具有亮红色发光的Tm3+/Ho3+掺杂NaErF4@NaYF4核壳纳米晶的可控制备及其上转换发光性能

尹玉; 陈杰; 刘蓉; 赵伟

具有亮红色发光的Tm³⁺/Ho³⁺掺杂NaErF₄@NaYF₄核壳纳米晶的可控制备及其上转换发光性能

尹玉¹,
陈杰^{1, 2, ,},
刘蓉¹,
赵伟¹

1.
吉林化工学院　化学与制药工程学院, 吉林 132022
2.
吉林化工学院　分析测试中心, 吉林 132022

基金项目: 国家自然科学基金 (51902125)；吉林省科技发展计划资助项目(YDZJ202101ZYTS029)；吉林市科技发展计划资助项目(20210103092)；第七批吉林省青年科技人才托举工程(QT202316)

详细信息

通讯作者:
陈杰，博士，副教授，硕士生导师，研究方向为稀土光功能材料的开发与应用　E-mail: jiechendr@163.com

中图分类号: O734;TB332
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出版历程
- 收稿日期: 2023-09-12
- 修回日期: 2023-10-25
- 录用日期: 2023-10-26
- 网络出版日期: 2023-11-16
- 刊出日期: 2024-07-15

Controllable preparation and upconversion luminescence properties of Tm³⁺/Ho³⁺ doped NaErF₄@NaYF₄ core-shell nanocrystals with bright red emission

YIN Yu¹,
CHEN Jie^{1, 2
, ,},
LIU Rong¹,
ZHAO Wei¹

1.
School of Chemistry and Pharmaceutical Engineering, Jilin Institute of Chemical Technology, Jilin 132022, China
2.
Center of Characterization and Analysis, Jilin Institute of Chemical Technology, Jilin 132022, China

Funds: National Natural Science Foundation of China (No. 51902125); Science and Technology Development Plan of Jilin Province (No. YDZJ202101ZYTS029); Science and Technology Development Plan of Jilin City (No. 20210103092); The seventh batch of Jilin Province young science and technology talents promotion Project (No. QT202316)

摘要

摘要: 为了获得具有红光发射的上转换纳米材料，以实现深层生物成像的应用，采用热分解法制备了一系列Tm³⁺/Ho³⁺掺杂NaErF₄ @ NaYF₄核壳上转换纳米晶，并对其形貌、结构和发光性能进行了表征。结果表明，所制备NaErF₄，NaErF₄:Tm³⁺和NaErF₄:Ho³⁺裸核均为六方相结构，呈现良好的球形形貌，平均粒径分别为23.19 nm，28.01 nm，27.89 nm。包覆NaYF₄惰性壳层后，样品晶型没有改变，形貌变为短棒状，平均长度增大至38.51 nm，37.82 nm，42.65 nm。在980 nm近红外光激发下，由于Er³⁺的⁴F_9/2→⁴I_15/2跃迁，所制备NaErF₄，NaErF₄:Tm³⁺和NaErF₄:Ho³⁺裸核均呈现明显的红光发射，且包覆NaYF₄惰性壳层后，发光强度和荧光寿命都明显增加，特别是NaErF₄@NaYF₄核壳样品的发光强度约是NaErF₄裸核的1787倍，荧光寿命达到2.04 ms。此外，与NaErF₄@NaYF₄纳米棒相比，NaErF₄:Tm³⁺/Ho³⁺@NaYF₄体系中的Tm³⁺、Ho³⁺充当了能量捕获中心且与Er³⁺之间发生能量传递，使其具有更大的红绿发射峰比值(R/G)，发光颜色更趋近于红色，与CIE色坐标颜色区域相一致。最后，根据发光强度与激发功率的关系，详细分析了上转换纳米晶的发光增强机制以及可能存在的能量传递过程。
- 上转换发光 /
- NaErF₄纳米晶 /
- 红光发射 /
- 核壳 /
- 掺杂
Abstract: In order to obtain upconversion nanomaterials with bright red emission for deep bioimaging applications, a series of Tm³⁺/Ho³⁺ doped NaErF₄@NaYF₄ core-shell upconversion nanocrystals were prepared by thermal decomposition method, and their morphology, structure and luminescence properties were characterized. The results show that NaErF₄, NaErF₄:Tm³⁺ and NaErF₄:Ho³⁺ bare core all exhibit hexagonal phase structure and good spherical morphology, with average sizes of 23.19 nm, 28.01 nm and 27.89 nm, respectively. After coating NaYF₄ inert shell, the crystal phase remains unchanged, but the morphology became short rod-like, and the average length increases to 38.51 nm, 37.82 nm, 42.65 nm. Under the excitation of 980 nm near-infrared light, NaErF₄, NaErF₄:Tm³⁺ and NaErF₄:Ho³⁺ show obvious red emission due to the ⁴F_9/2→⁴I_15/2 transition of Er³⁺, and the luminescence intensity and lifetime increase significantly after coating NaYF₄ inert shell. In particular, the luminescence intensity of NaErF₄@NaYF₄ core-shell sample is about 1787 times that of NaErF₄ bare core, and the lifetime is 2.04 ms. In addition, compared with NaErF₄@NaYF₄, the Tm³⁺/Ho³⁺ ions in the NaErF₄:Tm³⁺/Ho³⁺@NaYF₄ system act as energy trapping centers and generate energy transfer with Er³⁺, resulting in a larger red-green emission peak ratio (R/G), and the luminescence color is closer to red, which is consistent with the CIE color coordinate color region. Finally, according to the relationship between luminescence intensity and excitation power, the upconversion luminescence enhanced mechanism and the possible energy transfer process are analyzed in detail.
- upconversion luminescence /
- NaErF₄ nanocrystal /
- red emission /
- core-shell /
- doping

HTML全文

图 1 (a, g) NaErF₄, (b, h) NaErF₄:Tm³⁺, (c, i) NaErF₄:Ho³⁺, (d, j) NaErF₄@NaYF₄ , (e,k) NaErF₄:Tm³⁺@NaYF₄, (f, l)NaErF₄:Ho³⁺@NaYF₄纳米粒子的HRTEM图片和尺寸分布图

Figure 1. HRTEM images and size distributions of (a, g) NaErF₄, (b, h) NaErF₄:Tm³⁺, (c, i) NaErF₄:Ho³⁺, (d, j) NaErF₄@NaYF₄, (e, k) NaErF₄:Tm³⁺@NaYF₄, (f, l) NaErF₄:Ho³⁺@NaYF₄ nanoparticles

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图 2 (a) NaErF₄, (b) NaErF₄:Tm³⁺, (c) NaErF₄:Ho³⁺, (d) NaErF₄@NaYF₄, (e) NaErF₄:Tm³⁺@NaYF₄, (f) NaErF₄:Ho³⁺@NaYF₄纳米粒子的EDS谱图

Figure 2. EDS images of (a) NaErF₄, (b) NaErF₄:Tm³⁺, (c) NaErF₄:Ho³⁺, (d) NaErF₄@NaYF₄, (e) NaErF₄:Tm³⁺@NaYF₄, (f) NaErF₄:Ho³⁺@NaYF₄ nanoparticles

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图 3 NaErF₄, NaErF₄:Tm³⁺, NaErF₄:Ho³⁺裸核(a)以及NaErF₄@NaYF₄, NaErF₄:Tm³⁺@NaYF₄, NaErF₄:Ho³⁺@NaYF₄核壳纳米粒子(b)的XRD图

Figure 3. XRD patterns of NaErF₄, NaErF₄:Tm³⁺, NaErF₄:Ho³⁺ core (a) and NaErF₄@NaYF₄, NaErF₄:Tm³⁺@NaYF₄, NaErF₄:Ho³⁺@NaYF₄ core-shell nanoparticles (b)

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图 4 在980 nm激发下不同裸核纳米粒子的上转换发射光谱(a)和红绿发射峰比值(R/G)变化曲线(b)

Figure 4. (a) Upconversion emission spectra of different bare core nanoparticles under 980 nm excitation, (b) the ratio of red to green emission peaks (R/G)

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图 5 980 nm激发下(a) NaErF₄@NaYF₄, (b) NaErF₄:Tm³⁺@NaYF₄, (c) NaErF₄:Ho³⁺@NaYF₄核壳样品与对应裸核的上转换发射光谱对比图，不同核壳样品的(d)上转换发射光谱，(e)红绿发射峰强度比值(R/G)图

Figure 5. Comparison of emission spectra between bare core and core-shell samples under 980 nm excitation: (a) NaErF₄@NaYF₄, (b) NaErF₄:Tm³⁺@NaYF₄, (c) NaErF₄:Ho³⁺@NaYF₄, (d) the emission spectra and (e) the ratio of red to green emission intensity (R/G) of different core-shell samples

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图 6 不同裸核(a)和核壳(b)纳米粒子653 nm (Er³⁺, ⁴F_9/2→⁴I_15/2 )处发射峰强度与泵浦功率的对数图

Figure 6. Log-log plots of upconversion emission intensity at 653 nm (Er³⁺, ⁴F_9/2→⁴I_15/2 ) versus pumping power of bare core (a) and core-shell (b) nanoparticles

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图 7 NaErF₄@NaYF₄ (a), NaErF₄:Tm³⁺@NaYF₄ (b), NaErF₄:Ho³⁺@NaYF₄ (c)核壳纳米粒子的上转换发光机制图

Figure 7. Upconversion luminescence mechanism diagram of NaErF₄@NaYF₄ (a), NaErF₄:Tm³⁺@NaYF₄ (b), NaErF₄:Ho³⁺@NaYF₄ (c) core-shell nanoparticles

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图 8 980 nm激发下NaErF₄, NaErF₄:Tm³⁺, NaErF₄:Ho³⁺裸核(a)和NaErF₄@NaYF₄, NaErF₄:Tm³⁺@NaYF₄, NaErF₄:Ho³⁺@NaYF₄核壳纳米粒子中653 nm发射(b)的荧光衰减曲线

Figure 8. Decay curves of 653 nm emission in NaErF₄, NaErF₄:Tm³⁺, NaErF₄:Ho³⁺ core (a), NaErF₄@NaYF₄, NaErF₄:Tm³⁺@NaYF₄, NaErF₄:Ho³⁺@NaYF₄ core-shell nanoparticles under 980 nm excitation (b)

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图 9 980 nm激发下NaErF₄, NaErF₄:Tm³⁺, NaErF₄:Ho³⁺裸核(a)以及NaErF₄@NaYF₄, NaErF₄:Tm³⁺@NaYF₄, NaErF₄:Ho³⁺@NaYF₄核壳(b)纳米粒子的色坐标图

Figure 9. CIE diagram of NaErF₄, NaErF₄:Tm³⁺, NaErF₄:Ho³⁺ bare core (a) and NaErF₄@NaYF₄, NaErF₄:Tm³⁺@NaYF₄, NaErF₄:Ho³⁺@NaYF₄ core-shell (b) nanoparticles under 980 nm excitation

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表 1 NaErF₄, NaErF₄:Tm³⁺, NaErF₄:Ho³⁺以及NaErF₄@NaYF₄, NaErF₄:Tm³⁺@NaYF₄, NaErF₄:Ho³⁺@NaYF₄样品的色坐标参数

Table 1. CIE parameters of NaErF₄, NaErF₄:Tm³⁺, NaErF₄:Ho³⁺, NaErF₄@NaYF₄, NaErF₄:Tm³⁺@NaYF₄ and NaErF₄:Ho³⁺@NaYF₄ samples

No.	Samples	CIE(x,y)	CCT/K	Color
1	NaErF₄	(0.4608, 0.4652)	5067	Yellow
2	NaErF₄:0.5%Tm³⁺	(0.6649, 0.3123)	2962	Red
3	NaErF₄:0.5%Ho³⁺	(0.4638, 0.4969)	5103	Green-Yellow
4	NaErF₄@NaYF₄	(0.4711, 0.4984)	5083	Green-Yellow
5	NaErF₄:0.5%Tm³⁺@NaYF₄	(0.6138, 0.3764)	4080	Orange-Red
6	NaErF₄:0.5%Ho³⁺@NaYF₄	(0.5109, 0.4719)	4908	Orange
Notes: CIE—Chromaticity coordinate; CCT—Color Correlated Temperature.

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