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

doi:10.6023/A23040128

Acta Chimica Sinica ›› 2023, Vol. 81 ›› Issue (7): 763-770.DOI: 10.6023/A23040128 Previous Articles Next Articles

Article

Ag₂Se@Ag₂S核壳量子点的室温合成及其近红外荧光性能优化

郑文山^a, 高冠斌^a^,^b^,^*(), 邓浩^a, 孙涛垒^b^,^*()

a 武汉理工大学材料复合新技术国家重点实验室武汉 430070
b 武汉理工大学化学化工与生命科学学院神经退行性疾病纳米医药湖北省重点实验室武汉 430070

投稿日期:2023-04-11 发布日期:2023-05-11
基金资助:
国家自然科学基金(52273110); 国家自然科学基金(21975191); 湖北省自然科学基金(2021CFB299)

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

Wenshan Zheng^a, Guanbin Gao^a^,^b(), Hao Deng^a, Taolei Sun^b()

a State Key Laboratory of Advanced Technology for Materials Synthesis and Processing, Wuhan University of Technology, Wuhan 430070
b Hubei Key Laboratory of Nano Medicine for Neurodegenerative Diseases, School of Chemistry, Chemical Engineering and Life Science, Wuhan University of Technology, Wuhan 430070

Received:2023-04-11 Published:2023-05-11
Contact: *E-mail: gbgao@whut.edu.cn; suntl@whut.edu.cn
Supported by:
National Natural Science Foundation of China(52273110); National Natural Science Foundation of China(21975191); Natural Science Foundation of Hubei Province(2021CFB299)

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Abstract

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

Cite this article

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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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)

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)

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

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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Ag2Se@Ag2S核壳量子点的室温合成及其近红外荧光性能优化