CN111825064B - 一种水溶性ZnCuInX量子点的一步水相合成方法 - Google Patents
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- 238000001308 synthesis method Methods 0.000 title claims abstract description 10
- 239000008346 aqueous phase Substances 0.000 title claims abstract description 6
- 239000002243 precursor Substances 0.000 claims abstract description 22
- 239000011669 selenium Substances 0.000 claims abstract description 20
- 239000011259 mixed solution Substances 0.000 claims abstract description 18
- 229910052711 selenium Inorganic materials 0.000 claims abstract description 16
- 229910052717 sulfur Inorganic materials 0.000 claims abstract description 16
- CWERGRDVMFNCDR-UHFFFAOYSA-N thioglycolic acid Chemical compound OC(=O)CS CWERGRDVMFNCDR-UHFFFAOYSA-N 0.000 claims abstract description 15
- 150000001879 copper Chemical class 0.000 claims abstract description 14
- 150000002471 indium Chemical class 0.000 claims abstract description 14
- 150000003751 zinc Chemical class 0.000 claims abstract description 14
- 238000000034 method Methods 0.000 claims abstract description 12
- BUGBHKTXTAQXES-UHFFFAOYSA-N Selenium Chemical compound [Se] BUGBHKTXTAQXES-UHFFFAOYSA-N 0.000 claims abstract description 10
- 238000010992 reflux Methods 0.000 claims abstract description 10
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 claims abstract description 8
- 238000010438 heat treatment Methods 0.000 claims abstract description 8
- 239000011593 sulfur Substances 0.000 claims abstract description 8
- JPJALAQPGMAKDF-UHFFFAOYSA-N selenium dioxide Chemical compound O=[Se]=O JPJALAQPGMAKDF-UHFFFAOYSA-N 0.000 claims description 14
- 238000002156 mixing Methods 0.000 claims description 9
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 8
- 229940091258 selenium supplement Drugs 0.000 claims description 7
- ZOIORXHNWRGPMV-UHFFFAOYSA-N acetic acid;zinc Chemical compound [Zn].CC(O)=O.CC(O)=O ZOIORXHNWRGPMV-UHFFFAOYSA-N 0.000 claims description 6
- 229910000365 copper sulfate Inorganic materials 0.000 claims description 6
- ARUVKPQLZAKDPS-UHFFFAOYSA-L copper(II) sulfate Chemical group [Cu+2].[O-][S+2]([O-])([O-])[O-] ARUVKPQLZAKDPS-UHFFFAOYSA-L 0.000 claims description 6
- PSCMQHVBLHHWTO-UHFFFAOYSA-K indium(iii) chloride Chemical group Cl[In](Cl)Cl PSCMQHVBLHHWTO-UHFFFAOYSA-K 0.000 claims description 6
- 229910000033 sodium borohydride Inorganic materials 0.000 claims description 6
- 239000012279 sodium borohydride Substances 0.000 claims description 6
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 6
- 239000004246 zinc acetate Substances 0.000 claims description 6
- 239000012153 distilled water Substances 0.000 claims description 5
- 229910052979 sodium sulfide Inorganic materials 0.000 claims description 4
- GRVFOGOEDUUMBP-UHFFFAOYSA-N sodium sulfide (anhydrous) Chemical group [Na+].[Na+].[S-2] GRVFOGOEDUUMBP-UHFFFAOYSA-N 0.000 claims description 4
- JIAARYAFYJHUJI-UHFFFAOYSA-L zinc dichloride Chemical compound [Cl-].[Cl-].[Zn+2] JIAARYAFYJHUJI-UHFFFAOYSA-L 0.000 claims description 4
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- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 claims description 2
- ORTQZVOHEJQUHG-UHFFFAOYSA-L copper(II) chloride Chemical compound Cl[Cu]Cl ORTQZVOHEJQUHG-UHFFFAOYSA-L 0.000 claims description 2
- BVTBRVFYZUCAKH-UHFFFAOYSA-L disodium selenite Chemical compound [Na+].[Na+].[O-][Se]([O-])=O BVTBRVFYZUCAKH-UHFFFAOYSA-L 0.000 claims description 2
- 229910052700 potassium Inorganic materials 0.000 claims description 2
- 239000011591 potassium Substances 0.000 claims description 2
- 239000002244 precipitate Substances 0.000 claims description 2
- 229960001471 sodium selenite Drugs 0.000 claims description 2
- 239000011781 sodium selenite Substances 0.000 claims description 2
- 235000015921 sodium selenite Nutrition 0.000 claims description 2
- 239000006228 supernatant Substances 0.000 claims description 2
- 239000011592 zinc chloride Substances 0.000 claims description 2
- 235000005074 zinc chloride Nutrition 0.000 claims description 2
- NWONKYPBYAMBJT-UHFFFAOYSA-L zinc sulfate Chemical compound [Zn+2].[O-]S([O-])(=O)=O NWONKYPBYAMBJT-UHFFFAOYSA-L 0.000 claims description 2
- 229910000368 zinc sulfate Inorganic materials 0.000 claims description 2
- 229960001763 zinc sulfate Drugs 0.000 claims description 2
- 239000002245 particle Substances 0.000 abstract description 6
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- 230000007613 environmental effect Effects 0.000 abstract description 4
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- 230000007547 defect Effects 0.000 abstract description 2
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- 239000010949 copper Substances 0.000 description 13
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- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 12
- 229910021645 metal ion Inorganic materials 0.000 description 8
- 238000002189 fluorescence spectrum Methods 0.000 description 7
- 239000003381 stabilizer Substances 0.000 description 5
- 238000003756 stirring Methods 0.000 description 5
- 150000001768 cations Chemical class 0.000 description 4
- 238000001816 cooling Methods 0.000 description 4
- 239000000463 material Substances 0.000 description 4
- 238000003760 magnetic stirring Methods 0.000 description 3
- 239000012071 phase Substances 0.000 description 3
- 238000002441 X-ray diffraction Methods 0.000 description 2
- 239000004054 semiconductor nanocrystal Substances 0.000 description 2
- 230000002194 synthesizing effect Effects 0.000 description 2
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- 239000000090 biomarker Substances 0.000 description 1
- 229910052793 cadmium Inorganic materials 0.000 description 1
- 238000012512 characterization method Methods 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 238000000695 excitation spectrum Methods 0.000 description 1
- 229910001385 heavy metal Inorganic materials 0.000 description 1
- 238000002173 high-resolution transmission electron microscopy Methods 0.000 description 1
- 230000002209 hydrophobic effect Effects 0.000 description 1
- 229910052738 indium Inorganic materials 0.000 description 1
- APFVFJFRJDLVQX-UHFFFAOYSA-N indium atom Chemical compound [In] APFVFJFRJDLVQX-UHFFFAOYSA-N 0.000 description 1
- 239000011261 inert gas Substances 0.000 description 1
- 229910052745 lead Inorganic materials 0.000 description 1
- 230000031700 light absorption Effects 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 230000000877 morphologic effect Effects 0.000 description 1
- 239000002105 nanoparticle Substances 0.000 description 1
- 230000003287 optical effect Effects 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 238000005070 sampling Methods 0.000 description 1
- 239000004065 semiconductor Substances 0.000 description 1
- 229910052950 sphalerite Inorganic materials 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- WGPCGCOKHWGKJJ-UHFFFAOYSA-N sulfanylidenezinc Chemical compound [Zn]=S WGPCGCOKHWGKJJ-UHFFFAOYSA-N 0.000 description 1
- 238000005303 weighing Methods 0.000 description 1
- 229910052725 zinc Inorganic materials 0.000 description 1
- 229910052984 zinc sulfide Inorganic materials 0.000 description 1
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Abstract
本发明公开了一种水溶性ZnCuInX量子点的一步水相合成方法,属于纳米材料制备技术领域。其包括步骤:在巯基乙酸中加入可溶性的锌盐、铜盐和铟盐,配制成前驱体混合溶液;将前驱体混合溶液的pH值调节至7.0‑11.0;然后加入硼氢化物、硒源或硫源;在80‑120℃下反应加热回流0.5‑9h得水溶性ZnCuInX量子点。本发明制备的ZnCuInX量子点克服了传统有机法制备量子点疏水性的缺陷,在应用前无需通过配体交换。本发明具有反应条件温和可控,操作步骤简单,安全环保等特点。ZnCuInX量子点的最大荧光发射峰在610nm左右,近似球型形貌,颗粒大小约为5nm。
Description
技术领域
本发明涉及纳米材料制备技术领域,具体涉及一种水溶性ZnCuInX量子点的一步水相合成方法。
背景技术
量子点(quantum dots,简称QDs)又可称为半导体纳米晶体(semiconductornanocrystal),是一种由II-VI族或III-V族元素组成二元或三元的无机纳米粒子。量子点作为一种新型的纳米材料,从20世纪70年代末起就引起了研究者们广泛的关注。相对于传统荧光材料,量子点具有激发光谱宽,从紫外到可见光都可激发;荧光发射光谱窄并且成对称分布;量子点的发光颜色可以通过改变粒子的颗粒大小来调节;并且光化学稳定性高等优点。量子点由于具有独特的发光性质,在发光二极管、太阳能电池、光学生物标记等领域具有广泛的应用前景。
ZnCuInX(X=Se,S)量子点是一种不含Pb、Cd重金属的半导体纳米材料,由于其禁带宽度非常接近于太阳能电池材料的最佳禁带宽度,是很好的太阳能电池光吸收材料;通过改变量子点的粒径大小实现荧光发射从可见光到近红外,在发光二极管中具有广泛的应用前景。目前合成ZnCuInX(X=Se,S)量子点的方法中需要用到昂贵或有害的有机试剂,并且大多数反应都要求惰性气体保护或高温等苛刻的实验条件。另外,通过这些方法合成的量子点都是疏水性,在应用前还需要通过配体交换转换成水溶性量子点,在相转移过程中不可避免的会导致合成量子点的发光强度和稳定性降低,从而限制了量子点的大规模生产及应用。因此,开发一种低成本、简单、环境友好的合成水溶性的ZnCuInX(X=Se,S)量子点材料方法尤为重要。
综合以上因素,通过简单的一步水相反应合成了水溶性ZnCuInX量子点,该方法具有反应条件温和可控,操作步骤简单,安全环保等特点。
发明内容
本发明针对上述现有技术存在的问题,本发明的目的是提供一种水溶性ZnCuInX量子点的一步水相合成方法。
为实现本发明的目的,通过以下技术方案予以实现:
一种水溶性ZnCuInX量子点的一步水相合成方法,其特征在于:所述ZnCuInX中的X为Se或S;
包括以下步骤:
(1)在巯基乙酸中加入可溶性的锌盐、铜盐和铟盐,配制成前驱体混合溶液;
(2)将前驱体混合溶液的pH值调节至7.0-11.0;然后加入硼氢化物、硒源或硫源;在80-120℃下反应加热回流0.5-9h得水溶性ZnCuInX量子点。
优选地,在步骤(1)中:
可溶性的锌盐、铜盐和铟盐的总和与巯基乙酸的摩尔比为1:1.4-4。
优选地,在步骤(1)中:
可溶性的锌盐、铜盐和铟盐的体积比为88-35:1-5:10-60。
优选地,在步骤(1)中,所述可溶性的锌盐为氯化锌、醋酸锌、硝酸锌或硫酸锌中的至少一种;所述可溶性的铜盐为硫酸铜和/或氯化铜;所述可溶性铟盐为氯化铟。
优选地,在步骤(2)中,所述的硼氢化物是硼氢化钠和/或硼氢化钾,硒源为二氧化硒、硒粉或亚硒酸钠中的至少一种;所述硫源为硫化钠。
优选地,在步骤(2)中:
可溶性的锌盐、铜盐和铟盐的总和与硒源的摩尔比为1:0.05-0.5。
优选地,在步骤(2)中:
可溶性的锌盐、铜盐和铟盐的总和与硫源的摩尔比为1:0.2-0.8。
优选地,在步骤(2)后,将水溶性ZnCuInX量子点用无水乙醇纯化。
进一步优选地,将水溶性ZnCuInX量子点与无水乙醇以1:2的体积比混合,离心去除上层清液后加入蒸馏水直至离心所得沉淀溶解;得到纯化后的水溶性ZnCuInX量子点。
本发明选用可溶性的锌盐、铜盐和铟盐作为锌源、铜源和铟源,二氧化硒为硒源(硫化钠为硫源),巯基乙酸作为稳定剂,油浴为加热方式,在水相体系中一步合成水溶性的ZnCuInX(X=Se,S)量子点。
本发明制备的ZnCuInX(X=Se,S)量子点克服了传统有机法制备量子点疏水性的缺陷,在应用前无需通过配体交换。本发明具有反应条件温和可控,操作步骤简单,安全环保等特点。ZnCuInX(X=Se,S)量子点的最大荧光发射峰在610nm左右,近似球型形貌,颗粒大小约为5nm。
附图说明
图1为实施例1在不同回流时间下制备ZnCuInSe量子点的荧光发射光谱图;
图2为实施例2在不同的(Zn+Cu+In):S的摩尔比制备ZnCuInS量子点的荧光发射光谱图;
图3为实施例3在不同(Zn+Cu+In):Se的摩尔比制备ZnCuInSe量子点的荧光发射光谱图;
图4为实施例4制备ZnCuInSe量子点的高分辨透射电镜照片;
图5为实施例4制备ZnCuInSe量子点的X-射线衍射图。
具体实施方式
下面将结合本发明实施例中的附图,对本发明实施例中的技术方案进行清楚、完整地描述。其中,附图仅用于示例性说明,表示的仅是示意图,而非实物图,不能理解为对本专利的限制。对于本发明所属技术领域的普通技术人员来说,在不脱离本发明构思的前提下,还可以做出若干简单推演或替换,都应当视为属于本发明的保护范围。
本发明中,TGA是指巯基乙酸。
实施例1
(1)分别量取0.02mol/L醋酸锌38mL,0.02mol/L硫酸铜溶液2mL,0.02mol/L氯化铟溶液60mL放入三口烧瓶中得到阳离子混合溶液,然后加入0.3mL稳定剂TGA,其中(Zn2++Cu2++In3+):TGA的摩尔比为1:1.4,混合均匀后得金属离子的前驱体溶液;
(2)在步骤⑴中所得金属离子前驱体溶液中逐滴加入1mol/L氢氧化钠溶液,调节前驱体溶液的pH为10.0,然后在搅拌条件下将0.0444g二氧化硒和0.0454g硼氢化钠加入上述前驱体溶液中,其中(Zn+Cu+In):(Se)的摩尔比为1:0.2,二氧化硒与硼氢化钠的摩尔比为1:3;
(3)将步骤⑵所得的混合液充分进行磁力搅拌5min,置于100℃油浴中加热回流,分别在回流时间为10min,30min,1h,3h,5h,7h,9h时对溶液进行取样分析,所得样品自然冷却至室温,得到ZnCuInSe水溶性量子点;
(4)将步骤(3)制备得到的一系列ZnCuInSe量子点溶液分别与无水乙醇按照1:2的体积比混合均匀,然后离心去除上层清液,再加入一定量的蒸馏水将沉淀溶解后加入2倍体积的无水乙醇、离心,重复以上操作3次;将纯化后的ZnCuInSe量子点溶于蒸馏水中,得到橙色透明溶液,即为水溶性的ZnCuInSe量子点样品,该量子点的最大荧光发射峰在610nm左右。具体不同回流时间下的荧光发射图谱如图1所示。
实施例2
(1)分别量取0.02mol/L醋酸锌47mL,0.02mol/L硫酸铜溶液3mL,0.02mol/L氯化铟溶液50mL放入三口烧瓶中得到阳离子混合溶液,然后加入0.3mL稳定剂TGA,其中(Zn2++Cu2++In3+):TGA的摩尔比为1:1.4,混合均匀后得金属离子的前驱体溶液;
(2)在步骤⑴中所得金属离子前驱体溶液中逐滴加入1mol/L氢氧化钠溶液,调节前驱体溶液的pH为10.0,然后在搅拌条件下将一定量的硫化钠加入上述前驱体溶液中,其中调节(Zn+Cu+In):S的摩尔比分别为1:0.4、1:0.5、1:0.6、1:0.7四个不同的比例。
(3)将步骤⑵所得的混合液充分进行磁力搅拌5min,置于100℃油浴中加热回流30min,所得样品自然冷却至室温,得到ZnCuInS水溶性量子点;
(4)将步骤(3)制备得到的ZnCuInS量子点溶液分别与无水乙醇按照1:2的体积比混合均匀,然后离心去除上层清液,再加入一定量的蒸馏水将沉淀溶解后加入2倍体积的无水乙醇、离心,重复以上操作3次;将纯化后的ZnCuInS量子点溶于蒸馏水中,得到水溶性的ZnCuInS量子点样品,该量子点的最大荧光发射峰在540nm左右。其不同(Zn+Cu+In):S的摩尔比的荧光发射光谱图如图2所示。
实施例3
(1)分别量取0.02mol/L醋酸锌35mL,0.02mol/L硫酸铜溶液5mL,0.02mol/L氯化铟溶液60mL放入三口烧瓶中得到阳离子混合溶液,然后加入0.3mL稳定剂巯基乙酸(TGA),其中(Zn2++Cu2++In3+):TGA的摩尔比为1:1.4,混合均匀后得金属离子的前驱体溶液;
(2)在步骤⑴中所得金属离子前驱体溶液中逐滴加入1mol/L氢氧化钠溶液,调节前驱体溶液的pH为10.0,然后在搅拌条件下将一定量的二氧化硒和硼氢化钠加入上述前驱体溶液中,其中调节(Zn+Cu+In):Se的摩尔比分别为1:0.05、1:0.1、1:0.2三个不同的比例,二氧化硒与硼氢化钠的摩尔比为1:3;
(3)将步骤⑵所得的混合液充分进行磁力搅拌5min,置于100℃油浴中加热回流10min,所得样品自然冷却至室温,得到ZnCuInSe水溶性量子点;
(4)将步骤(3)制备得到的一系列ZnCuInSe量子点溶液分别与无水乙醇按照1:2的体积比混合均匀,然后离心去除上层清液,再加入一定量的蒸馏水将沉淀溶解后加入2倍体积的无水乙醇、离心,重复以上操作3次;将纯化后的ZnCuInSe量子点溶于蒸馏水中,得到橙色透明溶液,即为水溶性的ZnCuInSe量子点样品。其不同(Zn+Cu+In):Se的摩尔比的荧光发射光谱图如图3所示。
实施例4
(1)分别量取0.02mol/L醋酸锌68ml,0.02mol/L硫酸铜溶液2mL,0.02mol/L氯化铟溶液30mL放入三口烧瓶中得到阳离子混合溶液,然后加入0.3mL稳定剂TGA,其中(Zn2++Cu2++In3+):TGA的摩尔比为1:1.4,混合均匀后得金属离子的前驱体溶液;
(2)在步骤⑴中所得金属离子前驱体溶液中逐滴加入1mol/L氢氧化钠溶液,调节前驱体溶液的pH为10.0,然后在搅拌条件下将0.0111g二氧化硒和0.0114g硼氢化钠加入上述前驱体溶液中,其中(Zn+Cu+In):Se的摩尔比为1:0.05,二氧化硒与硼氢化钠的摩尔比为1:3;
(3)将步骤⑵所得的混合液充分进行磁力搅拌5min,置于100℃油浴中加热回流2h,所得样品自然冷却至室温,得到ZnCuInSe水溶性量子点;
(4)将步骤(3)制备得到的一系列ZnCuInSe量子点溶液分别与无水乙醇按照1:2的体积比混合均匀,然后离心去除上层清液,再加入一定量的蒸馏水将沉淀溶解后加入2倍体积的无水乙醇、离心,重复以上操作3次;将所得样品自然干燥得到ZnCuInSe量子点粉末样品。通过对其进行结构和形貌表征,ZnCuInSe量子点为闪锌矿结构,近似球型形貌,颗粒大小约为5nm。ZnCuInSe水溶性量子点的高分辨透射电镜和X-射线衍射图分别如图4、图5所示。
Claims (4)
1.一种水溶性ZnCuInX量子点的一步水相合成方法,其特征在于:所述ZnCuInX中的X为Se或S;
包括以下步骤:
(1)在巯基乙酸中加入可溶性的锌盐、铜盐和铟盐,配制成前驱体混合溶液;所述可溶性的锌盐为氯化锌、醋酸锌、硝酸锌或硫酸锌中的至少一种;所述可溶性的铜盐为硫酸铜和/或氯化铜;所述可溶性铟盐为氯化铟;所述可溶性的锌盐、铜盐和铟盐的总和与巯基乙酸的摩尔比为1:1.4-4;
(2)将前驱体混合溶液的pH值调节至7.0-11.0;然后加入硼氢化物、硒源或硫源;在80-120℃下反应加热回流0.5h得水溶性ZnCuInX量子点;所述的硼氢化物是硼氢化钠和/或硼氢化钾,硒源为二氧化硒、硒粉或亚硒酸钠中的至少一种;所述硫源为硫化钠;所述可溶性的锌盐、铜盐和铟盐的总和与硫源的摩尔比为1:0.2-0.8;所述可溶性的锌盐、铜盐和铟盐的总和与硒源的摩尔比为1:0.05-0.5。
2.根据权利要求1所述的水溶性ZnCuInX量子点的一步水相合成方法,其特征在于:在步骤(1)中:
可溶性的锌盐、铜盐和铟盐的体积比为88-35:1-5:10-60。
3.根据权利要求1或2所述的水溶性ZnCuInX量子点的一步水相合成方法,其特征在于:在步骤(2)中,将水溶性ZnCuInX量子点用无水乙醇纯化。
4.根据权利要求3所述的水溶性ZnCuInX量子点的一步水相合成方法,其特征在于:
将水溶性ZnCuInX量子点与无水乙醇以1:2的体积比混合,离心去除上层清液后加入蒸馏水直至离心所得沉淀溶解;得到纯化后的水溶性ZnCuInX量子点。
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