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

doi:10.13801/j.cnki.fhclxb.20231106.001

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

doi: 10.13801/j.cnki.fhclxb.20231106.001

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(YDZJ202101ZYTS029)；吉林市科技发展计划(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
计量
- 文章访问数: 251
- HTML全文浏览量: 233
- PDF下载量: 16
- 被引次数: 0
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: 2023-11-06
- 刊出日期: 2024-07-01

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 (51902125); Science and Technology Development Plan of Jilin Province (YDZJ202101ZYTS029); Science and Technology Development Plan of Jilin City (20210103092); The Seventh Batch of Jilin Province Young Science and Technology Talents Promotion Project (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28.01 nm、23.19 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37.82 nm、38.51 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，与色坐标(CIE)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 28.01 nm 23.19 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 37.82 nm, 38.51 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 chromaticity coordinate (CIE) 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 NaErF₄ ((a), (g))、NaErF₄∶Tm³⁺ ((b), (h))、NaErF₄∶Ho³⁺ ((c), (i))、NaErF₄@NaYF₄ ((d), (j))、NaErF₄∶Tm³⁺@NaYF₄ ((e), (k))、NaErF₄∶Ho³⁺@NaYF₄ ((f), (l))纳米粒子的HRTEM图像和尺寸分布图

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

d—Average diameter

下载: 全尺寸图片幻灯片

图 2 NaErF₄ (a)、NaErF₄∶Tm³⁺ (b)、NaErF₄∶Ho³⁺ (c)、NaErF₄@NaYF₄ (d)、NaErF₄∶Tm³⁺@NaYF₄ (e)、NaErF₄∶Ho³⁺@NaYF₄ (f)纳米粒子的EDS图谱

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

下载: 全尺寸图片幻灯片

图 3 NaErF₄、NaErF₄∶Tm³⁺、NaErF₄∶Ho³⁺裸核(a)及NaErF₄@NaYF₄、NaErF₄∶Tm³⁺@NaYF₄、NaErF₄∶Ho³⁺@NaYF₄核壳纳米粒子(b)的XRD图谱

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)

下载: 全尺寸图片幻灯片

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) (b)

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

下载: 全尺寸图片幻灯片

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

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; Emission spectra (d) and the ratio of red to green emission intensity (R/G) (e) of different core-shell samples

下载: 全尺寸图片幻灯片

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I_UC与泵浦功率P的对数图

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

下载: 全尺寸图片幻灯片

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

GSA—Ground state absorption; ESA—Excited state absorption

下载: 全尺寸图片幻灯片

图 8 980 nm激发(Ex)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(Em) (b)的荧光衰减曲线

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

τ—Lifetime

下载: 全尺寸图片幻灯片

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

Figure 9. Chromaticity coordinate (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

T_c—Color temperature

下载: 全尺寸图片幻灯片

表 1 NaErF₄、NaErF₄∶Tm³⁺、NaErF₄∶Ho³⁺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.	Sample	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
Note: CCT—Color correlated temperature.

下载: 导出CSV

参考文献(31)

[1]	WANG C C, ZHAO P R, YANG G L, et al. Reconstructing the intracellular pH microenvironment for enhancing photodynamic therapy[J]. Materials Horizons, 2020, 7(4): 1180-1185. doi: 10.1039/C9MH01824G
[2]	TAN L X, LI D N, ZHANG L J, et al. Preparation of multishell-structured NaYF₄:Yb, Tm, Nd@NaYF₄:Yb, Nd@SiO₂@ZnO nanospheres with effective NIR-induced photocatalytic activity[J]. The Journal of Physical Chemistry C, 2020, 124(33): 18081-18090. doi: 10.1021/acs.jpcc.0c04528
[3]	XU M M, GE W Y, ZHANG X M, et al. Bi-functional NaBiF₄: Er³⁺, Tm³⁺ nanoparticles for optical thermometry and anti-counterfeiting applications[J]. Optics & Laser Technology, 2022, 145: 107529.
[4]	YAO Y, XIE G M, ZHANG X, et al. Fast detection of E. coli with a novel fluorescent biosensor based on a FRET system between UCNPs and GO@Fe₃O₄ in urine specimens[J]. Analytical Methods: Advancing Methods and Applications, 2021, 13(19): 2209-2214.
[5]	ÖRÜCÜ H, TABANLI S, ERDEM M, et al. Bright white light up-conversion luminescence from Yb³⁺/Er³⁺/Tm³⁺ tridoped gadolinium gallium garnet nano-crystals for multicolor and white light-emitting diodes[J]. Optical Materials, 2022, 131: 112613.
[6]	WU Q X, XU Z, WAGEH S, et al. The dynamic variation of upconversion luminescence dependent on shell Yb³⁺ contents in NaYF₄:Yb³⁺, Tm³⁺@NaYF₄:Yb³⁺, Er³⁺ nanoparticles[J]. Journal of Alloys and Compounds, 2022, 891: 162067. doi: 10.1016/j.jallcom.2021.162067
[7]	XIE Y L, CHEN Q, WANG M, et al. Highly doped NaErF₄-based nanocrystals for multi-tasking application[J]. Journal of Rare Earths, 2021, 39(12): 1467-1476. doi: 10.1016/j.jre.2021.04.014
[8]	LI H, WANG X, LI X L, et al. Clearable shortwave-infrared-emitting NaErF₄ nanoparticles for noninvasive dynamic vascular imaging[J]. Chemistry of Materials, 2020, 32(8): 3365-3375. doi: 10.1021/acs.chemmater.9b04784
[9]	SHANG Y F, HAO S W, LYU W Q, et al. Confining excitation energy of Er³⁺-sensitized upconversion nanoparticles through introducing various energy trapping centers[J]. Journal of Materials Chemistry C, 2018, 6(15): 3869-3875. doi: 10.1039/C7TC05742C
[10]	YU B, ZHOU X P, TANG X S, et al. Enhancing the red upconversion of water-soluble β-NaErF₄:Yb nanocrystals through Ca²⁺ doping[J]. Journal of Sol-Gel Science and Technology, 2020, 93(3): 473-478. doi: 10.1007/s10971-019-05215-9
[11]	XIE W Y, AN X T, CHEN L, et al. Tunable phase and upconverting luminescence of Gd³⁺ co-doped NaErF₄:Yb³⁺ nanostructures[J]. Materials Research Bulletin, 2017, 95: 509-514. doi: 10.1016/j.materresbull.2017.08.033
[12]	SHI L C, HU J S, WU X F, et al. Upconversion core/shell nanoparticles with lowered surface quenching for ﬂuorescence detection of Hg²⁺ ions[J]. Dalton Transactions, 2018, 47(46): 16445-16452. doi: 10.1039/C8DT02853B
[13]	YU Z C, ZHOU H F, ZHOU G J, et al. Optical-magnetic bifunctional properties and mechanistic insights on upconversion of NaYF₄:Yb, Ho, Tm@NaGdF₄ with a tunable nanodumbbell morphology[J]. Physical Chemistry Chemical Physics, 2017, 19(47): 31675-31683. doi: 10.1039/C7CP05011A
[14]	陈杰, 高忆欣, 王超, 等. 六角柱形NaErF₄和NaErF₄@NaYF₄核壳微粒制备及多色上转换荧光调控性能[J]. 发光学报, 2022, 43(2): 209-217. doi: 10.37188/CJL.20210373 CHEN Jie, GAO Yixin, WANG Chao, et al. Preparation and polychromatic upconversion luminescence of hexagonal NaErF₄ and NaErF₄@NaYF₄ core-shell particles[J]. Chinese Journal of Luminescence, 2022, 43(2): 209-217(in Chinese). doi: 10.37188/CJL.20210373
[15]	CHOI J E, KIM D, JANG H S. Intense upconversion red emission from Gd-doped NaErF₄:Tm-based core/shell/shell nanocrystals under 980 and 800 nm near infrared light excitations[J]. Chemical Communications, 2019, 55(16): 2261-2264. doi: 10.1039/C8CC09031A
[16]	JOSHI R, PERALA R S, SHELAR S B, et al. Super bright red upconversion in NaErF₄:0.5%Tm@NaYF₄:20%Yb nanoparticles for anti-counterfeit and bioimaging applications[J]. Applied Materianls & Interfaces, 2021, 13(2): 3481-3490.
[17]	PAN T T, SUN L Y, GAO R Y, et al. Efficient modulation of upconversion luminescence in NaErF₄-based core-shell nanocrystals[J]. New Journal of Chemistry, 2020, 44(22): 9153-9157.
[18]	晏旭, 梁作芹, 张晓波, 等. 花菁衍生物/上转换纳米复合材料的制备与发光性质[J]. 复合材料学报, 2023, 40(6): 3562-3570. YAN Xu, LIANG Zuoqin, ZHANG Xiaobo, et al. Preparation and luminescence properties of cyanine dye-sensitized upconversion nanocomposites[J]. Acta Materiae Compositae Sinica, 2023, 40(6): 3562-3570(in Chinese).
[19]	BORODZIUK A, BARANOWSKI M, WOJCIECHOWSKI T, et al. Excitation efficiency determines the upconversion luminescence intensity of β-NaYF₄:Er³⁺, Yb³⁺ nanoparticles in magnetic fields up to 70 T[J]. Nanoscale, 2020, 12(39): 20300-20307. doi: 10.1039/D0NR04252H
[20]	陈杰, 王超, 尹玉, 等. SiO₂@Gd₂O₃:Yb³⁺, Ln³⁺ (Ln=Er, Tm, Ho)核壳微球的制备及上转换发光性能[J]. 复合材料学报, 2023, 40(7): 4072-4081. CHEN Jie, WANG Chao, YIN Yu, et al. Preparation and upconversion luminescence properties of SiO₂@Gd₂O₃:Yb³⁺, Ln³⁺ (Ln=Er, Tm, Ho) core-shell microspheres[J]. Acta Materiae Compositae Sinica, 2023, 40(7): 4072-4081(in Chinese).
[21]	ZHANG X J, GAO R Y, WANG Z J, et al. Effect of excitation mode on the upconversion luminescence of β-NaYF₄: Yb/Er nanocrystals[J]. Chemical Physics Letters, 2021, 779: 138880. doi: 10.1016/j.cplett.2021.138880
[22]	CHEN J, WANG C, YIN Y, et al. Upconversion luminescence enhancement and color modulation in Yb³⁺/Er³⁺/Ln³⁺ (Ln = Tm, Ho) tri-doped YF₃ microrods[J]. Optical Materials, 2023, 140: 113839. doi: 10.1016/j.optmat.2023.113839
[23]	SHUAI P F, GUO Q F, LIAO L B, et al. Structure, optical characteristics and temperature sensing performance studies of Cs₃YF₆:Er³⁺, Yb³⁺ up-conversion material with cryolite structure[J]. Journal of Solid State Chemistry, 2022, 306: 122720. doi: 10.1016/j.jssc.2021.122720
[24]	CHEN J, GUO J J, CHEN L Y, et al. Optimized luminescent intensity of Ca₂MgWO₆:Er³⁺, Yb³⁺ up-conversion phosphors by uniform design and response surface methodology[J]. Journal of Luminescence, 2022, 248: 118958. doi: 10.1016/j.jlumin.2022.118958
[25]	PRZYBYLSKA D, GRZYB T, ERDMAN A, et al. Anti-counterfeiting system based on luminescent varnish enriched by NIR-excited nanoparticles for paper security[J]. Scientific Reports, 2022, 12(1): 19388. doi: 10.1038/s41598-022-23686-9
[26]	CHEN Q S, XIE X J, HUANG B L, et al. Confining excitation energy in Er³⁺-sensitized upconversion nanocrystals through Tm³⁺-mediated transient energy trapping[J]. Angewandte Chemie, 2017, 129(26): 7713-7717.
[27]	SONG Y, GONG G, XIE S W, et al. Synthesis and inkjet printing of NaYF₄:Ln³⁺@NaYF₄ core-shell nanoparticles with enhanced upconversion fluorescence for anti-counterfeiting applications[J]. Journal of Nanoscience and Nanotechnology, 2020, 20(3): 1511-1519.
[28]	JIN L M, CHEN X, SIU C K, et al. Enhancing multiphoton upconversion from NaYF₄:Yb/Tm@NaYF₄ core-shell nanoparticles via the use of laser cavity[J]. ACS Nano, 2017, 11(1): 843-849. doi: 10.1021/acsnano.6b07322
[29]	YANG H J, LI X B, ZHANG R R, et al. Preparation and properties of Nd³⁺ doped Gd₂O₃ near-infrared phosphor[J]. Ceramics International, 2021, 47(6): 8510-8517. doi: 10.1016/j.ceramint.2020.11.218
[30]	TANG R J, WANG J X, XU Y S, et al. Controlled synthesis and upconversion luminescence properties of heterogeneous isomorphic Yb³⁺/Er³⁺ co-doped Na_0.9Ca_0.9Gd_1.1F₆ nanorods with multiple luminescence centers[J]. CrystEngComm, 2022, 24(2): 251-259.
[31]	AN J X, ZHANG S, LIU R W, et al. Luminescent properties of Dy³⁺/Eu³⁺ doped fluorescent glass for white LED based on oxyfluoride matrix[J]. Journal of Rare Earths, 2021, 39(1): 26-32. doi: 10.1016/j.jre.2020.01.013