摘要
荧光半导体纳米晶由于其良好的光电性质,在生物荧光标记、LEDs、太阳能电池等领域都有重要的应用,相对于传统的含有剧毒重金属二元荧光半导体纳米晶,四元CuZnInS_3纳米晶是一种“绿色”环保的半导体材料,因此更具实际应用价值。在本文中,我们发展了一种合成高质量的四元CuZnInS_3纳米晶的方法,这种方法简单,制备的纳米晶尺寸、组成可控,光学性能在可见和近红区可调。获得的纳米晶具有良好的化学和热稳定性,在LEDs等领域有着广泛的应用前景。
在不同实验条件下研究了Cu,Zn,In三种金属前体的成核温度,对三种前体的反应活性进行系统研究,为多元纳米晶合成提供了一种普适的方法。基于反应单体活性实验的结果,我们以四元CuZnInS_3纳米晶为模型体系,通过反应温度的调控和配体的复合作用,制备了尺寸可调、组成一致的四元CuZnInS_3纳米晶,它的荧光光谱发光范围可从620nm调节到780nm,发光效率可达65%左右。
通过调节Zn/Cu反应单体的比率,在相同的反应温度下合成了尺寸相同,带隙高度可调的四元纳米晶,粒子的发光范围可从可见区覆盖到近红外区(500nm到900nm),纳米晶的发光效率随着组分的改变最高可达70%。瞬态荧光光谱表征证明四元纳米晶分别来自本征态激子发光和缺陷发光,晶体中锌的含量增加可有效的减少多元纳米晶中的缺陷,提高了纳米晶的发光效率。
CuZnInS_3纳米晶的化学稳定性、光化学稳定性和热稳定性的研究结果表明:粒子的稳定性随着样品中各元素组分的变化而改变,当锌含量较多时,粒子具有良好的稳定性,而当粒子中铜的含量较多时,粒子的稳定性则较差。采用热循环表面离子层吸附反应法,在铜含量较多的样品外面包覆了宽带隙的ZnS壳层,进一步改善了其稳定性和荧光效率。在应用方面,将所得的黄光CuZnInS_3纳米晶制备成膜,铺展到蓝光LEDs上,得到了发暖白光的LEDs发射器,显示了该材料在照明领域应用的可行性。
Luminescent Colloidal semiconductor nanocrystals are of significant technology interest as they impact many applications including light emitting diodes (LEDs), biomedical labeling,lighting, etc. While existing examples of light emitting semiconductor nanocrysal s such as II-VI, II-V, III-V, IV-IV are numerous, most suffer from a number of disadvantages such as containing highly toxic elements, using extremely expensive and hazard raw materials, needing to surface modification to improve their properties. At an extend work, I-III-VI semiconductor nanocrysal s such as CuInS_2 have been successfully prepared recently due to their avoiding some of disadvantages as described above. The progress on the synthesis of such nanocrysal emitters brought the quality of I-III-VI nanocrysal s, especially the optical properties (quantum yield of about 5%) could not up to a level comparable to that of CdSe NCs,Therefore, it is a big challenge for scientists to develop greener, stable, high emissive semiconductor nanocrystals now.
CuInS_2 is a direct band gap semiconductor material with a band gap of 1.45 eV, which means that it would be possible to develop color-tunable CuInS_2 nanocrystal emitters from the visible to near-infrared(NIR) regions ,the near-infrared fluorescence materials are a better biological fluorescent labeling materials due to its near-infrared fluorescence is suitble for in vivo deep tissue imaging. More importantly, the nanoctrystals do not contain the toxic elements. At present, the ternary quantum dots have poor fluorescence quantum yield (<5%) and size distribution, poor chemical stability. Although our previous work have synthesized nearly monodisperse CuInS_2 (from 2 to 20nm) using greener approach. Nevertherless the resulted nanocrystals had poor quntum yield and stability. Forther studies indicxates that the emissive efficiency of nanocrystals can reach up to 30% and the stability of nanocrysals is also greatly improved after the growth of ZnS shell on the surface of nanocrysals. Therefore, it is still chanlenge on synthesis of CuInS_2 quantum dots with high quanum yield. ,It is found that the introduction of zinc can increase the fluorescence efficiency and stability of CuInS_2 Nanocrystals. In this article we systematically studied the reaction activity of three metal precursors under different experimental conditions, synthesized nearly monodisperse quaternary CuZnInS_3 nanocrystals with adjustable sizes and compositions. To improve the stability and quantum yield, we prepared CuZnInS_3 /ZnS core/shell nanocrystals. Preliminary application on preparation of QDs-LEDs white light emitter by using CuZnInS_3 nanoctysals. The main content of the thesis as following:
1. To avoid phase separation on synthesis of multinary nanocrystals, we systematically studied the reaction activity of three metal precursors (Cu, Zn, In) under different experimental conditions. Experimental results showed that the formation temperature of CuxS, ZnS, In2S3 respectively are 80℃, 120℃, 160℃in the absence of dodecanethiol. It is noted that the reaction temperature is adopted to quatitaify the reactivity of three metal precursors. Thus, the reactivity of three metal precursors is Cu > In> Zn. When dodecanethiol is used as ligand, the formation temperature of Cu2S, ZnS, In2S3 respectively are 60℃, 100℃, 140℃(Cu> In> Zn), indicating that dodecanethiol further balanced the reactivity of three metals. Therefore, the formation temperature of quaternary nanocrystals is above 140℃. This conclusion is necessary for choosing sutable reaction temperatures to prepare quaternary CuZnInS_3 nanocrystlas.
2. We study the effects of ligand, reaction additives, reaction temperature on the size control of quaternary CuZnInS_3 nanocrystals. The experimental results showed that the size of particles is independent of the variety of ligand concentrations and reaction additives. Based on the understanding the growth mechanism of quaternary nanocrystals, we finally synthesized nearly monodisperse CuZnInS_3 nanocrystals (2 nm - 7.5 nm) by aid of reaction temperature. The resulted nanocrystals have identical element composition (Cu:Zn:In =1:1:1 in particle), the fluorescence spectra can range from 620 nm to 780 nm, and the emissive efficiency can reach up to 65%. The experimental results reveal that the growth mechanism of quatunary nanoctysals is simiar to that reported on preparation of InAs nanocrystals where reaction temperature is dominatant the size of nanocrystals.
3. In order to prepared quaternary nanocrystals with wide emission range, we preared the quaternary nanocrystals with different compositions by simple changing the ratio of precursors and particle sizes. As as result the as prepared nanocrysgtals exhigled a wide the emission range which cover the whole visible region to NIR (500 nm to 900 nm). Importantly, the photoluminescence quantum yield of nanocrystals can reach up to 70% without any surface modification such as wide band gap ZnS shell used. It is noted that quntum yield of nanocrystals varied with different elemental composition where the almost constant quantum yields of 70% was observed with increase of the ratio of Zn vs Cu from1:1 to 20:1, and subsequently decreased significantly below the ratio of 1:1. It should be noted that these particles had similar sizes as determined by TEM, and were under the radius of their Bohr exciton, which excluded the sizes contributed the variety of quantym yields of nanocrystals. This fact indicates that the notable characterization of multinary NCs differencing binary NCs is that quantum yields of particles fluctuated depending on their composition defects and surface defects, and improve the emission efficiency of nanocrystals. PL decay of the sample with Zn:Cu ratio of 1:2 and 3:1 were characterized, indicating that the extensive elimination of the internal defects and thus suppressed non-radiative recombination process for high Zn vs Cu ratuio. As a result the plain NCs presented emission efficiency as high as 70%
4. Stabilites experimental showed that the CuZnInS_3 nanocrystals possese well chemical photochemical and thermal stabilities. However, the nanocrysals with high ratio Cu vs Zn showed poor stabilities. To resolve this problem, a wide band gap semiconductor was used to passivate the surface of nanoctrysals for improvment the stabilities and quantum yields of nanocrystals. For example, CuZnInS_3/ZnS core/shell nanocrystals was prepared by using thermal- cycling and successive ionic layer adsorption and reaction (TC-SILAR). As a result, the stability of paticle was successfully improved. Meanwhile, the photoluminescence quantum yield of CuZnInS_3/ZnS core/shell nanocrystals can reach up to 60%. Finally, a simple QDs-LED lighting device was fabricated by coating CuZnInS_3 nanocrystals on the surface of the blue LEDs to produce war white light, indicating the feasibilities in lighting field.
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