Journal of Luminescence 223 (2020) 117237
Available online 28 March 2020
0022-2313/© 2020 Elsevier B.V. All rights reserved.
Temperature induced emission enhancement and investigation of
Nd
3þ
→Yb
3þ
energy transfer efficiency in NaGdF
4
:Nd
3þ
, Yb
3þ
, Er
3þ
upconverting nanoparticles
I. Mikalauskaite , G. Pleckaityte , L. Sinusaite , V. Plausinaitiene , A. Katelnikovas
*
,
A. Beganskiene
Institute of Chemistry, Vilnius University, Naugarduko 24, LT-03225, Vilnius, Lithuania
A R T I C L E INFO
Keywords:
Downconversion
Upconversion
Temperature induced luminescence
NaGdF
4
Nd
3þ
co-doping
ABSTRACT
Inorganic upconverting nanoparticles that can be excited with 808 nm laser radiation are gaining much attention
recently. Living tissues, as well as water do not heat up as intensively when embedded upconverting nano-
particles are excited under such wavelength if compared to commonly used 980 nm laser radiation for excitation.
To this end, a series of NaGd
0.995-x
Yb
x
Nd
0.005
F
4
nanoparticles were synthesized in order to investigate energy
transfer efficiency between Nd
3þ
and Yb
3þ
dopants under 808 nm laser excitation to better suit biological ap-
plications. The impact of Yb
3þ
concentration increase on crystal phase formation as well as downconversion (DC)
properties was investigated. Temperature dependent luminescence measurements in NIR region revealed that no
thermal quenching of Nd
3þ
Yb
3þ
pair in NaGdF
4
system was observed in the entire 77–500 K temperature
range. Finally, Er
3þ
ions were introduced in the investigated system in order to obtain multiple excitation and
visualisation tool with performance in both VIS and NIR regions. The effective energy difference (ΔE) was also
calculated from the thermally coupled levels (TCLs) of Er
3þ
. The promising results and observations of syn-
thesized compounds will be discussed, as NaGd
0.475
Yb
0.5
Er
0.02
Nd
0.005
F
4
has a potential to be used as a lumi-
nescent temperature sensor.
1. Introduction
Upconverting (UC) nanoparticles (NPs) have been considered as a
beneficial luminescent tool in tissue and cell imaging fields. Despite the
promising future perspectives, the performance improvement of these
nanomaterials is still necessary in order to meet the requirements for
practical application. The major challenges that limit the successful
application of such nanomaterials in biomedical field are overheating of
biological tissues when 980 nm laser is used for excitation, and low
luminescence efficiency of upconversion process [1]. The conventional
bio-imaging techniques utilize fluorescent dyes or quantum dots. In this
sense, the upconverting NPs have lots of advantages, because the near
infrared (NIR) radiation used to excite these NPs, can penetrate deeper
into the tissue (several centimetres [1]) if compared to short wavelength
radiation used to excite fluorescent dyes or quantum dots. Moreover, UC
NPs provide narrower emission bands (lines) and weaker auto-
fluorescence [2,3]. Recently, a 915 nm excitation wavelength was pro-
posed for NaYbF
4
system yielding lower temperature rise of biological
tissue sample over the prolonged irradiation [4]. Another way of shifting
excitation to even shorter wavelengths is adding Nd
3þ
ions into the
inorganic matrices. Neodymium ions are frequently considered as an
alternative sensitizer in UC systems since they possess larger absorption
cross-section [5] than Yb
3þ
ions, and several absorption bands in the
NIR region where absorption of water is relatively weak. Thus, a deep
tissue imaging using NIR emission of Nd
3þ
ions is also considered as an
advantageous approach, which eliminates the negative impact of the
biological components from the outcoming signal [6,7]. To avoid any
overheating and suppression of signal due to the interaction with bio-
logical tissue, an emission in the second near infrared (NIR-II) biological
window has been proposed as a subject for investigation. There are
several lanthanide ions (i.e., Tm
3þ
, Nd
3þ
, Yb
3þ
, Pr
3þ
, Er
3þ
, and Ho
3þ
)
possessing emission bands in the NIR-II region. These bands can be
employed in bio-imaging through downconversion (DC) approach
[8–10]. The advantage of Nd
3þ
doping is the shift of excitation wave-
length to ca. 808 nm, what significantly reduces the overheating effect.
Besides, an additional combination of DC and UC emission in single
* Corresponding author.
E-mail address: arturas.katelnikovas@chf.vu.lt (A. Katelnikovas).
Contents lists available at ScienceDirect
Journal of Luminescence
journal homepage: http://www.elsevier.com/locate/jlumin
https://doi.org/10.1016/j.jlumin.2020.117237
Received 15 November 2019; Received in revised form 19 March 2020; Accepted 21 March 2020