CN100503774C - Cadmium sulfide bare quantum spot and preparation process - Google Patents

Cadmium sulfide bare quantum spot and preparation process Download PDF

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CN100503774C
CN100503774C CN 200510031067 CN200510031067A CN100503774C CN 100503774 C CN100503774 C CN 100503774C CN 200510031067 CN200510031067 CN 200510031067 CN 200510031067 A CN200510031067 A CN 200510031067A CN 100503774 C CN100503774 C CN 100503774C
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quantum dots
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CN1952038A (en
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汪勇先
许荣辉
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中国科学院上海应用物理研究所
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Abstract

本发明公开了一种硫化镉裸量子点,其为颗粒状纳米晶,其荧光发射峰λmax为415-420nm,半高峰宽为80~100nm。 The present invention discloses a bare CdS quantum dots, which is a particulate nanocrystal, emission band λmax which is 415-420nm, peak half-width of 80 ~ 100nm. 本发明还公开了其采用水热合成法,将Cd/S摩尔比为1~1.2∶1的水溶性无机镉盐与L-半胱氨酸,在pH9~13的反应体系中进行反应的制备方法。 The present invention also discloses a hydrothermal synthesis method, the Cd / S molar ratio of water-soluble inorganic salts of cadmium and L- cysteine ​​1 to 1.2 to prepare a reaction is carried out in a reaction system in pH9 ~ 13 method. 本发明方法简单、易操作,成本低;制备出了<10nm的不同粒径的CdS裸量子点,与现有产品相比,具有稳定性高、荧光发射峰形好、半高峰宽较窄、单色性好等优点,既为裸量子点的表面修饰赢得了宝贵的时间又提高了其荧光性能,使之经过表面修饰等后续处理后可用于生物组织标记。 The method of the present invention is simple, easy to operate, low cost; Preparation of a <10nm different particle sizes of bare CdS quantum dots, compared with the conventional product, having high stability, good fluorescence emission peak shape, half-height peak width is narrow, and good monochromaticity, both for the modified surface of the bare quantum dot won valuable time and improves its fluorescent properties, so that after subsequent processing after surface modification can be used for biological tissue marker.

Description

硫化镉裸量子点及其制备方法 Bare CdS quantum dots and preparation method

絲领⑧ Silk collar ⑧

本发明涉及纳米材料领域,特别涉及一种硫化镉(CdS)裸量子点及其 The present invention relates to the field of nano material, particularly to a cadmium sulfide (CdS) and bare QDs

制备方法。 Preparation.

背录技术 Back record technology

量子点(quantumdots, QDs)又可称为半导体纳米晶体(semiconductornanocrystal),作为一种最新型的荧光材料,与传统的有机染料分子相比量子点确实具有多种优势。 Quantum dots (quantumdots, QDs) may be called a semiconductor nanocrystal (semiconductornanocrystal), as a new type of fluorescent material, as compared with the conventional quantum dot organic dye molecules do have a number of advantages. 其中最大的优点在于有丰富的颜色。 The biggest advantage is that there is a wealth of color. 不同种类的纳米半导体材料能够按尺寸变化产生一个发光波长不同的、颜色分明的标记物家族,这是染料分子根本无法实现的。 Different types of nano-semiconductor materials can produce a different emission wavelength, color family distinct markers by dimensional change, which is impossible to achieve a dye molecule. 此外,它激发光谱宽,且连续分布,而发射光谱单色性好,且颜色可调,并能够承受多次的激发和光发射,有持久的稳定性。 Further, it is broad excitation spectrum, and a continuous distribution, good color and emission spectrum, and the color is adjustable and able to withstand multiple excitation and emission light, lasting stability. 量子点表面经修饰后再联接上生物特异性物质(如Protein A、抗体、链霉亲和素等)由于其尺寸小(一般仅20-30nm)可作为荧光探针,在生物化学、分子生物学、细胞生物学、基因组学、蛋白质组学、药物筛选、生物大分子相互作用等研究中有极广的应用前景。 Quantum dot surface modified material after coupling the biospecific (e.g., Protein A, an antibody, streptavidin, avidin, etc.) because of its small size (typically only 20-30nm) as a fluorescent probe in biochemistry, molecular biology science, the study of cell biology, genomics, proteomics, drug screening, and other biological molecules interact in a very broad application prospects. 因此,近二十多以来,国内外的无机材料学家们对无机半导体纳米材料进行了广泛而深入的研究。 Therefore, nearly twenty, inorganic materials scientists at home and abroad for inorganic semiconductor nanomaterials carried out extensive and in-depth research.

目前量子点制备中常常存在着量子点粒径分布不均匀、裸量子点稳定性较低、荧光发射峰不对称及其半高峰宽较宽等问题。 Quantum Dot Preparation currently there is often non-uniform particle size distribution of the quantum dot, the quantum dot bare low stability, and the fluorescence emission peak asymmetry problems width at half height. 尽管国际上的一些研究小组采取了一些对应措施(如表面修饰、金属有机法等)改善这些不足[见:Xiaohu Gao, Yuanyuan Cui, Richard M Levenson, Leland WK Chung &Shuming Nie: In vivo cancer targeting and imaging with semiconductor quantumdots. iVi^i?/otec/z"o/ 2004, 22: 969 - 976 .],但是表面修饰仍然没有解决裸量子 Although some research groups internationally adopted some countermeasures (such as surface-modified metal organic method, etc.) to improve these deficiencies [See: Xiaohu Gao, Yuanyuan Cui, Richard M Levenson, Leland WK Chung & Shuming Nie: In vivo cancer targeting and imaging .? with semiconductor quantumdots iVi ^ i / otec / z "o / 2004, 22:. 969 - 976], but still does not solve the bare surface modification quantum

3点稳定性差的问题。 3:00 poor stability. 目前国际上较为流行金属有机法制备量子点产品。 Currently the more popular products prepared quantum dot organic metal method. 该法制备所得的量子点粒度可控、荧光发射峰窄,有着极为突出的优点。 The resulting quantum dots Preparation of controlled particle size, narrow emission peak, has a very prominent advantages. 但是,该法也有无法逃避的缺点:①是无法制备裸量子点,金属有机法制得的量子点表面往往包裹了一层有机层,如TOPO(氧化三辛基膦,极毒且昂贵)这为后续量子点的表面修饰丧失了许多可能优化发展的选择;②金属有机法不仅有毒、易燃而且原料极为昂贵,所以在实际应用中受到了很大的限制。 However, this method also has drawbacks inescapable: ① the bare quantum dot is not prepared, the organic metal surface of the quantum dot method were often wrapped layer of organic, such as TOPO (trioctylphosphine oxide, highly toxic and expensive) which is subsequent modification of the surface of the quantum dot may be selected to optimize the loss of many development; ② organic metal method is not only toxic, flammable and very expensive raw materials, it has been greatly limited in practical application.

相对于具有有机包覆层的量子点,许多无机合成方法制得的量子点的表面只含有构成体相组成的粒子,如CdS QDs仅具有构成硫化镉的镉离子或者硫离子,故又称其为裸量子点。 With respect to the organic coating layer having a quantum dot, the surface of the quantum dot number of inorganic synthetic methods containing only phase particles constituting the composition, such as cadmium sulfide CdS QDs only composed of ions or cadmium sulfide, it is also known that bare quantum dots. 其中水法是最常见的方法之一[见:YaoJian-Xi»Zhao Gao-LingjHan GaoRong: The effect of the ratio of thiourea to Cd2+on the properties of CdS nanoparticles. M'crae/ec的"/c2003,66:115-120.],这或许是因为方法的简便和反应条件容易到达的缘故。水法的反应温度一般都低于水溶液的正常沸点(即100'C左右),因此水法所得产品的结构大多属于无定形物质(nanopartide),而不是真正意义上的纳米晶,导致其在条件变化的情况下非常容易发生结构转变;另一方面就是产品的荧光发射峰常常不尖锐、不对称甚至出现杂质肩峰,其荧光发射峰的半高峰宽也常常很宽, 一般都大于120nm[Yao Jian-Xi etc. The effect of the ratioof thiourea to Cd2+ on the properties of CdS nanoparticles. MicroelectronicEngineering 2003(65): 115-120; Lucia Pedone etc. Synthesis and charaterizationof CdS nanoparticles embedded in a polymethylmethacrylate marix. J. Colloidand Interface Science Wherein the water method is the most common method [see: YaoJian-Xi »Zhao Gao-LingjHan GaoRong: The effect of the ratio of thiourea to Cd2 + on the properties of CdS nanoparticles M'crae / ec of" / c2003,. 66: 115-120], perhaps because the sake of simplicity and the reaction conditions of the process the temperature of the water within easy reach of the reaction process are generally lower than the normal boiling point of the aqueous solution (i.e. about 100'C), so that the resulting product water law. most belong to the structure of amorphous material (nanopartide), but not in the sense of real nanocrystals, leading to structural changes occur very easily in case of changing conditions; on the other hand is the peak fluorescence emission products are often not sharp, asymmetric or even impurities shoulder, its fluorescence emission peak half height width is often very wide, generally greater than 120nm [Yao Jian-Xi etc. the effect of the ratioof thiourea to Cd2 + on the properties of CdS nanoparticles MicroelectronicEngineering 2003 (65):. 115 -120; Lucia Pedone etc. Synthesis and charaterizationof CdS nanoparticles embedded in a polymethylmethacrylate marix J. Colloidand Interface Science. 2005(281 ):495-500]。作为可以分辨的生物荧光量子点,水法制备的半导体纳米晶己经失去实际应用价值。另外有报道用水热合成法(简称水热法),在密闭装置(高压釜)中,采用水为溶剂,在高压升温条件下进行反应,制备得到5nm大小(由谢乐公式计算XRD衍射峰的半峰宽得到)、晶胞参数a=0.5818nm的球状立方P-CdS纳米晶(见:①苏宜等:纳米ZnS、 CdS水热合成及其表征,《应用化学》,1996, 13: 56),但未揭示该CdS纳米晶荧光发射性质的有关数据或图谱,无法得知是否为具有荧光发射性能的CdS裸量子点。 2005 (281): 495-500] As can be resolved bioluminescence quantum dots, prepared by Method semiconductor nanocrystals water loses practical value have also been reported hydrothermal synthesis (referred to as hydrothermal method), the obturator (. autoclave), using water as a solvent, the reaction at elevated temperature under high pressure, prepared 5nm size (half-value width obtained by the Scherrer formula XRD diffraction peak), unit cell parameters a = 0.5818nm spherical cubic P- CdS nanocrystals (see: Su Yi et ①: nano ZnS, CdS hydrothermal synthesis and characterization, "applied Chemistry", 1996, 13:56), but did not reveal the data about the maps or nanocrystalline fluorescence emission properties of the CdS, not know whether to have a bare CdS quantum dot fluorescence emission properties.

发明内容 SUMMARY

本发明要解决的技术问题是提供一种具有颗粒状纳米晶结构,荧光发射 The present invention is to solve the technical problem of providing a particulate having a nanocrystalline structure, the fluorescence emission

峰形好、半髙峰宽较窄的硫化镉(CdS)裸量子点。 Good peak shape, the half-value width narrower Gao cadmium sulfide (CdS) bare quantum dots.

本发明CdS裸量子点的颗粒状纳米晶结构,其X光粉晶衍射(XRD)图谱发现两套晶体参数:一为六方结构的硫镉矿(Greenockite)的XRD谱、另一则是计算机算出的立方硫化镉的XRD谱(晶胞参数a-0.58304nm)。 Bare CdS nanocrystals quantum dots granular structure of the present invention, an X-ray powder diffraction (XRD) pattern of the crystal was found two parameters: a structure of a hexagonal cadmium sulfur ore (greenockite) an XRD spectrum, and the other is computer calculated the XRD spectra of CdS cube (cell parameters a-0.58304nm).

本发明CdS裸量子点的荧光发射峰入max —般在415-420nm范围,半高峰宽一般为80〜100nm,较佳地为80nm。 The present invention is fluorescence emission peak bare CdS quantum dots into the max - generally in the range of 415-420nm, half-height peak width is generally 80~100nm, preferably a 80nm.

本发明要解决的另一技术问题是提供上述硫化锅裸量子点的制备方法。 Another technical problem to be solved by the present invention is to provide a method for preparing the vulcanization pot bare quantum dots. 其具体技术方案为:采用水热合成法,将Cd/S摩尔比为1〜1.2:1的醋酸镉或水溶性无机镉盐与L-半胱氨酸,在pH9〜13的反应体系中进行反应;其中醋酸镉或水溶性无机镉盐在反应体系中的浓度为5〜54.5mmol/L, L-半胱氨酸在反应体系中的浓度为4.5〜50mmol/L。 The specific technical scheme: hydrothermal synthesis method, the Cd / S molar ratio of 1~1.2: cadmium acetate or cadmium salts and water-soluble inorganic L- cysteine ​​1 is carried out in a reaction system in pH9~13 response; wherein the concentration of water-soluble inorganic or cadmium acetate, cadmium salts in the reaction system is 5~54.5mmol / L, L- cysteine ​​concentration in the reaction system is 4.5~50mmol / L.

本发明制备方法为硫化镉量子点的生成提供高温高压的动力学条件,控制硫化镉晶体成核速率与生长速率的相对大小而得到尺寸大小可控的硫化镉纳米晶。 Dynamic conditions of the present invention is a method of preparation of CdS quantum dots generate high temperature and pressure to provide the control relative sizes of CdS crystal nucleation rate and growth rate of the size controllable obtained CdS nanocrystals. 在研究过程中发现,调控硫化镉量子点尺寸的因素有:原料种类、原料配比、反应物浓度、反应混合物的pH值。 In the course of the study we found that the regulation of CdS quantum dot size factors are: type of raw material, raw material ratio, reactant concentration, pH of the reaction mixture. 影响产品荧光发射性能的因素有:反应混合物的pH值、纳米晶的晶型、高温高压停留时间。 Factors that affect product performance are fluorescence emission follows: pH of the reaction mixture, the crystalline form nanocrystalline, high temperature and pressure the residence time. 影响产品稳定性的因素除了避光保存,还有制得产品的尺寸,因为众所周知,尺寸越小,产品的比表面积越大,而稳定性则下降。 In addition to the factors affecting the stability of the product stored in the dark, as well as the size of the product were, as we all know, the smaller the size, the larger the surface area of ​​the product, while stability decreased.

具体而言,本发明选用的原料种类为:镉源可以采用醋酸镉或水溶性无 Specifically, the present invention selects the type of material: the source of cadmium acetate, cadmium or water may be used without

机镉盐,如氯化镉、硝酸镉或硫酸镉等易溶性镉盐,其中采用醋酸镉制得的 Machine cadmium salts such as cadmium chloride, cadmium sulfate, cadmium nitrate, or other soluble salts of cadmium, which is prepared using cadmium acetate

量子点荧光发射效果最好;而硫源可以采用硫化钠、硫代硫酸钠及含巯基化 Best quantum dot fluorescence emission; sodium sulfide and sulfur source may be used, sodium thiosulfate and thiol-containing

5合物等含硫化合物,本发明优选L-半胱氨酸,因使用其非常利于控制反应体 Sulfur compounds such as compound 5, preferably L- cysteine ​​present invention, which is very beneficial to the use thereof to control the reaction

系的粘度及硫源的存在形态,进而便于控制制得的量子点尺寸。 The viscosity and the presence of forms of sulfur source system, and thus easy to control the size of the quantum dots prepared.

本发明最优选醋酸镉及L-半胱氨酸作为反应原料,因为无需洗涤等进一步处理,制得的CdS量子点即具有较佳的荧光发射性能。 Most preferably the present invention cadmium acetate and L- cysteine ​​as the starting material, because no further washing treatment, the CdS quantum dots prepared i.e. having a preferred fluorescence emission performance.

原料配比是影响量子点尺寸的最主要因素之一。 Ratio of raw materials is one of the most important factors that affect the size of the quantum dots. 一般而言,Cd/S(Cd2+/S2')远离1时硫化镉半导体纳米晶的尺寸较大。 In general, Cd / S (Cd2 + / S2 ') remote from 1:00 larger CdS nanocrystals size. 这可能是由于当一种成分明显多于另外一种成分时有利于形成较少数量的晶核,此时体系的粘度低,晶体生长的传质变得容易进行,因此得到大尺寸晶体。 This may favor the formation of crystal nuclei due to the smaller number of significantly more than one component as another component, the low viscosity of the system at this time, the mass transfer for crystal growth becomes easy, thereby obtaining a large-sized crystals. 相反,当Cd/S(Cd2+/S2')接近l时由于生成的晶核多,导致体系的粘度增大,传质困难,因此得到小尺寸纳米晶。 In contrast, when the Cd / S (Cd2 + / S2 ') is generated due to the proximity l multi-nuclei, the viscosity of the system increases, the mass transfer is difficult, so to obtain a small-sized nanocrystals.

反应物在反应体系中的浓度对纳米晶尺寸的影响也是非常明显的。 Effects of concentrations of the reactants in the reaction system of nanocrystals size is also very obvious. 反应物浓度的增大有利于体系粘度的升高,也能使纳米晶尺寸变小,但浓度太高, Increasing reactant concentrations favor increased viscosity of the system, but also make nanocrystalline size becomes small, but the concentration is too high,

如醋酸镉或水溶性无机镉盐在反应体系中的浓度超过54.5mmol/L, L-半胱氨酸在反应体系中的浓度超过50mmol/L,则量子点团聚越明显,制得的产品还需进一步的分离;相反,浓度如果太低,如醋酸镉或水溶性无机镉盐在反应体系中的浓度低于5mmol/L, L-半胱氨酸在反应体系中的浓度低于4.5mmol/L,将得到大颗粒的产品(大于10nm),而得不到量子点。 The concentrations of cadmium acetate, cadmium or water-soluble inorganic salt in the reaction system is more than 54.5mmol / L, L- cysteine ​​concentration in the reaction system is more than 50mmol / L, the more obvious the quantum dot agglomeration, the resulting products are also further separation is; the contrary, if the concentration is too low, such as the concentration of cadmium acetate, cadmium or water-soluble inorganic salt in the reaction system is less than 5mmol / L, L- cysteine ​​concentration in the reaction system is lower than 4.5mmol / L, the product obtained large particles (greater than 10nm), but not the quantum dots. 本发明优选醋酸镉或水溶性无机镉盐在反应体系中的浓度为25〜54.5mmol/L, L-半胱氨酸在反应体系中的浓度为22.5〜50mmol/L。 Preferably the concentration of cadmium acetate or water-soluble inorganic salts of cadmium in the reaction system of the present invention is 25~54.5mmol / L, L- cysteine ​​concentration in the reaction system is 22.5~50mmol / L. 同时,本发明为便于调控反应及直观理解,两个主要反应物采取相同的浓度,而且均为反应物各自的起始浓度。 Meanwhile, the present invention is to facilitate the reaction and regulation intuitive understanding, adopt the same two principal reactant concentrations, and are the respective start concentration of the reactants. 一般认为水热法制备硫化镉量子点的反应物起始浓度应该远远低于O.lmol,L",但是本发明人通过实验发现最佳的反应物起始浓度介于0.01〜0.1mol丄"之间,较佳地为0.05〜0.1mol丄-'。 The reaction was generally believed that the initial concentration of CdS quantum dots prepared by hydrothermal method should be much less than O.lmol, L ", the present inventors found through experiments that the optimum range of the initial concentration of reactants 0.01~0.1mol Shang "between, preferably a 0.05~0.1mol Shang - '.

反应混合物的pH值对产物粒度的影响基本上也是通过改变体系的粘度来实现的。 Effect of pH of the reaction mixture to a particle size of the product is achieved by substantially changing the viscosity of the system. pH增大,粘度升高,不利于传质,有利于得到大量的小晶核,因此纳米晶尺寸变小。 increase of pH, viscosity, and not conducive to mass transfer, it is advantageous for obtaining large number of small nuclei, so small in size nanocrystals. 此外反应混合物的pH值对荧光发射性能也是有影响 In addition the pH of the reaction mixture is going to affect the performance of the fluorescence emission

6的。 6. 较适宜的pH值一般控制在10-12之间,小于10和大于12均会使产品的荧光发射性能下降,原因可能是环境的变化使得量子点表面的结构发生了变化,进而影响到了其荧光发射性能。 More suitable pH value is generally controlled between 10 and 12, less than 10, and 12 are greater than the fluorescence emission properties of the product will decrease, probably due to changes in the environment such that the surface of the quantum dot structure changes, thereby affecting its fluorescence emission properties.

本发明所用的水热合成法,是在高压釜中加压升温进行,可为单一高温或两阶段升温。 Hydrothermal synthesis method used in the present invention, is a pressurized heating in an autoclave, the temperature may be raised to a single or two-stage. 具体而言,加压升温至较低温度T,: 80〜11CTC、维持时间t1: 0〜3小时,再至较高温度丁2: U0〜150。 Specifically, pressurized heated to a lower temperature T ,: 80~11CTC, maintenance time t1: 0~3 hours, and then to a higher temperature but-2: U0~150. C、维持时间t2:至少2小时;其中总维持时间t,+t2》5小时。 C, maintained time t2: at least 2 hours; wherein the total maintenance time t, + t2 "5 hours. 较佳地,温度T,为8(TC、维持时间ti为3小时。总维持时间优选为5~8小时。优选升温至110°C-150°C。由于温度高低对晶体成核与晶体生长有不同影响,即较低温相对有利于成核,较高温则有利于晶体长大。当体系温度从8(TC升高到15(TC时,得到的纳米晶尺寸总 Preferably, the temperature T, was found 8 (TC, duration ti was 3 hours. The total holding time is preferably 5 to 8 hours. Preferably heated to 110 ° C-150 ° C. Since the temperature level of crystal nucleation and crystal growth have different effects, i.e. relatively low temperatures favor nucleation, higher temperature is advantageous for crystal growth. when the temperature of the system from the 8 (TC raised to 15 (TC, the resulting total dimensions of nanocrystals

是在不断增大,故可得到从小到大不同粒径的量子点。 Is increasing, it can be obtained from small to large quantum dots of different sizes. 温度对量子点荧光发射性能不是很直接的,它是通过改变产品尺寸进而改变其荧光发射波长实现的;同样,温度对量子点的稳定性也是通过改变产品尺寸进而影响的。 The temperature of the quantum dot fluorescence emission properties is not straightforward, which is in turn changes its fluorescence emission wavelength realized by changing the size of the product; likewise, the temperature stability of the quantum dots is affected by varying the size of the product further. 本发明如果采用单一高温(即110〜150°C),优选高温维持时间为6〜8h,时间太短,则结晶不够完全,而高温停留时间更长对量子点的尺寸大小、荧光发射性能及稳定性能基本上没有影响,反而徒增制备时间。 If the present invention uses a single temperature (i.e. 110~150 ° C), the high-temperature maintaining time is preferably 6~8h, time is too short, the crystallization is incomplete, and the temperature stay longer size of the quantum dots, and the fluorescence emission properties stable performance had essentially no effect, but create more preparation time. 而如果高温分为两段,低温段时间的延长往往会使得量子点尺寸减小、荧光发射性能增强、稳定性下降。 If the extension is divided into two high-temperature, low temperature so that the period of time tends to reduce the size of the quantum dot fluorescence emission performance enhanced stability.

本发明水热法与现有水法的最大差别之一是反应温度,其一般都要远远高于水溶液正常压力下的沸点,其制备出了〈10nm的不同粒径的CdS纳米晶(nanocrystal),成为真正意义上的量子点,本发明的CdS量子点结晶完美,具有稳定性高、荧光发射峰形好、半高峰宽较窄、单色性好等优点,故本发明制备方法不仅克服了水法制备所得的量子点结构不稳定、荧光发射峰形态欠佳等缺陷,同时也避免了金属有机法的毒性与高成本,且简单、易操作;而且利用本发明水热法,可制备出粒度可控的硫化镉量子点。 Hydrothermal largest difference between the present invention and the conventional water method is the reaction temperature, which typically have much higher than the boiling point of the aqueous solution under normal pressure, preparing a <CdS different sizes of 10nm nanocrystalline (NanoCrystal ), quantum dots become real sense, CdS quantum dots of the present invention is a perfect crystal, high stability, good fluorescence emission peak shape, half-height peak width is narrow, good color, etc., so the production method of the present invention not only overcomes preparation of the resulting aqueous quantum dot structure is unstable emission peak shape defects such as poor, while avoiding the high cost and the toxicity of the metal-organic method, and simple, easy to operate; hydrothermal method and the use of the present invention, may be prepared a controllable particle size CdS quantum dots. 更可贵的在于,本发明硫化镉量子点具有超强的稳定性和表面无任何包裹的"裸体性",为量子点以后的表面修饰保留了许许多多的可能性;换言之,本发明为进一步获得可作为荧光材料、并具有更佳荧光性能的表面修饰的CdS量子点提供了大量裸量子点原材料,使这些CdS裸量子点经过表面修饰等后续处 Even more valuable that the CdS quantum dots of the present invention has superior stability and surface free "nude" of any package for the subsequent quantum dot surface modification retains many possibilities; in other words, the present invention further to obtain surface-modified CdS quantum dots as fluorescent material, and fluorescence having better properties of quantum dots provide a large number of bare material, these bare CdS quantum dot at a subsequent surface modification through

理后可用于生物组织标记。 After treatment of biological tissue marker can be used. 附闺说明 Description attached Gui

图1为本发明一实施例CdS量子点(纳米晶)的XRD图谱。 Embodiment of Figure 1 CdS quantum dots (nanocrystals) embodiment of a XRD pattern of the present invention. 图2为本发明实施例1 CdS量子点的AFM照片(A)及荧光发射谱图(B)。 Figure 2 1 CdS quantum dots embodiment of the present invention, AFM image (A) and fluorescence emission spectrum (B).

图3为本发明实施例2 CdS量子点的AFM照片(A)及荧光发射谱图(B)。 FIG 3 2 CdS quantum dots embodiment of the present invention, AFM image (A) and fluorescence emission spectrum (B).

图4为本发明实施例3 CdS量子点的AFM照片(A)及荧光发射谱图(B)。 Figure 4 3 CdS quantum dots embodiment of the present invention, AFM image (A) and fluorescence emission spectrum (B).

图5为本发明实施例4 CdS量子点的AFM照片(A)及荧光发射谱图(B)0 FIG 5 4 CdS quantum dots embodiment of the present invention, AFM image (A) and fluorescence emission spectrum (B) 0

图6为本发明实施例5 CdS量子点的AFM照片(A)及荧光发射谱图(B)。 Figure 6 5 CdS quantum dots embodiment of the present invention, AFM image (A) and fluorescence emission spectrum (B).

图7为实施例2放置在反应原溶液中46天后的荧光发射谱图。 Example 2 FIG. 7 is placed in a reaction solution 46 days after the original fluorescence emission spectrum. 具体实施方式 Detailed ways

本发明通过以下的实施例作进一步阐述,但并不限制本发明的范围。 The present invention is further illustrated by the following examples, but do not limit the scope of the present invention. 实施例1 Example 1

Cd/S比例按1.2量取0.05 (mol/L)醋酸镉60ml与0.05 (mol/L) L-半胱氨酸50ml混合于高压反应釜内胆中(醋酸镉在反应体系中的浓度为27mmol/L, L-半胱氨酸的反应浓度为22.5mmol/L),用浓度为lmol/L氢氧化钾溶液调节溶液的酸碱度,使之pH为ll。 Cd / S ratio of 1.2 was weighed 0.05 (mol / L) and cadmium acetate 60ml 0.05 (mol / L) L- cysteine ​​50ml were mixed in the autoclave bladders (cadmium acetate concentration in the reaction system was 27mmol / L, the reaction L- cysteine ​​concentration is 22.5mmol / L), at a concentration of lmol / L potassium hydroxide solution to adjust the solution pH, so a pH of ll. 将高压反应釜密闭,通电加热加压到13(TC,并进行磁力搅拌。高温阶段保温7小时。经过自然冷却降温并确保高压釜内压力降到常压后打开釜盖,将反应釜内物料转移至一磨口瓶 The sealed autoclave, pressurized to resistance heating 13 (TC, and magnetic stirring. Phase incubation temperature for 7 hours. After cooling and natural cooling ensure that atmospheric pressure in the autoclave dropped to open the tank cover, the autoclave were transfer to a jar mill

中,避光保存。 Protected from light. 得到的产品表征数据:原子力显微镜(AFM)照片及荧光发射谱图见图2所示,该硫化镉量子点的尺寸为6.6nm左右,X max在417nm,半高峰宽为80nm。 Product characterization data obtained: atomic force microscopy (AFM) photograph and fluorescence emission spectra shown in Figure 2, the size of the CdS quantum dots is about 6.6nm, X max at 417nm, the peak half width of 80nm. 实施例2 Example 2

Cd/S比例按1量取0.05 (mol/L)醋酸镉60ml与0.05 (mol/L) L-半胱氨酸60ml混合于高压反应釜内胆中(醋酸镉在反应体系中的浓度为25mmol/L, L-半胱氨酸的反应浓度为25mmol/L),用浓度为lmol/L氢氧化钾溶液调节溶液的酸碱度,使之pH为12。 Cd / S 1 ratio by volume taken 0.05 (mol / L) and cadmium acetate 60ml 0.05 (mol / L) L- cysteine ​​60ml were mixed in the autoclave bladders (cadmium acetate concentration in the reaction system was 25mmol / L, the reaction L- cysteine ​​concentration is 25mmol / L), at a concentration of lmol / L potassium hydroxide solution to adjust the solution pH, so a pH of 12. 将高压反应釜密闭,通电加热加压到13(TC,并进行磁力搅拌。高温阶段保温7小时。经过自然冷却降温并确保高压釜内压力降到常压后打开釜盖,将反应釜内物料转移至一磨口瓶中,避光保存。得到的产品表征数据:原子力显微镜(AFM)照片及荧光发射谱图见图3所示,该硫化镉量子点的尺寸为2.0nm,入max在416nm,半高峰宽为80nm。实施例3 The sealed autoclave, pressurized to resistance heating 13 (TC, and magnetic stirring. Phase incubation temperature for 7 hours. After cooling and natural cooling ensure that atmospheric pressure in the autoclave dropped to open the tank cover, the autoclave were was transferred to a mill jar, protected from light product obtained characterizing data: atomic force microscopy (AFM) photograph and fluorescence emission spectra shown in Figure 3, the size of the CdS quantum dots is 2.0 nm, the max of 416nm , half height width of 80nm. Example 3

Cd/S比例按1.2量取0.10 (mol/L)醋酸镉60ml与0.10 (mol/L) L-半胱氨酸50ml混合于高压反应釜内胆中(醋酸镉在反应体系中的浓度为54.5mmoi/L, L-半胱氨酸的反应浓度为45.4mmol/L),用浓度为lmol/L氢氧化钾溶液调节pH为12。 Cd / S ratio of 1.2 was weighed 0.10 (mol / L) and cadmium acetate 60ml 0.10 (mol / L) L- cysteine ​​50ml were mixed in the autoclave bladders (cadmium acetate concentration in the reaction system was 54.5 mmoi / L, the reaction L- cysteine ​​concentration is 45.4mmol / L), at a concentration of lmol / L potassium hydroxide solution adjusted to pH 12. 将高压反应釜密闭,通电加热加压到i3(TC,并进行磁力搅拌。高温阶段保温6小时。经过自然冷却降温并确保高压釜内压力降到常压后打开釜盖,将反应釜内物料转移至一磨口瓶中,避光保存。得到的产品表征数据:原子力显微镜(AFM)照片及荧光发射谱图见图4所示,该硫化镉量子点的尺寸为4.998mn、 10.469mn,后者为前者的两倍左右,估计后者是二聚体;Amax在419nm,半高峰宽为83nm;其X光粉晶衍射(XRD) The sealed autoclave, pressurized to resistance heating i3 (TC, and magnetic stirring. Phase incubation temperature for 6 hours. After cooling and natural cooling ensure that atmospheric pressure in the autoclave dropped to open the tank cover, the autoclave were was transferred to a mill jar, protected from light product obtained characterizing data: atomic force microscopy (AFM) photograph and fluorescence emission spectra shown in Figure 4, the size of the quantum dot is CdS 4.998mn, 10.469mn, after by approximately twice the former, which is estimated dimer; Amax at 419nm, half-height peak width of 83 nm; an X-ray powder diffraction (XRD)

图谱如图1所示,图中发现两套晶体参数:"•"为六方结构的硫镉矿(Greenockite)的XRD谱、"'"则是计算机算出的立方硫化镉的XRD谱(晶 Pattern shown in FIG. 1, FIG crystal parameters found in two: "•" is the XRD spectra cadmium sulfur ore hexagonal structure (greenockite), a " '" is calculated by the computer cubic CdS XRD spectrum (Form

9胞参数a^0.58304nm);结合原子力显微镜(AFM)照片可见产品尺寸为5nm左右,具有非常明显的量子限域效应,有较大强度的荧光发射。 9 cell parameters a ^ 0.58304nm); binding atomic force microscope (AFM) photograph of about 5 nm visible dimensions, with a very significant quantum confinement effect, a greater intensity of fluorescence emission. 实施例4 Example 4

Cd/S比例按1.2量取0.05 (mol/L)醋酸镉60ml与0.05 (mol/L) L-半胱氨酸50ml混合于高压反应釜内胆中(醋酸镉在反应体系中的浓度为27mmol/L, L-半胱氨酸的反应浓度为22.5mmol/L),用浓度为lmol/L氢氧化钾溶液调节溶液pH为9。 Cd / S ratio of 1.2 was weighed 0.05 (mol / L) and cadmium acetate 60ml 0.05 (mol / L) L- cysteine ​​50ml were mixed in the autoclave bladders (cadmium acetate concentration in the reaction system was 27mmol / L, the reaction L- cysteine ​​concentration is 22.5mmol / L), at a concentration of lmol / L potassium hydroxide solution to adjust the solution to pH 9. 将高压反应釜密闭,通电加热到80'C,并进行磁力搅拌保温3小时。 The sealed autoclave, heated to 80 'C. power, and magnetically stirred for 3 hours. 升温到110'C,高温阶段保温2小时。 Raised to 110'C, the high temperature stage incubated for 2 hours. 经过自然冷却降温并确保高压釜内压力降到常压后打开釜盖,将反应釜内物料转移至一磨口瓶中,避光保存。 After natural cooling down and ensure that atmospheric pressure in the autoclave dropped to open the tank cover, the contents of the autoclave reaction were transferred to a mill jar, protected from light. 得到的产品表征数据:原子力显微镜(AFM)照片及荧光发射谱图见图5所示,该硫化镉量子点的尺寸为2.026913nm、2.457682nm、24.15842nm,其中最后一个为聚集体的尺寸;入max在416nm,半高峰宽为82nm。 Product characterization data obtained: atomic force microscopy (AFM) photograph and fluorescence emission spectra shown in Figure 5, the size of the quantum dot is CdS 2.026913nm, 2.457682nm, 24.15842nm, wherein one of the final size of the aggregates; into max at 416nm, the peak half width of 82nm.

实施例5 Example 5

Cd/S比例按1.2量取0.05 (mol/L)醋酸镉60ml与0,05 (mol/L) L-半胱氨酸50ml混合于高压反应釜内胆中(醋酸镉在反应体系中的浓度为27mmoi/L, L-半胱氨酸的反应浓度为22.5mmol/L),用浓度为lmol/L氢氧化钾溶液调节溶液的pH为13。 Cd / S ratio of 1.2 was weighed 0.05 (mol / L) and cadmium acetate 60ml 0,05 (mol / L) L- cysteine ​​50ml were mixed in the autoclave interior concentration (cadmium acetate in the reaction system is 27mmoi / L, the reaction L- cysteine ​​concentration is 22.5mmol / L), at a concentration of lmol / L potassium hydroxide solution to adjust the pH of the solution 13. 将高压反应釜密闭,通电加热加压到140°C,并进行磁力搅拌。 The sealed autoclave, pressurized to resistance heating 140 ° C, and magnetic stirring. 高温阶段保温8小时。 Stage incubation temperature for 8 hours. 经过自然冷却降温并确保高压釜内压力降到常压后打开釜盖,将反应釜内物料转移至一磨口瓶中,避光保存。 After natural cooling down and ensure that atmospheric pressure in the autoclave dropped to open the tank cover, the contents of the autoclave reaction were transferred to a mill jar, protected from light. 得到的产品表征数据:原子力显微镜(AFM)照片及荧光发射谱图见图6所示,该硫化镉量子点的尺寸为5.582757nm、 11.90723nm,后者基本上是前者的两倍,可以认为后者是二聚体;入max在419nm,半高峰宽为99ran。 Product characterization data obtained: atomic force microscopy (AFM) photograph and fluorescence emission spectra as shown in Figure 6, the size of the quantum dot is CdS 5.582757nm, 11.90723nm, which is substantially twice as much, can be considered the who are dimers; in the max 419nm, half-height peak width 99ran.

实施例6 Example 6

Cd/S比例按1.2量取0.01 (mol/L)醋酸镉60ml与0.01 (mol/L) L-半胱氨酸50ml混合于高压反应釜内胆中(醋酸镉在反应体系中的浓度为5.4mmol/L, L-半胱氨酸的反应浓度为4.5mmol/L),用浓度为lmoi/L氢氧化钾溶液调节溶液pH为9。 Cd / S ratio of 1.2 was weighed 0.01 (mol / L) and cadmium acetate 60ml 0.01 (mol / L) L- cysteine ​​50ml were mixed in the autoclave bladders (cadmium acetate concentration in the reaction system is 5.4 mmol / L, L- cysteine ​​concentration of the reaction was 4.5mmol / L), a concentration of lmoi / L potassium hydroxide solution to adjust the solution to pH 9. 将高压反应釜密闭,通电加热到11(TC,并进行磁力搅拌保温6小时。经过自然冷却降温并确保高压釜内压力降到常压后打开釜盖,将反应釜内物料转移至一磨口瓶中,避光保存。得到的产品表征数据:原子力显微镜(AFM)照片及荧光发射谱图显示,该硫化镉量子点的尺寸为7.142913nm、 7.204682nm;入max在417nm,半高峰宽为83nm。 The sealed autoclave, conduction heating to 11 (TC, and incubated with magnetic stirring for 6 hours. After cooling and natural cooling ensure that atmospheric pressure in the autoclave dropped to open the tank cover, the contents of the autoclave reaction were transferred to a ground port flask, protected from light product obtained characterizing data: atomic force microscopy (AFM) and fluorescence emission spectra show pictures, the size of the quantum dot is CdS 7.142913nm, 7.204682nm; in the max 417nm, half-height peak width of 83nm. .

为便于调控反应及直观理解,下列实施例中镉源、硫源两个主要反应物采取相同的浓度,而且均为反应物各自的起始浓度。 To facilitate regulation of the reaction and intuitive understanding, the following embodiment examples cadmium source, sulfur source adopt the same two principal reactant concentrations, and are the respective start concentration of the reactants. 实际上,影响到体系粘度的应是反应体系中的浓度,因此如采用其它反应物起始浓度,只要其在反应体系中的反应浓度在本发明范围即可。 In fact, it affects the viscosity of the system should be in a concentration in the reaction system, so as to use other starting concentration thereof of the reaction, insofar as the concentration in the reaction system in the present invention range.

上述实施例中的镉源、硫源购自国药集团。 The above-described embodiments cadmium sources, sulfur sources available from Sinopharm.

可见,本发明CdS裸量子点的荧光发射峰形好、半高峰宽较窄,说明其粒径大小分布较均匀,而且单色性好。 Be seen, the present invention is good bare CdS quantum dot fluorescence emission peak shape, half-height peak width is narrow, indicating that a more uniform particle size distribution, and good color.

试验实施例1本发明CdS裸量子点的稳定性试验- Stability Test Test Example bare CdS quantum dots 1 Invention -

选用实施例2为样品,放在反应原溶液中保存了46天后再进行荧光发射性能测定。 Example 2 A sample selected, in the original reaction solution was stored for 46 days after fluorescence emission performance. 图谱如图7所示,荧光图谱左边的荧光发射峰尖锐而比较对称,与右边的倍频峰相比强度大。 Pattern shown in Figure 7, the fluorescence emission spectra peak fluorescence left sharp and more symmetrical, the peak frequency large compared with the right intensity. 鉴于样品尺寸小(2nm),且放在反应原溶液中保存了46天还有强荧光,可见本发明水热法制备的硫化镉量子点稳定性极高。 In view of the small sample size (2nm), and the solution was placed in the reaction the original stored 46 days there strong fluorescence, visible high hydrothermal stability of the present invention prepared by Method CdS quantum dots.

ii ii

Claims (7)

1、一种硫化镉裸量子点,其为颗粒状纳米晶,其荧光发射峰λmax为415-420nm,半高峰宽为80~100nm。 A bare CdS quantum dots, which is a particulate nanocrystal, emission band λmax which is 415-420nm, peak half-width of 80 ~ 100nm.
2、 如权利要求1所述的硫化镉裸量子点,其特征在于其半高峰宽为 2, the bare CdS quantum dots as claimed in claim 1, characterized in that it is a half-height width
3、 如权利要求1所述的硫化镉裸量子点的制备方法,其特征在于其采用水热合成法,将Cd/S摩尔比为1〜1.2:1的醋酸镉与L-半胱氨酸,在pH9〜 13的反应体系中进行反应;其中醋酸镉在反应体系中的浓度为5〜 54.5mmol/L, L-半胱氨酸在反应体系中的浓度为4.5〜50mmol/L。 3. The method for producing bare CdS quantum dot according to claim 1, characterized in that hydrothermal synthesis method, the Cd / S molar ratio of 1~1.2: 1, and cadmium acetate L- cysteine , in a reaction system in pH9~ 13; cadmium acetate in which the concentration of the reaction system was 5~ 54.5mmol / L, L- cysteine ​​concentration in the reaction system is 4.5~50mmol / L.
4、 如权利要求3所述的制备方法,其特征在于所述水热合成法是在高压釜中加压升温至温度T,: 80〜110'C、维持时间t,: 0〜3小时,再至温度T2: 110〜150°C、维持时间t2:至少2小时;其中总维持时间t,+t2》5小时。 4. The preparation process according to claim 3, wherein said hydrothermal synthesis is pressurized in an autoclave heated to a temperature T ,: 80~110'C, maintenance time t ,: 0~3 hours, again to a temperature T2: 110~150 ° C, maintained time t2: at least 2 hours; wherein the total maintenance time t, + t2 "5 hours.
5、 如权利要求4所述的制备方法,其特征在于该温度T,为80'C,维持时间t,为3小时。 5. The preparation method claimed in claim 4, characterized in that the temperature T, was found 80 'C., maintaining time t, 3 hours.
6、 如权利要求4所述的制备方法,其特征在于该总维持时间为5〜8小时。 6, prepared as claimed in claim 4, characterized in that the total duration of 5 ~ 8 hours.
7、 如权利要求3所述的制备方法,其特征在于醋酸镉在反应体系中的浓度为25〜54.5mmol/L, L-半胱氨酸在反应体系中的浓度为22.5〜 50mmol/L» 7. The method of preparation as claimed in claim 3, characterized in that the concentration of cadmium acetate in the reaction system is 25~54.5mmol / L, L- cysteine ​​concentration in the reaction system is 22.5~ 50mmol / L »
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CN101074369B (en) 2007-06-27 2012-04-18 哈尔滨工业大学 Cds quantum point doped with cobalt inside lattice-ion and its production
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Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US6501091B1 (en) 1998-04-01 2002-12-31 Massachusetts Institute Of Technology Quantum dot white and colored light emitting diodes
CN1547238A (en) 2003-12-02 2004-11-17 武汉大学 Method for preparing CdSe quantum point

Patent Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US6501091B1 (en) 1998-04-01 2002-12-31 Massachusetts Institute Of Technology Quantum dot white and colored light emitting diodes
CN1547238A (en) 2003-12-02 2004-11-17 武汉大学 Method for preparing CdSe quantum point

Non-Patent Citations (4)

* Cited by examiner, † Cited by third party
Title
有机-无机复合CdS纳米晶的制备及表征. 楼文静,陈淼.材料科学与工程学报,第23卷第6期. 2005
有机溶剂热生长技术制备纳米CdS及其与聚苯胺复合膜的光学性能. 钟淮珍,李国强,何晓云,陈日耀,郑曦,陈震.发光学报,第25卷第5期. 2004
水热法合成CdS/ZnO核壳结构纳米微粒. 孙聆东,付雪峰,钱程,廖春生,严纯华.《高等学校化学学报》,第22卷第6期. 2001
硫化镉纳米离子的制备. 周锋,马强,唐亚平,张世曦,李辰沙,梁彤祥.《材料工程》,第2004卷第10期. 2004

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