Upconversion Spectroscopic Investigation of Single Nanoparticles

doi:10.15541/jim20160131

Abstract

Abstract:

Upconversion nanoparticles (UCNPs) have made a significant and valuable contribution to photophysics and biomedicine, due to their specific spectroscopic characteristics. However, the ensemble spectroscopy of UCNPs is limited for the electronic behavior in average effect, which ignores the fact that the nanoparticles are heterogeneous. Towards the research focus on heterogeneous intrinsic structure, unique photophysical phenomena, and advanced applications, the optical characterization of single UCNPs are promoted to a frontier breakthrough of UCNPs community. Electronic behavior detection aimed at a single nanoparticle displays signals from the micro-structure of nanoparticles, while single nanoparticle spectroscopy offers clear insight into the interplay between intrinsic and extrinsic influences without noise, and subsequently gives instructions for the high quality preparation of UCNPs. Single nanoparticle optical characterization possesses a powerful capacity to explore the crystalline structure anisotropy related optical differences, or some unexpected unique optical phenomena at sub-micron and even nano-scale. In this review, the importance of single UCNPs characterization and single particle detection methods are overviewed, in which the considerable emphasis is placed on the specific spectroscopic study of single UCNPs Showing fantastic photophysical phenomena beyond ensemble measurement. Finally, this review identifies promising opportunities in which single UCNPs characterization technique can accelerate on-going research with a remarkable depth and breadth, facilitate discovery of upconversion nanoparticles that overcome fundamental limitations of current ensemble level.

Key words: upconversion, lanthanides, single nanoparticle, spectroscopy, review

CLC Number:

TQ174

ZHOU Jia-Jia, QIU Jian-Rong. Upconversion Spectroscopic Investigation of Single Nanoparticles[J]. Journal of Inorganic Materials, 2016, 31(10): 1023-1030.

Figures/Tables 8

Fig. 1 Schematic diagram of confocal microscopic fluorescent scanning system from upconversion nanoparticles

Fig. 2 Schematic experimental configuration for capturing UC luminescence of nanoparticles using a suspended-core microstructured optical-fiber dip sensor[9]

Fig. 3 Schematic diagram of the experimental setup used for luminescence acquisition of an optically trapped upconversion nanoparticle[35]

Table 1 Photostability and brightness assessment of single UCNPs

UCNPs	Particle size/nm	Monitoring wavelength/nm	Assessing mode	Power density /(W·cm^-2)	Time range /min	Ref.
β-NaYF₄: Yb³⁺, Er³⁺	~27	550/650	photostability	5 ×10⁶	60	[24]
NaGdF₄: Yb³⁺, Er³⁺@NaGdF₄	~40	550/650	photostability	150	240	[23]
YVO₄: Yb³⁺, Er³⁺	~39	520/550/650	photostability	8×10³	8	[41]
NaYF₄ : Yb³⁺, Ho³⁺, Tm³⁺@NaYF₄	~22	450/475/545/645	photostability	8×10⁶	360	[42]
β-NaYF₄: Yb³⁺/Er³⁺	~10	550/650	photostability	10⁶	60	[29]
β-NaGdF₄: Yb³⁺, Er³⁺@NaYF₄	~20	520/550/650	brightness	/	/	[43]
β-NaGdF₄: Yb³⁺, Er³⁺@NaGdF₄ @SiO₂@NPTAT-doped SiO₂	~39	550	photostability	/	15	[14]
β-NaGdF₄: Yb³⁺, Tm³⁺@NaGdF₄ @SiO₂@NPTAT-doped SiO₂	~38	480
NaYbF₄: Er³⁺@NaYF₄@SiO₂@rhodamine B isothiocyanate-doped SiO₂	~24	650

Fig. 4 (a) Integrated upconrersion luminescence intensity (~400- 850 nm) as a function of excitation irradiance for a series of Tm3+-doped nanoparticles. (b) Luminescence intensity of single 8 nm UCNPs with 20% (blue circles) and 2% (red circles) Er3+, each with 20%Yb3+, plotted as a function of excitation intensity. Confocal luminescence images taken at points shown in (b) of single UCNPs containing a mixture of 2% and 20% Er3+. (c) Emission spectra of single β-NaYF4: 20% Yb3+-2% Tm3+ nanoparticle excited with 980 nm laser illumination at the power density of ~1.1×107 W/cm2[13, 30, 44]

Fig. 5 (a-d) Emission spectra of UC from β-NaYF4: Tm3+-Yb3+ single micro-rod in the transitions of Tm3+: (a) 1G4→3F4, (b) 3F3→3H6, 1D2→3F3, (c) 1G4→3H5, (d) 3H4→3H6, respectively. (e-h) The dependence of the corresponding spectra on emission polarization angle (φem). (i, j) UC luminescence spectra of a single nanodisk, whose a axis or c axis is parallel to horizontal plane, recorded at excitation polarization angles varying from 0° to 360°, with no polarizer placed in the detection part. (k) Emission spectra from a single NaYF4: Er3+, Yb3+ UCNR immobilized on a surface for two perpendicular emission polarization angles. Purple (blue) line represents recovered emission parallel (perpendicular) to the optical axis of the NaYF4: Er3+, Yb3+ UCNR. Inset represents these two different polarizations of the electric field that gives the two distinct spectra. (l) Two dimensional map represents emission intensity of red band as a function of emission polarization angle[27, 31]

Fig. 6 Lifetime tuning scheme and time-resolved confocal images for NaYF4: Yb, Tm upconversion nanocrystals[10]

Fig. 7 (a) AFM image showing the nanoassembly approach: The 60 nm gold nanosphere is attached to the UCNPs with the help of the AFM tip. The yellow arrow indicates the polarization axis of the excitation light. (b) Upconversion emission spectra of the nanoparticle without (violet curve) and with (blue curve) the gold nanosphere in close vicinity. (c) Rise (upper) and decay times (lower) of the green (left) and red (right) emission with the color code as in part (b). (d) Schematic of the tip-enhancement of a single Upconversion nanoparticle. (e) Upconversion emission spectra with retracted and approached tip, respectively. (f) Decay curves for red emission detected with and without tip at 660 nm[26, 55]

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