Supplementary Information for

A facile hydrothermal synthesis of highly luminescent NaYF4:Yb3+/Er3+ upconversion

nanoparticles and their biomonitoring capability

Rafia Rafique, Seung Hoon Baek, Le Minh Tu Phan, Sung-Jin Chang, Anam Rana Gul, Tae

Jung Park*

Department of Chemistry, Institute of Interdisciplinary Convergence Research, Research

Institute of Halal Industrialization Technology, Chung-Ang University, 84 Heukseok-ro,

Dongjak-gu, Seoul 06974, Republic of Korea

* Corresponding author. Tel.: +82 2 820 5220, fax: +82 2 825 4736.

E-mail address: tjpark@cau.ac.kr (T. J. Park)

S1
Table S1. Characteristics and experimental conditions of as-prepared particlesa

Reactants
NaF conc. Phase Morphology Aspect ratioc Figure#
conc.b

0.1 M 1.0 M (7.5 mL) Cubic, hexagonal 1.07±0.10 a

0.1 M 1.0 M (9.0 mL) Cubic, hexagonal 1.01±0.07 b

Irregular rod
0.1 M 0.5 M (7.5 mL) Orthorhombic c
shape

0.1 M 0.5 M (9.0 mL) Cubic, hexagonal 1.02±0.08 d

0.2 M 1.0 M (7.5 mL) Cubic, hexagonal 1.02±0.12 e

0.2 M 1.0 M (9.0 mL) Cubic, hexagonal 1.04±0.07 f

0.2 M 0.25 M (7.5 mL) Orthorhombic 3.47±0.37 g

0.2 M 0.25 M (9.0 mL) Orthorhombic 3.35±0.41 h

a
0.2 M sodium citrate, 3 mL DI water, 22.5 mL ethanol, 150 mg CTAB
b
Molar concentration of reactant [Ln(NO3)3] represents the total quantity of Y3+ and doped
lanthanide ions such as Yb3+ and Er3+.
c
Standard deviation calculated by collecting at least 100 particles

S2
Fig. S1. Size distribution of as-prepared particles with different molar proportions of

reactants and NaF with different volumes as well (Table S1). Size distribution was measured

by collecting at least 100 spherical shape particles.

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Table S2. Description of experimental conditions to obtain high luminescent particles a

Molar conc. of Yb3+ (%) Molar conc. of Er3+ (%) Reaction time (h)

20 2 2, 3, 5

30 2 2, 3, 5

20 3 3, 5

30 3 3, 5

20 4 3, 5

30 4 3, 5
a
0.2 M sodium citrate, 3 mL DI water, 22.5 mL ethanol, 150 mg CTAB, 190oC
0.2 M [Ln(NO3)3], 7.5 mL of 1.0 M NaF

S4
Fig. S2. Size distribution of NaYF4:Yb3+/Er3+, UCNP synthesized at 190oC for 2-h

hydrothermal reaction time, (A) 20% Yb3+/2% Er3+ and (B) 30% Yb3+/2% Er3+

concentrations. The size distribution was calculated by collecting at least 100 particles.

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Fig. S3. Size distribution of NaYF4:Yb3+/Er3+, UCNP synthesized at 190oC for 3-h

hydrothermal reaction time, (A) 20% Yb3+/2% Er3+, (B) 20% Yb3+/3% Er3+, (C) 20%

Yb3+/4% Er3+, (D) 30% Yb3+/2% Er3+, (E) 30% Yb3+/3% Er3+, (F) 30% Yb3+/4% Er3+

concentrations. The size distribution was calculated by collecting at least 100 particles.

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Fig. S4. Size distribution of NaYF4:Yb3+/Er3+, UCNP synthesized at 190oC for 5-h

hydrothermal reaction time, (A) 20% Yb3+/2% Er3+, (B) 20% Yb3+/3% Er3+, (C) 20%

Yb3+/4% Er3+, (D) 30% Yb3+/2% Er3+, (E) 30% Yb3+/3% Er3+, (F) 30% Yb3+/4% Er3+

concentrations. The size distribution was calculated by collecting at least 100 particles.

S7
 3+ 3+
20% Yb ,3% Er (3h)
3+ 3+

Intensity (a.u.)
20% Yb ,3% Er (5h)

500 550 600 650 700

Wavelength (nm)

Fig. S5. The comparison of best emission spectra of NaYF4:Yb3+/Er3+ synthesized with 3-

and 5-h hydrothermal reaction times. The spectra show that maximum luminescence obtained

at NaYF4:20%Yb3+/3%Er3+ with 5-h hydrothermal reaction time.

S8
Fig. S6. Photoluminescence spectra of red and green emission intensity of NaYF4:Yb3+/Er3+.

The results depicted that luminescence intensity increased with increasing reaction time in all

synthesized UCNP. Interestingly, the intensity of green emission becomes significantly

stronger than red emission at 20% Yb3+ whereas red emission is high at 30% Yb3+ with

different Er3+ concentrations. Maximum green and red intensities were observed at

NaYF4:20%Yb3+/3%Er3+ with 5-h hydrothermal reaction time. The overall green and red

emission intensity at 20% Yb3+ are ~4 and ~2.6 times, respectively, higher than green and red

emission at 30% Yb3+.

S9
Table S3. Best obtained experimental conditions of as-prepared particles with strong UC
luminescence

Optimized
Optimization factors Phase Morphology Size (nm)
conditions

Reactant concentration 0.2 M Good

NaF concentration 1.0 M (7.5 mL) hexagonal 80.09 ±

Spherical
with small 8.95
Dopant concentration 20%Yb3+/3%Er3+
cubic peaks

Reaction time 5h

S10
Fig. S7. UC luminescence emission spectra of the best selected (Table S3) UCNP solution

(60 μg/mL) observed at 540 nm for green emission band (green line), and 655 nm for red

emission band (red line) using 980-nm laser irradiation with 7-ns pulse width excitation from

an OPO, optical parametric oscillator system pumped by Nd:YAG laser (GCR-150, 355 nm).

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