Ag2Se@Ag2S核壳量子点的室温合成及其近红外荧光性能优化

doi:10.6023/A23040128

摘要/Abstract

在Ag₂Se量子点表面生长宽禁带无机壳层以消除表面缺陷是提高其光致发光性能的有效方法. 与Ag₂Se相比, Ag₂S带隙更宽, 晶格常数相似, 是Ag₂Se量子点的理想壳层. 然而, 室温下精确制备Ag₂Se@Ag₂S核壳量子点仍然是一个挑战. 分别采用胶体原子层沉积(c-ALD)法和一锅水相法在室温下合成了油溶性和水溶性的Ag₂Se@Ag₂S核壳量子点, 并通过调控配体链长优化了水溶性Ag₂Se@Ag₂S核壳量子点近红外荧光性能. 在c-ALD法中, 以1-十二硫醇(DDT)包裹的Ag₂Se量子点作为种子, 以油胺(OAM)配位的Ag(OAM-Ag)和Na₂S作为壳层前驱体, 制备的油溶性Ag₂Se@Ag₂S核壳结构量子点暂无荧光发射, 随后尝试通过高温退火但仍无法恢复其荧光发射能力. 接着, 在一锅水相法中, 以巯基羧酸(HS-(CH₂)_x-COOH)配位的水溶性Ag₂Se量子点为种子, 巯基羧酸配位的Ag⁺和Na₂S作为壳层前驱体, 成功制备出在1270 nm处具有近红外荧光增强的水溶性Ag₂Se@Ag₂S核壳量子点. 通过改变直链配体巯基羧酸的链长度(x=2, 5, 10, 13), 发现以中等链长(x=10)的11-巯基十一酸(MUA)为配体的水溶性Ag₂Se@Ag₂S核壳量子点具有最强的荧光发射. 本文为Ag₂Se@Ag₂S核壳量子点制备提供了参考.

关键词: Ag₂Se@Ag₂S, 核壳量子点, 室温合成, 近红外荧光, 配体优化

Ag₂Se quantum dots (QDs) is a narrow band-gap (ca. 0.15 eV) nanomaterial, which exhibits great potential in near-infrared (NIR) fluorescence emission. However, the bad photoluminescence (PL) performance caused by defects in QDs has limited its application greatly. It is an effective way to improve the photoluminescence performance of Ag₂Se QDs by growing a wide band gap inorganic shell to eliminate surface defects. For Ag₂Se QDs, Ag₂S is an ideal shell due to its wider bandgap (ca. 1 eV) and similar lattice constants (0.488 nm for cubic Ag₂S and 0.499 nm for cubic Ag₂Se). However, the precise preparation of Ag₂Se@Ag₂S core-shell QDs at room temperature remains a challenge. In this study, oil-soluble and water-soluble Ag₂Se@Ag₂S core-shell QDs were synthesized by colloidal atomic layer deposition (c-ALD) and one-pot aqueous phase synthesis at room temperature, respectively. The NIR fluorescence properties of water-soluble Ag₂Se@Ag₂S core-shell QDs were optimized by regulating ligand chain length. In c-ALD, the oil-soluble Ag₂Se@Ag₂S core-shell QDs were prepared with 1-dodecanethiol (DDT) coated Ag₂Se QDs as seeds, oleamine (OAM) coordinated Ag (OAM-Ag) and Na₂S as shell precursors, the resultant product showed no fluorescence emission. After high temperature annealing, the fluorescence emission of this oil-soluble Ag₂Se@Ag₂S core-shell QDs could not be recovered. Subsequently, water-soluble Ag₂Se@Ag₂S core-shell QDs with enhanced NIR fluorescence emission at 1270 nm were prepared by using mercaptocarboxylic (HS-(CH₂)_x-COOH) coordinated Ag₂Se QDs as seeds, (HS-(CH₂)_x-COOH) coordinated Ag^＋ and Na₂S as shell precursors in one-pot water phase synthesis. By changing the chain length (x=2, 5, 10, 13) of HS-(CH₂)_x-COOH ligand, it is found that the water-soluble Ag₂Se@Ag₂S core-shell QDs which took medium chain length (x=10) 11-mercaptoundecanoic acid (MUA) as the ligand exhibited the strongest fluorescence emission. This work provides a reference for the preparation of Ag₂Se@Ag₂S core-shell QDs at room temperature.

Key words: Ag₂Se@Ag₂S, core-shell QDs, room temperature synthesis, near-infrared fluorescence, ligand optimization

引用此文

郑文山, 高冠斌, 邓浩, 孙涛垒. Ag₂Se@Ag₂S核壳量子点的室温合成及其近红外荧光性能优化[J]. 化学学报, 2023, 81(7): 763-770.

Wenshan Zheng, Guanbin Gao, Hao Deng, Taolei Sun. Room Temperature Synthesis and Near-infrared Fluorescence Performance Optimization of Ag₂Se@Ag₂S Core-shell Quantum Dots[J]. Acta Chimica Sinica, 2023, 81(7): 763-770.

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图/表 4

图1. (a) c-ALD法制备油溶性Ag2Se@Ag2S核壳量子点的反应流程示意图, (b) Ag2Se@DDT种子的TEM图(插图左为粒径统计直方图, 右为高分辨细节图), (c~i) c-ALD法制备的油溶性Ag2Se@Ag2S核壳量子点的TEM图(c) (插图为粒径统计直方图)、高角环形暗场像(d)、电子能谱扫描Ag (e)、Se (f)、S (g)原子分布图, 以及Se与S叠加图(h)、Ag与Se与S叠加图(i), (j~k) Ag2Se@DDT种子(下)和c-ALD制备的油溶性Ag2Se@Ag2S核壳量子点(上)的Ag 3d轨道的高解析电子能谱仪(HR-XPS)(j)和S 2p轨道的XPS精细谱(k)

Figure 1. (a) Schematic diagram of the preparation process of oil-soluble Ag2Se@Ag2S core-shell QDs obtained by c-ALD, (b) TEM image (insert: size distribution rectangular diagram and high-resolution TEM image) of Ag2Se@DDT seeds, (c~i) TEM image (insert: size distribution rectangular diagram) (c), HAADF image (d), single element of Ag (e), Se (f), S (g) distribution and the overlap of Se, S (h) and Ag, Se, S (i) by EDS mapping of oil-soluble Ag2Se@Ag2S core-shell QDs, (j~k) high resolution X-ray photoelectron spectrometer (HR-XPS) spectra of Ag 3d region (j) and S 2p region (k) of Ag2Se@DDT seeds (bottom line) and oil-soluble Ag2Se@Ag2S core-shell QDs (top line)

图2. (a)一锅水相法制备水溶性Ag2Se@Ag2S核壳量子点的反应流程示意图, (b) Ag2Se@MUA种子的TEM图(插图左为粒径统计直方图, 右为高分辨细节图), (c~i)一锅水相法制得的水溶性Ag2Se@Ag2S核壳量子点的TEM图(c)(插图为粒径统计直方图)、高角环形暗场像(d)、电子能谱扫描Ag (e)、Se (f)、S (g)原子分布图以及Se与S叠加图(h)、Ag与Se与S叠加图(i), (j~k) Ag2Se@MUA种子(下)和一锅水相法制备的水溶性Ag2Se@Ag2S核壳量子点(上)的Ag 3d轨道的XPS精细谱(j)和S 2p轨道的XPS精细谱(k)

Figure 2. (a) Schematic diagram of the preparation process of water-soluble Ag2Se@Ag2S core-shell QDs obtained by one-pot aqueous synthesis, (b) TEM image (insert: size distribution rectangular diagram and high-resolution TEM image) of Ag2Se@MUA seeds, (c~i) TEM image (insert: size distribution rectangular diagram) (c), HAADF image (d), single element of Ag (e), Se (f), S (g) distribution and the overlap of Se, S (h) or Ag, Se, S (i) by EDS mapping of water-soluble Ag2Se@Ag2S core-shell QDs, (j~k) HR-XPS spectra of Ag 3d region (j) and S 2p region (k) of Ag2Se@MUA seeds (bottom line) and water-soluble Ag2Se@Ag2S core-shell QDs (top line)

图3. (a)油溶性Ag2Se@DDT种子(黑色)和c-ALD法制备的油溶性Ag2Se@Ag2S核壳量子点(红色)的近红外荧光发射光谱(激发波长为808 nm), (b)水溶性Ag2Se@MUA种子(黑色)和一锅水相法制备的水溶性Ag2Se@Ag2S核壳量子点(红色)的近红外荧光发射光谱(激发波长为808 nm), (c)油溶性Ag2Se@DDT种子(黑色)和c-ALD法制备的油溶性Ag2Se@Ag2S核壳量子点(红色)粉末XRD衍射图, (d)水溶性Ag2Se@MUA种子(黑色)和一锅水相法制备的水溶性Ag2Se@Ag2S核壳量子点(红色)的粉末XRD衍射图.

Figure 3. (a) PL emission spectra of Ag2Se@DDT seeds (black) and oil-soluble Ag2Se@Ag2S core-shell QDs (red) obtained by c-ALD with an excitation wavelength of 808 nm, (b) PL emission spectra of Ag2Se@MUA seeds (black) and water-soluble Ag2Se@Ag2S core-shell QDs (red) obtained by one-pot aqueous synthesis with an excitation wavelength of 808 nm, (c) powder XRD patterns of Ag2Se@DDT seeds (black) and oil-soluble Ag2Se@Ag2S core-shell QDs (red) obtained by c-ALD, (d) powder XRD patterns of water-soluble Ag2Se@MUA seeds (black) and Ag2Se@Ag2S core-shell QDs (red) obtained by one-pot aqueous synthesis

图4. (a)不同链长巯基羧酸修饰的Ag2Se量子点的荧光发射光谱, (b~d)以Ag2Se@MHA (b), Ag2Se@MUA (c), Ag2Se@MTA (d)为种子, 以不同链长巯基羧酸为壳层配体制备的核壳量子点的荧光发射光谱, (e)不同Ag2Se量子点种子及核壳量子点的荧光强度对比, (f) Ag2Se@MUA量子点(绿色)及以其为种子以MUA为壳层配体制备的核壳量子点(红色)的荧光衰退曲线.(激发波长均为808 nm)

Figure 4. (a) PL emission spectra of Ag2Se seeds with different mercaptocarboxylic acids ligand. (b~d) PL emission spectra of Ag2Se@Ag2S core-shell QDs which took Ag2Se@MHA (b), Ag2Se@MUA (c), Ag2Se@MTA (d) as seeds and with different mercaptocarboxylic acids as shell ligand. (e) Comparison of PL intensity of different Ag2Se seeds and different Ag2Se@Ag2S core-shell QDs. (f) PL decay curves of Ag2Se@MUA seeds (green) and Ag2Se@Ag2S core-shell QDs with MUA as shell ligand (red). All PL emission spectra were obtained with an excitation wavelength of 808 nm

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Ag₂Se@Ag₂S核壳量子点的室温合成及其近红外荧光性能优化

Room Temperature Synthesis and Near-infrared Fluorescence Performance Optimization of Ag₂Se@Ag₂S Core-shell Quantum Dots

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