in order to obtain Ag 2 E with higher fluorescence intensity, it is preferable to add 1-200 equivalent of mercaptan to Te, Se or S in the reaction between the dichalcogen compound as the precursor and the silver raw material, in order to obtain For quantum dots with higher fluorescence intensity, it is more preferable to add 5 to 1,000 equivalents, and even more preferably to add 50 to 10,000 equivalents. The mercaptan is not particularly limited. For example, octadecyl mercaptan: C 18 H 37 SH; hexadecyl mercaptan: C 16 H 33 SH; tetradecyl mercaptan: C 14 H 29 SH; dodecyl mercaptan : C 12 H 25 SH; Decane mercaptan: C 10 H 21 SH; Octyl mercaptan: C 8 H 17 SH and the like.

又，於本實施方式中，反應方法並無特別限定，為了獲得螢光半高寬較窄之量子點，重要的是合成平均粒徑均勻之Ag2 Te、Ag2 Se及Ag2 S。因此，較佳為於已加熱之溶劑中對作為前驅物之二硫屬元素化合物迅速地添加銀原料，以120℃以上250℃以下進行加熱。Furthermore, in this embodiment, the reaction method is not particularly limited. In order to obtain quantum dots with a relatively narrow fluorescent half-height width, it is important to synthesize Ag 2 Te, Ag 2 Se, and Ag 2 S with uniform average particle diameters. Therefore, it is preferable to quickly add the silver raw material to the dichalcogen compound as the precursor in the heated solvent, and heat at 120°C or higher and 250°C or lower.

又，於本實施方式中，於進行反應時，需要具有如下輔助性作用之化合物，該作用係藉由配位或螯合等使前驅物之金屬於反應溶液中游離。In addition, in this embodiment, when the reaction is performed, a compound having an auxiliary effect is required to release the metal of the precursor in the reaction solution by coordination or chelation.

作為具有上述作用之化合物，可列舉能夠與銀進行錯合之配位基。例如，較佳為磷系配位基、胺系配位基、硫醇系配位基、羧酸系配位基，其中，就其效率較高之方面而言，尤佳為硫醇系配位基。Examples of compounds having the above-mentioned effects include ligands capable of complexing with silver. For example, phosphorus-based ligands, amine-based ligands, thiol-based ligands, and carboxylic acid-based ligands are preferred. Among them, thiol-based ligands are particularly preferred in terms of higher efficiency. Bit base.

藉此，適當地進行Ag與硫屬元素之反應，可製造以Ag與硫屬元素為基礎，且於近紅外區域具有發光性及較窄之螢光半高寬之量子點。Thereby, the reaction between Ag and chalcogen is carried out appropriately, and it is possible to manufacture quantum dots based on Ag and chalcogen, and have luminescence in the near-infrared region and a narrow fluorescent half-height width.

又，根據本實施方式之量子點之製造方法，可不包含以Cd、Hg、Pb為代表之規制對象重金屬、與以金屬醯胺及有機鋰化合物為代表之於大氣下表現高反應之反應劑作為中間物而合成量子點。藉此，可利用可實用化，可進行量產，且安全性優異之製法來合成量子點。 實施例In addition, the method for manufacturing quantum dots according to this embodiment may not include heavy metals to be regulated, represented by Cd, Hg, and Pb, and reactants that exhibit high reactivity in the atmosphere, represented by metal amides and organolithium compounds. Intermediate to synthesize quantum dots. Thereby, it is possible to synthesize quantum dots by a manufacturing method that can be put into practical use, can be mass-produced, and is excellent in safety. Example

以下，藉由本發明之實施例及比較例對本發明之效果進行說明。再者，本發明不受以下實施例任何限定。Hereinafter, the effects of the present invention will be described by the examples and comparative examples of the present invention. In addition, the present invention is not limited at all by the following examples.

[作為近紅外區域中之吸收材料之量子點的合成] ＜原料＞ 實驗中，於合成在近紅外區域進行吸收之銀硫屬化合物(Ag2 E系)量子點時，使用以下原料。 (溶劑) 十八烯：Aldrich股份有限公司製造、出光興產股份有限公司製造 三辛基膦：北興產業股份有限公司 十二烷硫醇：Arkema公司製造 (銀原料) 乙酸銀：岸田化學股份有限公司製造 (碲原料) 碲(4 N：99.99%)：新興化學股份有限公司製造、或Aldrich公司製造 ＜測定機器＞ 紫外-可見光分光光度計：日立股份有限公司製造 V-770 掃描穿透式電子顯微鏡(STEM)：日立股份有限公司製造 SU9000 X射線繞射裝置(XRD)：Bruker公司製造 D2 PHASER[Synthesis of quantum dots as absorbing materials in the near-infrared region] <Raw materials> In the experiment, the following raw materials were used when synthesizing quantum dots of silver chalcogen compounds (Ag 2 E series) that absorb in the near-infrared region. (Solvent) Octadecene: manufactured by Aldrich Co., Ltd., and manufactured by Idemitsu Kosan Co., Ltd. Trioctylphosphine: Beixing Industrial Co., Ltd. Dodecyl mercaptan: manufactured by Arkema Co., Ltd. (silver raw material) Silver acetate: Kishida Chemical Co., Ltd. Manufactured by the company (tellurium raw material) Tellurium (4 N: 99.99%): manufactured by Xinxing Chemical Co., Ltd. or manufactured by Aldrich Co., Ltd. <Measurement equipment> Ultraviolet-visible spectrophotometer: manufactured by Hitachi Co., Ltd. V-770 scanning transmissive electronics Microscope (STEM): SU9000 manufactured by Hitachi Co., Ltd. X-ray diffraction device (XRD): D2 PHASER manufactured by Bruker

[實施例1] 向100 mL反應容器中添加乙酸銀166.9 mg、ODE 10.0 mL、TOP 10.0 mL。然後，一面於惰性氣體(N2 )氛圍下攪拌，一面進行加熱而使原料溶解。如此，ODE與TOP之合計溶劑量為20 mL。又，ODE/TOP之比率為1.0。[Example 1] To a 100 mL reaction vessel, 166.9 mg of silver acetate, 10.0 mL of ODE, and 10.0 mL of TOP were added. Then, while stirring under an inert gas (N 2 ) atmosphere, heating is performed to dissolve the raw materials. In this way, the total solvent volume of ODE and TOP is 20 mL. Also, the ratio of ODE/TOP is 1.0.

向該溶液中添加0.25 M之三辛基碲化膦(Te-TOP)2.0 mL，以110℃歷時10分鐘，一面攪拌一面進行加熱。Add 2.0 mL of 0.25 M trioctyl phosphine telluride (Te-TOP) to the solution, and heat at 110°C for 10 minutes while stirring.

向該溶液中添加DDT 2.0 mL，以190℃歷時10分鐘，一面攪拌一面進行加熱。將所獲得之反應溶液(Ag2 Te)冷卻至室溫。Add 2.0 mL of DDT to the solution and heat it at 190°C for 10 minutes while stirring. The obtained reaction solution (Ag 2 Te) was cooled to room temperature.

向所獲得之反應液中添加乙醇，產生沈澱，實施離心分離而回收沈澱。然後，向該沈澱中添加甲苯并使其分散而獲得Ag2 Te量子點之分散溶液。Ethanol was added to the obtained reaction solution to generate a precipitate, which was subjected to centrifugal separation to recover the precipitate. Then, toluene was added to the precipitate and dispersed to obtain a dispersion solution of Ag 2 Te quantum dots.

利用紫外可見分光計測定所獲得之反應溶液，獲得圖2所示之紫外可見近紅外吸收光譜。如圖2所示，於1150.0 nm處出現吸收峰。該吸收峰之峰頂與波谷(valley)之吸光度比為約2.1。The obtained reaction solution was measured with an ultraviolet-visible spectrometer to obtain the ultraviolet-visible-near-infrared absorption spectrum shown in FIG. 2. As shown in Figure 2, an absorption peak appears at 1150.0 nm. The ratio of the absorbance between the top of the absorption peak and the valley is about 2.1.

當藉由STEM觀察實施例1中所獲得之量子點時，多個量子點之平均粒徑為3.1～3.5 nm，且為1 nm以上15 nm以下。又，90%以上之量子點之各粒徑包含於平均粒徑±0.7 nm中。即，90%以上之量子點之各粒徑包含於平均粒徑±30%中，可均勻地生成多個量子點之粒徑。When the quantum dots obtained in Example 1 are observed by STEM, the average particle size of the plurality of quantum dots is 3.1-3.5 nm, and is 1 nm or more and 15 nm or less. In addition, more than 90% of the particle diameters of the quantum dots are contained in the average particle diameter ±0.7 nm. That is, more than 90% of the particle diameters of the quantum dots are included in the average particle diameter ±30%, and the particle diameters of multiple quantum dots can be uniformly generated.

於實施例1中所獲得之量子點之XRD光譜中，如圖3所示，於40°附近觀察到波峰，確認到Ag2 Te固溶體之生成。In the XRD spectrum of the quantum dots obtained in Example 1, as shown in FIG. 3, a wave peak was observed near 40°, and the formation of Ag 2 Te solid solution was confirmed.

其次，對實施例1中所獲得之量子點進行配位基交換實驗，結果如圖10A及圖10B所示，藉由添加3-巰基丙酸(MPA)，而發生自上層之己烷層向下層之二甲基亞碸(DMSO)層的迅速移動。Next, a ligand exchange experiment was performed on the quantum dots obtained in Example 1. The results are shown in Figures 10A and 10B. By adding 3-mercaptopropionic acid (MPA), the hexane layer from the upper layer The rapid movement of the lower DMSO layer.

由此確認到於本實施例中所獲得之量子點之周圍配位之配位基的迅速交換。Thus, it was confirmed that the ligands coordinated around the quantum dots obtained in this example rapidly exchanged.

[實施例2] 向100 mL反應容器中添加乙酸銀166.9 mg、ODE 8.5 mL、TOP 9.0 mL。然後，一面於惰性氣體(N2 )氛圍下攪拌，一面進行加熱而使原料溶解。如此，ODE與TOP之合計溶劑量為17.5 mL。又，ODE/TOP之比率為約0.94。[Example 2] To a 100 mL reaction vessel, 166.9 mg of silver acetate, 8.5 mL of ODE, and 9.0 mL of TOP were added. Then, while stirring under an inert gas (N 2 ) atmosphere, heating is performed to dissolve the raw materials. In this way, the total solvent volume of ODE and TOP is 17.5 mL. Also, the ratio of ODE/TOP is about 0.94.

向該溶液中添加0.25 M之Te-TOP 2.0 mL，以110℃歷時10分鐘，一面攪拌一面進行加熱。Add 2.0 mL of 0.25 M Te-TOP to the solution and heat it at 110°C for 10 minutes while stirring.

向該溶液中添加DDT 2.0 mL，以190℃歷時10分鐘，一面攪拌一面進行加熱。將所得之反應溶液(Ag2 Te)冷卻至室溫。將所得之反應溶液(Ag2 Te)冷卻至室溫。Add 2.0 mL of DDT to the solution and heat it at 190°C for 10 minutes while stirring. The resulting reaction solution (Ag 2 Te) was cooled to room temperature. The resulting reaction solution (Ag 2 Te) was cooled to room temperature.

向所獲得之反應液中添加乙醇，產生沈澱，實施離心分離而回收沈澱。然後，向該沈澱中添加甲苯并使其分散而獲得Ag2 Te量子點之分散溶液。Ethanol was added to the obtained reaction solution to generate a precipitate, which was subjected to centrifugal separation to recover the precipitate. Then, toluene was added to the precipitate and dispersed to obtain a dispersion solution of Ag 2 Te quantum dots.

於藉由紫外可見分光計對所獲得之反應溶液進行測定時之紫外可見近紅外吸收光譜中，如圖4所示，於1250.0 nm處出現吸收峰。該吸收峰之峰頂與波谷(valley)之吸光度比為約2.0。In the ultraviolet-visible-near-infrared absorption spectrum when the obtained reaction solution was measured by an ultraviolet-visible spectrometer, as shown in Figure 4, an absorption peak appeared at 1250.0 nm. The ratio of the absorbance between the top of the absorption peak and the valley is about 2.0.

當藉由STEM觀察實施例2中所獲得之量子點時，多個量子點之平均粒徑為3.1～3.7 nm，且為1 nm以上15 nm以下。又，90%以上之量子點之各粒徑包含於平均粒徑±0.7 nm中。即，90%以上之量子點之各粒徑包含於平均粒徑±30%中，可均勻地生成多個量子點之粒徑。When the quantum dots obtained in Example 2 are observed by STEM, the average particle diameter of the plurality of quantum dots is 3.1-3.7 nm, and is 1 nm or more and 15 nm or less. In addition, more than 90% of the particle diameters of the quantum dots are contained in the average particle diameter ±0.7 nm. That is, more than 90% of the particle diameters of the quantum dots are included in the average particle diameter ±30%, and the particle diameters of multiple quantum dots can be uniformly generated.

又，於實施例2中所獲得之量子點之XRD光譜中，如圖5所示，於40°附近觀察到波峰，確認到Ag2 Te固溶體之生成。In addition, in the XRD spectrum of the quantum dots obtained in Example 2, as shown in FIG. 5, a peak was observed near 40°, and the formation of Ag 2 Te solid solution was confirmed.

[實施例3] 向100 mL反應容器中添加乙酸銀166.9 mg、ODE 7.5 mL、TOP 7.5 mL。然後，一面於惰性氣體(N2 )氛圍下攪拌，一面進行加熱而使原料溶解。如此，ODE與TOP之合計溶劑量為15 mL。又，ODE/TOP之比率為1.0。[Example 3] To a 100 mL reaction vessel, 166.9 mg of silver acetate, 7.5 mL of ODE, and 7.5 mL of TOP were added. Then, while stirring under an inert gas (N 2 ) atmosphere, heating is performed to dissolve the raw materials. In this way, the total solvent volume of ODE and TOP is 15 mL. Also, the ratio of ODE/TOP is 1.0.

向該溶液中添加0.25 M之Te-TOP 2.0 mL，以110℃歷時10分鐘，一面攪拌一面進行加熱。Add 2.0 mL of 0.25 M Te-TOP to the solution and heat it at 110°C for 10 minutes while stirring.

向該溶液中添加DDT 2.0 mL，以190℃歷時10分鐘，一面攪拌一面進行加熱。將所得之反應溶液(Ag2 Te)冷卻至室溫。將所得之反應溶液(Ag2 Te)冷卻至室溫。Add 2.0 mL of DDT to the solution and heat it at 190°C for 10 minutes while stirring. The resulting reaction solution (Ag 2 Te) was cooled to room temperature. The resulting reaction solution (Ag 2 Te) was cooled to room temperature.

向所獲得之反應液中添加乙醇，產生沈澱，實施離心分離而回收沈澱。然後，向該沈澱中添加甲苯并使其分散而獲得Ag2 Te量子點之分散溶液。Ethanol was added to the obtained reaction solution to generate a precipitate, which was subjected to centrifugal separation to recover the precipitate. Then, toluene was added to the precipitate and dispersed to obtain a dispersion solution of Ag 2 Te quantum dots.

於藉由紫外可見分光計對所獲得之反應溶液進行測定時之紫外可見近紅外吸收光譜中，如圖6所示，於1350.0 nm處出現吸收峰。該吸收峰之峰頂與波谷(valley)之吸光度比為約1.8。In the ultraviolet-visible-near-infrared absorption spectrum when the obtained reaction solution was measured by an ultraviolet-visible spectrometer, as shown in Figure 6, an absorption peak appeared at 1350.0 nm. The ratio of the absorbance between the top of the absorption peak and the valley is about 1.8.

當藉由STEM觀察實施例3中所獲得之量子點時，多個量子點之平均粒徑為3.1～3.7 nm，且為1 nm以上15 nm以下。又，90%以上之量子點之各粒徑包含於平均粒徑±0.7 nm中。即，90%以上之量子點之各粒徑包含於平均粒徑±30%中，可均勻地生成多個量子點之粒徑。When the quantum dots obtained in Example 3 are observed by STEM, the average particle diameter of the plurality of quantum dots is 3.1-3.7 nm, and is 1 nm or more and 15 nm or less. In addition, more than 90% of the particle diameters of the quantum dots are contained in the average particle diameter ±0.7 nm. That is, more than 90% of the particle diameters of the quantum dots are included in the average particle diameter ±30%, and the particle diameters of multiple quantum dots can be uniformly generated.

又，於實施例3中所獲得之量子點之XRD光譜中，如圖7所示，於39.9°附近觀察到波峰，確認到Ag2 Te固溶體之生成。In addition, in the XRD spectrum of the quantum dots obtained in Example 3, as shown in Fig. 7, a peak was observed near 39.9°, and the formation of Ag 2 Te solid solution was confirmed.

[實施例4] 向100 mL反應容器中添加乙酸銀166.9 mg、ODE 5.0 mL、TOP 6.0 mL。然後，一面於惰性氣體(N2 )氛圍下攪拌，一面進行加熱而使原料溶解。如此，ODE與TOP之合計溶劑量為11 mL。又，ODE/TOP之比率為約0.83。[Example 4] To a 100 mL reaction vessel, 166.9 mg of silver acetate, 5.0 mL of ODE, and 6.0 mL of TOP were added. Then, while stirring under an inert gas (N 2 ) atmosphere, heating is performed to dissolve the raw materials. In this way, the total solvent volume of ODE and TOP is 11 mL. Also, the ratio of ODE/TOP is about 0.83.

向該溶液中添加0.25 M之Te-TOP 2.0 mL，以110℃歷時10分鐘，一面攪拌一面進行加熱。Add 2.0 mL of 0.25 M Te-TOP to the solution and heat it at 110°C for 10 minutes while stirring.

向該溶液中添加DDT 2.0 mL，以190℃歷時10分鐘，一般攪拌一面進行加熱。將所獲得之反應溶液(Ag2 Te)冷卻至室溫。Add 2.0 mL of DDT to the solution and heat it at 190°C for 10 minutes. Generally, it is heated while stirring. The obtained reaction solution (Ag 2 Te) was cooled to room temperature.

向所獲得之反應液中添加乙醇，產生沈澱，實施離心分離而回收沈澱。然後，向該沈澱中添加甲苯并使其分散而獲得Ag2 Te量子點之分散溶液。Ethanol was added to the obtained reaction solution to generate a precipitate, which was subjected to centrifugal separation to recover the precipitate. Then, toluene was added to the precipitate and dispersed to obtain a dispersion solution of Ag 2 Te quantum dots.

於藉由紫外可見分光計對所獲得之反應溶液進行測定時之紫外可見近紅外吸收光譜中，如圖8所示，於1450.0 nm處出現吸收峰。該吸收峰之峰頂與波谷(valley)之吸光度比為約1.6。In the ultraviolet-visible-near-infrared absorption spectrum when the obtained reaction solution was measured by an ultraviolet-visible spectrometer, as shown in Figure 8, an absorption peak appeared at 1450.0 nm. The ratio of the absorbance between the top of the absorption peak and the valley is about 1.6.

當藉由STEM觀察實施例4中所獲得之量子點時，多個量子點之平均粒徑為3.1～3.7 nm，且為1 nm以上15 nm以下。又，90%以上之量子點之各粒徑包含於平均粒徑±0.7 nm中。即，90%以上之量子點之各粒徑包含於平均粒徑±30%中，可均勻地生成多個量子點之粒徑。When the quantum dots obtained in Example 4 are observed by STEM, the average particle size of the plurality of quantum dots is 3.1-3.7 nm, and is 1 nm or more and 15 nm or less. In addition, more than 90% of the particle diameters of the quantum dots are contained in the average particle diameter ±0.7 nm. That is, more than 90% of the particle diameters of the quantum dots are included in the average particle diameter ±30%, and the particle diameters of multiple quantum dots can be uniformly generated.

又，於本實施例中所獲得之量子點之XRD光譜中，如圖9所示，於40.1°附近觀察到波峰，確認到Ag2 Te固溶體之生成。In addition, in the XRD spectrum of the quantum dots obtained in this example, as shown in FIG. 9, a peak was observed near 40.1°, and the formation of Ag 2 Te solid solution was confirmed.

[作為近紅外區域中之螢光材料之量子點的合成] ＜原料＞ 實驗中，於合成在近紅外區域進行發光之銀硫屬化合物(Ag2 E系)量子點時，使用以下原料。 (溶劑) 十八烯：Aldrich股份有限公司製造、出光興產股份有限公司製造 十二烷硫醇：Arkema公司製造 (銀原料) 乙酸銀：岸田化學股份有限公司製造 (二硫屬元素化合物) 二苯基二碲化物：東京化成(TCI)公司製造 (碲原料) 碲(4 N：99.99%)：新興化學股份有限公司製造、或Aldrich公司製造 ＜測定機器＞ 螢光分光計：Ocean Optics製造 NIRQuest512-1.9 紫外-可見光分光光度計：日立股份有限公司製造 V-770 X射線繞射裝置(XRD)：Bruker公司製造 D2 PHASER 掃描穿透式電子顯微鏡(STEM)：日立股份有限公司製造 SU9000[Synthesis of quantum dots as fluorescent materials in the near-infrared region] <Raw materials> In the experiment, the following raw materials were used when synthesizing quantum dots of silver chalcogenide compounds (Ag 2 E series) that emit light in the near-infrared region. (Solvent) Octadecene: manufactured by Aldrich Co., Ltd., and manufactured by Idemitsu Kosan Co., Ltd. Dodecyl mercaptan: manufactured by Arkema Co., Ltd. (silver raw material) Silver acetate: manufactured by Kishida Chemical Co., Ltd. (dichalcogen compound) 2 Phenyl ditelluride: manufactured by Tokyo Chemical Industry (TCI) (Tellurium raw material) Tellurium (4 N: 99.99%): manufactured by Shin Shin Chemical Co., Ltd., or manufactured by Aldrich Corporation <Measurement equipment> Fluorescence spectrometer: NIRQuest512 manufactured by Ocean Optics -1.9 Ultraviolet-visible spectrophotometer: V-770 manufactured by Hitachi Co., Ltd. X-ray diffraction device (XRD): D2 PHASER manufactured by Bruker Co., Ltd. Scanning transmission electron microscope (STEM): SU9000 manufactured by Hitachi Co., Ltd.

[實施例5] 向100 mL反應容器中添加二苯基二碲化物123.0 mg、十二烷硫醇(DDT)15.0 mL、十八烯(ODE)15.0 mL。然後，一面於惰性氣體(N2 )氛圍下攪拌，一面進行加熱而使原料溶解。[Example 5] To a 100 mL reaction vessel, 123.0 mg of diphenyl ditelluride, 15.0 mL of dodecyl mercaptan (DDT), and 15.0 mL of octadecene (ODE) were added. Then, while stirring under an inert gas (N 2 ) atmosphere, heating is performed to dissolve the raw materials.

向該溶液中添加乙酸銀204.0 mg，以185℃歷時10分鐘，一面攪拌一面進行加熱。將所獲得之反應溶液(Ag2 Te)冷卻至室溫。204.0 mg of silver acetate was added to the solution and heated at 185°C for 10 minutes while stirring. The obtained reaction solution (Ag 2 Te) was cooled to room temperature.

向所獲得之反應液中添加乙醇，產生沈澱，實施離心分離而回收沈澱。然後，向該沈澱中添加甲苯并使其分散而獲得Ag2 Te量子點之分散溶液。Ethanol was added to the obtained reaction solution to generate a precipitate, which was subjected to centrifugal separation to recover the precipitate. Then, toluene was added to the precipitate and dispersed to obtain a dispersion solution of Ag 2 Te quantum dots.

藉由紫外可見分光計測定所獲得之反應溶液。其結果如圖11之紫外可見近紅外吸收光譜之測定結果所示，於1219.0 nm、1400.0 nm及1420.0 nm處獲得吸收極大。又，如圖12之近紅外螢光光譜之測定結果所示，於1322.5 nm處獲得螢光極大。又，基於圖12，螢光半高寬為約150 nm，小於200 nm。The obtained reaction solution was measured by an ultraviolet-visible spectrometer. The results are shown in the measurement results of the ultraviolet-visible-near-infrared absorption spectra in Fig. 11. The absorption peaks are obtained at 1219.0 nm, 1400.0 nm, and 1420.0 nm. In addition, as shown in the measurement result of the near-infrared fluorescence spectrum in Fig. 12, the maximum fluorescence is obtained at 1322.5 nm. Also, based on Fig. 12, the fluorescence FWHM is about 150 nm, which is less than 200 nm.

又，自圖13A及圖13B所示之STEM照片可知，多個量子點之平均粒徑為2.4～2.7 nm，且為1 nm以上15 nm以下。又，90%以上之量子點之各粒徑包含於平均粒徑±0.7 nm中。即，可知90%以上之量子點之各粒徑包含於平均粒徑±30%中，可均勻地生成多個量子點之粒徑。In addition, it can be seen from the STEM photographs shown in FIG. 13A and FIG. 13B that the average particle size of the plurality of quantum dots is 2.4 to 2.7 nm, and is 1 nm or more and 15 nm or less. In addition, more than 90% of the particle diameters of the quantum dots are contained in the average particle diameter ±0.7 nm. That is, it can be seen that more than 90% of the particle diameters of the quantum dots are contained in the average particle diameter ±30%, and the particle diameters of a plurality of quantum dots can be uniformly generated.

又，基於圖14所示之Ag2 Te之XRD光譜之峰值，可證明生成了Ag2 Te固溶體。 Furthermore, based on the peak of the XRD spectrum of Ag 2 Te shown in Fig. 14, it can be proved that a solid solution of Ag 2 Te was formed.

[實施例6] 向100 mL反應容器中添加二苯基二碲化物123.0 mg、十二烷硫醇(DDT)30.0 mL。然後，一面於惰性氣體(N2 )氛圍下攪拌，一面進行加熱而使原料溶解。[Example 6] To a 100 mL reaction vessel, 123.0 mg of diphenyl ditelluride and 30.0 mL of dodecyl mercaptan (DDT) were added. Then, while stirring under an inert gas (N 2 ) atmosphere, heating is performed to dissolve the raw materials.

向該溶液中添加乙酸銀204.0 mg，以175℃歷時20分鐘，一面攪拌一面進行加熱。將所獲得之反應溶液(Ag2 Te)冷卻至室溫。204.0 mg of silver acetate was added to the solution and heated at 175°C for 20 minutes while stirring. The obtained reaction solution (Ag 2 Te) was cooled to room temperature.

向所獲得之反應液中添加乙醇，產生沈澱，實施離心分離而回收沈澱。然後，向該沈澱中添加甲苯使其分散而獲得Ag2 Te量子點之分散溶液。Ethanol was added to the obtained reaction solution to generate a precipitate, which was subjected to centrifugal separation to recover the precipitate. Then, toluene was added to the precipitate and dispersed to obtain a dispersion solution of Ag 2 Te quantum dots.

於藉由紫外可見分光計對所獲得之反應溶液進行測定時之紫外可見近紅外吸收光譜中，與實施例5之圖11同樣地，於1219.0 nm、1400.0 nm及1420.0 nm處存在吸收極大。又，於反應溶液之近紅外螢光光譜中，與實施例5之圖12同樣地，於1322.5 nm處存在螢光極大，螢光半高寬為約150 nm，小於200 nm。In the ultraviolet-visible-near-infrared absorption spectrum when the obtained reaction solution was measured by an ultraviolet-visible spectrometer, similar to FIG. 11 of Example 5, there were absorption maxima at 1219.0 nm, 1400.0 nm, and 1420.0 nm. In addition, in the near-infrared fluorescence spectrum of the reaction solution, similar to FIG. 12 of Example 5, there is a maximum fluorescence at 1322.5 nm, and the fluorescence half-height is about 150 nm, which is less than 200 nm.

當藉由STEM觀察本實施例中所獲得之量子點時，與實施例5之圖13同樣地，多個量子點之平均粒徑為2.4～2.7 nm，且為1 nm以上15 nm以下。又，90%以上之量子點之各粒徑包含於平均粒徑±0.7 nm中。即，90%以上之量子點之各粒徑包含於平均粒徑±30%中，可均勻地生成多個量子點之粒徑。When the quantum dots obtained in this example are observed by STEM, the average particle diameter of the plurality of quantum dots is 2.4 to 2.7 nm, and is 1 nm or more and 15 nm or less, as in FIG. 13 of Example 5. In addition, more than 90% of the particle diameters of the quantum dots are contained in the average particle diameter ±0.7 nm. That is, more than 90% of the particle diameters of the quantum dots are included in the average particle diameter ±30%, and the particle diameters of multiple quantum dots can be uniformly generated.

又，於本實施例中所獲得之量子點之XRD光譜中，觀察到與實施例5之圖14相同之波峰，確認到Ag2 Te固溶體之生成。In addition, in the XRD spectrum of the quantum dots obtained in this example, the same peaks as in Fig. 14 of Example 5 were observed, and the formation of Ag 2 Te solid solution was confirmed.

[實施例7] 向100 mL反應容器中添加二苯基二碲化物41.0 mg、十二烷硫醇(DDT)10.0 mL、十八烯(ODE)5 mL。然後，一面於惰性氣體(N2 )氛圍下攪拌，一面進行加熱而使原料溶解。[Example 7] To a 100 mL reaction vessel, 41.0 mg of diphenylditelluride, 10.0 mL of dodecyl mercaptan (DDT), and 5 mL of octadecene (ODE) were added. Then, while stirring under an inert gas (N 2 ) atmosphere, heating is performed to dissolve the raw materials.

向該溶液中添加乙酸銀68.0 mg，以180℃歷時15分鐘，一面攪拌一面進行加熱。將所獲得之反應溶液(Ag2 Te)冷卻至室溫。68.0 mg of silver acetate was added to the solution and heated at 180°C for 15 minutes while stirring. The obtained reaction solution (Ag 2 Te) was cooled to room temperature.

向所獲得之反應液中添加乙醇，產生沈澱，實施離心分離而回收沈澱。然後，向該沈澱中添加甲苯并使其分散而獲得Ag2 Te量子點之分散溶液。Ethanol was added to the obtained reaction solution to generate a precipitate, which was subjected to centrifugal separation to recover the precipitate. Then, toluene was added to the precipitate and dispersed to obtain a dispersion solution of Ag 2 Te quantum dots.

於藉由紫外可見分光計對所獲得之反應溶液進行測定時之紫外可見近紅外吸收光譜中，與實施例5之圖11同樣地，於1219.0 nm、1400.0 nm及1420.0 nm處存在吸收極大。又，於反應溶液之近紅外螢光光譜中，與實施例5之圖12同樣地，於1322.5 nm處存在螢光極大，螢光半高寬為約150 nm，小於200 nm。In the ultraviolet-visible-near-infrared absorption spectrum when the obtained reaction solution was measured by an ultraviolet-visible spectrometer, similar to FIG. 11 of Example 5, there were absorption maxima at 1219.0 nm, 1400.0 nm, and 1420.0 nm. In addition, in the near-infrared fluorescence spectrum of the reaction solution, similar to FIG. 12 of Example 5, there is a maximum fluorescence at 1322.5 nm, and the fluorescence half-height is about 150 nm, which is less than 200 nm.

當藉由STEM觀察本實施例中所獲得之量子點時，與實施例5之圖13同樣地，多個量子點之平均粒徑為2.4～2.7 nm，且為1 nm以上15 nm以下。又，90%以上之量子點之各粒徑包含於平均粒徑±0.7 nm中。即，90%以上之量子點之各粒徑包含於平均粒徑±30%中，可均勻地生成多個量子點之粒徑。When the quantum dots obtained in this example are observed by STEM, the average particle diameter of the plurality of quantum dots is 2.4 to 2.7 nm, and is 1 nm or more and 15 nm or less, as in FIG. 13 of Example 5. In addition, more than 90% of the particle diameters of the quantum dots are contained in the average particle diameter ±0.7 nm. That is, more than 90% of the particle diameters of the quantum dots are contained in the average particle diameter ±30%, and the particle diameters of multiple quantum dots can be uniformly generated.

又，於本實施例中所獲得之量子點之XRD光譜中，觀察到與實施例5之圖14相同之波峰，確認到Ag2 Te固溶體之生成。In addition, in the XRD spectrum of the quantum dots obtained in this example, the same peaks as in Fig. 14 of Example 5 were observed, and the formation of Ag 2 Te solid solution was confirmed.

[比較例1] 向100 mL反應容器中添加氯化銀143.3 mg、ODE 10.0 mL、TOP 10.0 mL。然後，一面於惰性氣體(N2 )氛圍下攪拌，一面進行加熱而使原料溶解。[Comparative Example 1] A 100 mL reaction vessel was charged with 143.3 mg of silver chloride, 10.0 mL of ODE, and 10.0 mL of TOP. Then, while stirring under an inert gas (N 2 ) atmosphere, heating is performed to dissolve the raw materials.

向該溶液中添加碲粉末63.8 mg，以115℃歷時10分鐘，一面攪拌一面進行加熱。63.8 mg of tellurium powder was added to the solution and heated at 115°C for 10 minutes while stirring.

向該溶液中添加DDT 2.0 mL，以200℃歷時10分鐘，一面攪拌一面進行加熱。將所獲得之反應溶液(Ag2 Te)冷卻至室溫。反應溶液變成黑色懸濁液，關於所獲得之溶液，完全未於近紅外區域確認到吸收峰。Add 2.0 mL of DDT to the solution and heat it at 200°C for 10 minutes while stirring. The obtained reaction solution (Ag 2 Te) was cooled to room temperature. The reaction solution turned into a black suspension, and with respect to the obtained solution, no absorption peak was confirmed in the near-infrared region at all.

[比較例2] 向100 mL反應容器中添加氧化銀231.7 mg、ODE 10.0 mL、TOP 10.0 mL。然後，一面於惰性氣體(N2 )氛圍下攪拌，一面進行加熱而使原料溶解。[Comparative Example 2] A 100 mL reaction vessel was charged with 231.7 mg of silver oxide, 10.0 mL of ODE, and 10.0 mL of TOP. Then, while stirring under an inert gas (N 2 ) atmosphere, heating is performed to dissolve the raw materials.

向該溶液中添加碲粉末63.8 mg，以115℃歷時10分鐘，一面攪拌一面進行加熱。63.8 mg of tellurium powder was added to the solution and heated at 115°C for 10 minutes while stirring.

向該溶液中添加DDT 2.0 mL，以200℃歷時10分鐘，一面攪拌一面進行加熱。將所獲得之反應溶液(Ag2 Te)冷卻至室溫。反應溶液變成黑色懸濁液，關於所獲得之溶液，完全未於近紅外區域確認到吸收峰。Add 2.0 mL of DDT to the solution and heat it at 200°C for 10 minutes while stirring. The obtained reaction solution (Ag 2 Te) was cooled to room temperature. The reaction solution turned into a black suspension, and with respect to the obtained solution, no absorption peak was confirmed in the near-infrared region at all.

[比較例3] 向100 mL反應容器中添加碲38.3 mg、十二烷硫醇15.0 mL、十八烯15 mL。然後，一面於惰性氣體(N2 )氛圍下攪拌，一面進行加熱而使原料溶解。[Comparative Example 3] To a 100 mL reaction vessel, 38.3 mg of tellurium, 15.0 mL of dodecyl mercaptan, and 15 mL of octadecene were added. Then, while stirring under an inert gas (N 2 ) atmosphere, heating is performed to dissolve the raw materials.

向該溶液中添加乙酸銀204.0 mg，以185℃歷時10分鐘，一面攪拌一面進行加熱。將所獲得之反應溶液(Ag2 Te)冷卻至室溫。反應溶液變成黑色懸濁液，關於所獲得之溶液，完全未於近紅外區域確認到螢光。204.0 mg of silver acetate was added to the solution and heated at 185°C for 10 minutes while stirring. The obtained reaction solution (Ag 2 Te) was cooled to room temperature. The reaction solution turned into a black suspension, and with respect to the obtained solution, fluorescence was not confirmed in the near-infrared region at all.

基於以上實驗結果可知，根據實施例1～7，所獲得之量子點均為Ag2 Te所表示之奈米晶體，可使平均粒徑成為1 nm以上15 nm以下之範圍內。又，可知平均粒徑較佳為可調整為1 nm以上10 nm以下，更佳為可調整為1 nm以上5 nm以下。關於使用作為硫屬元素之Se或S之Ag2 Se或Ag2 S，基於化學見解，亦推測獲得相同結果。Based on the above experimental results, it can be seen that according to Examples 1-7, the obtained quantum dots are all nanocrystals represented by Ag 2 Te, and the average particle size can be within the range of 1 nm to 15 nm. In addition, it can be seen that the average particle diameter is preferably adjustable to 1 nm or more and 10 nm or less, and more preferably adjustable to 1 nm or more and 5 nm or less. Regarding Ag 2 Se or Ag 2 S using Se or S as the chalcogen element, based on chemical knowledge, it is also assumed that the same result was obtained.

又，可知根據實施例1～4，藉由銀原料與Te-TOP而合成Ag2 Te，吸收波長均為800 nm～1700 nm之近紅外區域之範圍。又，可知於本實施例中，較佳為可於1100 nm～1500 nm之近紅外區域具有吸收波長，更佳為可於1300 nm～1450 nm之近紅外區域具有吸收波長。可知於本實施例中，吸收峰之峰頂與波谷(valley)之吸光度比可設為約1.5以上，可進一步使對比度明確化。In addition, it can be seen that according to Examples 1 to 4, Ag 2 Te is synthesized from a silver raw material and Te-TOP, and the absorption wavelength is in the near infrared region of 800 nm to 1700 nm. Furthermore, it can be seen that in this embodiment, it is preferable to have an absorption wavelength in the near-infrared region of 1100 nm to 1500 nm, and more preferably to have an absorption wavelength in the near-infrared region of 1300 nm to 1450 nm. It can be seen that in this embodiment, the absorbance ratio between the top of the absorption peak and the valley can be set to be about 1.5 or more, which can further clarify the contrast.

又，可知於實施例1～4之實驗中，對ODE與TOP之量(溶劑量)及ODE/TOP之比率進行了各種變更，藉此，能夠根據目的而自由地控制近紅外區域中觀察到之吸收峰波長。In addition, it can be seen that in the experiments of Examples 1 to 4, various changes were made to the amount of ODE and TOP (amount of solvent) and the ratio of ODE/TOP, thereby allowing free control of the observation in the near-infrared region according to the purpose. The absorption peak wavelength.

於本實施例中，於5 mL～30 mL之範圍內調整了溶劑量。再者，更佳為於10 mL～25 mL之範圍內調整溶劑量。又，於0.5～1.5之範圍內調整了ODE/TOP之比率。再者，較佳為將ODE/TOP之比率設為0.8～1.0之範圍。In this example, the amount of solvent was adjusted within the range of 5 mL to 30 mL. Furthermore, it is more preferable to adjust the amount of solvent within the range of 10 mL to 25 mL. In addition, the ratio of ODE/TOP has been adjusted within the range of 0.5 to 1.5. Furthermore, it is preferable to set the ratio of ODE/TOP to the range of 0.8 to 1.0.

又，可知根據實施例5～7，能夠合成於近紅外區域具有發光波長之量子點。 [產業上之可利用性]In addition, it can be seen that according to Examples 5 to 7, it is possible to synthesize quantum dots having emission wavelengths in the near-infrared region. [Industrial availability]

根據本發明，可不使用於大氣下進行操作時表現較高之反應性之反應劑，且不經由包含有毒規制對象重金屬之中間物而穩定地合成於800 nm至1700 nm之任意範圍之區域具有吸收帶，且顯示高亮度之近紅外螢光之銀硫屬化物量子點。而且，藉由將本發明之量子點應用於光通信裝置等，可於裝置中獲得優異之近紅外吸收及近紅外發光特性。尤其能夠將本發明之量子點應用於紅外線感測器之光吸收層之量子點層。According to the present invention, it is not necessary to use a reactant that exhibits high reactivity when operating under the atmosphere, and it can be synthesized stably in the region of any range from 800 nm to 1700 nm without passing through intermediates containing toxic regulated heavy metals. It is a silver chalcogenide quantum dot with high-brightness near-infrared fluorescence. Moreover, by applying the quantum dots of the present invention to optical communication devices, etc., excellent near-infrared absorption and near-infrared luminescence characteristics can be obtained in the device. In particular, the quantum dot of the present invention can be applied to the quantum dot layer of the light absorption layer of an infrared sensor.

本案基於2019年8月15日提出申請之日本專利特願2019-149026。其內容全部預先包含於本文中。This case is based on Japanese Patent Application No. 2019-149026 filed on August 15, 2019. All its contents are included in this article in advance.

1:量子點 1a:核 1b:殼 2:有機配位基1: Quantum dots 1a: nuclear 1b: shell 2: Organic ligand

圖1A係本發明之實施方式中之量子點之模式圖。 圖1B係本發明之實施方式中之量子點之模式圖。 圖2係實施例1中之Ag2 Te之吸收(Absorption)光譜。 圖3係實施例1中之Ag2 Te之X射線繞射(Xray Diffraction：XRD)光譜。 圖4係實施例2中之Ag2 Te之吸收(Absorption)光譜。 圖5係實施例2中之Ag2 Te之X射線繞射(Xray Diffraction：XRD)光譜。 圖6係實施例3中之Ag2 Te之吸收(Absorption)光譜。 圖7係實施例3中之Ag2 Te之X射線繞射(Xray Diffraction：XRD)光譜。 圖8係實施例4中之Ag2 Te之吸收(Absorption)光譜。 圖9係實施例4中之Ag2 Te之X射線繞射(Xray Diffraction：XRD)光譜。 圖10A係表示本實施例中所獲得之量子點之配位基交換實驗中之溶液之狀態變化的圖像。 圖10B係表示圖10A之一部分之模式圖。 圖11係實施例5中之Ag2 Te之吸收(Absorption)光譜。 圖12係實施例5中之Ag2 Te之螢光(Photoluminescence：PL)光譜。 圖13A係實施例5中之Ag2 Te之掃描穿透式電子顯微鏡(Scanning transmission electron microscope：STEM)照片。 圖13B係表示圖13A之一部分之模式圖。 圖14係實施例5中之Ag2 Te之X射線繞射(Xray Diffraction：XRD)光譜。Fig. 1A is a schematic diagram of a quantum dot in an embodiment of the present invention. Fig. 1B is a schematic diagram of a quantum dot in an embodiment of the present invention. FIG. 2 is the absorption spectrum of Ag 2 Te in Example 1. FIG. 3 is the X-ray diffraction (Xray Diffraction: XRD) spectrum of Ag 2 Te in Example 1. 4 is the absorption spectrum of Ag 2 Te in Example 2. 5 is the X-ray diffraction (Xray Diffraction: XRD) spectrum of Ag 2 Te in Example 2. FIG. 6 shows the absorption spectrum of Ag 2 Te in Example 3. FIG. FIG. 7 is the X-ray diffraction (Xray Diffraction: XRD) spectrum of Ag 2 Te in Example 3. FIG. 8 is the absorption spectrum of Ag 2 Te in Example 4. FIG. 9 is the X-ray diffraction (Xray Diffraction: XRD) spectrum of Ag 2 Te in Example 4. FIG. 10A is an image showing the state change of the solution in the ligand exchange experiment of the quantum dot obtained in this example. Fig. 10B is a schematic diagram showing a part of Fig. 10A. FIG. 11 is the absorption spectrum of Ag 2 Te in Example 5. FIG. FIG. 12 is the fluorescence (Photoluminescence: PL) spectrum of Ag 2 Te in Example 5. FIG. FIG. 13A is a scanning transmission electron microscope (STEM) photograph of Ag 2 Te in Example 5. FIG. Fig. 13B is a schematic diagram showing a part of Fig. 13A. 14 is the X-ray diffraction (Xray Diffraction: XRD) spectrum of Ag 2 Te in Example 5.

Claims (12)

一種量子點，其特徵在於：其係含有銀及硫屬元素之Ag2 E(E為碲、硒或硫中之至少一種)所表示之奈米晶體，且 平均粒徑為1 nm以上15 nm以下。A quantum dot characterized in that it is a nanocrystal represented by Ag 2 E (E is at least one of tellurium, selenium or sulfur) containing silver and chalcogen elements, and has an average particle size of 1 nm or more and 15 nm the following. 如請求項1之量子點，其吸收波長為800 nm～1700 nm之近紅外區域之範圍。For example, the quantum dot of claim 1 has an absorption wavelength in the range of the near-infrared region from 800 nm to 1700 nm. 如請求項1或2之量子點，其螢光波長為800～1700 nm之近紅外區域之範圍，且螢光半高寬為200 nm以下。For example, the quantum dot of claim 1 or 2 has a fluorescence wavelength in the near-infrared region of 800-1700 nm, and a fluorescence half-height width of 200 nm or less. 如請求項1至3中任一項之量子點，其中上述量子點之表面被配位基覆蓋。The quantum dot according to any one of claims 1 to 3, wherein the surface of the quantum dot is covered with ligands. 如請求項4之量子點，其中上述配位基選自膦系、脂肪族硫醇系、脂肪族胺系及脂肪族羧酸系中之至少任一種或兩種。The quantum dot of claim 4, wherein the ligand is selected from at least any one or two of phosphine, aliphatic thiol, aliphatic amine, and aliphatic carboxylic acid. 一種量子點之製造方法，其特徵在於：藉由銀原料與含硫屬元素之三辛基膦，以200℃以下合成表示為Ag2 E(E為碲、硒或硫中之至少任一種)之量子點。A method for manufacturing quantum dots, characterized in that: using silver raw materials and chalcogen-containing trioctyl phosphine, the synthesis is expressed as Ag 2 E (E is at least one of tellurium, selenium or sulfur) at a temperature below 200°C Of quantum dots. 如請求項6之量子點之製造方法，其中以180℃以下使上述銀原料與上述含硫屬元素之三辛基膦反應。The method for manufacturing a quantum dot according to claim 6, wherein the above-mentioned silver raw material is reacted with the above-mentioned chalcogen-containing trioctylphosphine at a temperature of 180°C or lower. 如請求項6或7之量子點之製造方法，其中向混合有上述銀原料與上述含硫屬元素之三辛基膦之溶液中添加十二烷硫醇(DDT)。According to claim 6 or 7, the method for manufacturing quantum dots, wherein dodecyl mercaptan (DDT) is added to the solution in which the silver raw material and the chalcogen-containing trioctyl phosphine are mixed. 一種量子點之製造方法，其特徵在於：藉由銀原料與二硫屬元素化合物來合成表示為Ag2 E(E為碲、硒或者硫中之至少任一種)之量子點。A method for manufacturing quantum dots, which is characterized by synthesizing quantum dots represented by Ag 2 E (E is at least any one of tellurium, selenium, or sulfur) from silver raw materials and dichalcogen compounds. 如請求項9之量子點之製造方法，其係於包含硫醇之溶劑中合成上述量子點。Such as the method for manufacturing quantum dots of claim 9, which is to synthesize the above quantum dots in a solvent containing mercaptan. 如請求項9或10之量子點之製造方法，其係以120℃以上250℃以下使上述二硫屬化合物與上述銀原料反應。According to claim 9 or 10, the method for producing quantum dots involves reacting the above-mentioned dichalcogen compound with the above-mentioned silver raw material at a temperature above 120°C and below 250°C. 如請求項6至11中任一項之量子點之製造方法，其係不包含以鎘、汞及鉛為代表之規制對象重金屬、與以金屬醯胺及有機鋰化合物為代表之於大氣下表現高反應性之反應劑作為中間物，而合成上述量子點。For example, the method for manufacturing quantum dots in any one of claims 6 to 11 does not include heavy metals that are regulated by cadmium, mercury, and lead, and the atmospheric performance represented by metal amides and organolithium compounds Highly reactive reactants are used as intermediates to synthesize the aforementioned quantum dots.
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