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Absolute quantum yield measurements of colloidal NaYF4: Er3+, Yb3+

upconverting nanoparticles†
John-Christopher Boyer‡ and Frank C. J. M. van Veggel*
Received 13th April 2010, Accepted 13th May 2010
DOI: 10.1039/c0nr00253d

In this communication we describe a technique for measuring the

absolute quantum yields (QYs) of upconverting nanomaterials based
on the use of a commercially available fluorimeter and an integrating
sphere. Using this setup, we have successfully acquired luminescence
efficiency data (pump laser, absorbed pump, and visible emitted
intensities) for lanthanide-doped upconverting nanoparticles. QYs in
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the range of 0.005% to 0.3% were measured for several NaYF4: 2%

Er3+, 20% Yb3+ nanoparticles with particle sizes ranging from 10 to
100 nm while a QY of 3% was measured for a bulk sample.

In this communication we describe a technique for the quantitative

measurement of the absolute quantum yields (QYs) of several
upconverting materials based on the use of a commercially avail-
able fluorimeter and an integrating sphere. Upconversion is the
generation of higher energy light from lower energy radiation,
usually near-infrared (NIR) or infrared (IR), typically through the
use of lanthanide ions doped into a solid-state host. These materials
have an assorted range of applications such as display phosphors,1–3
telecommunication,4 biolabels,5,6 lasers,7 and security labeling.8,9
Based on this intense interest, it is surprising to find so few publi-
cations in the literature dealing with the QYs of these materials
where the intensities of the emitted and absorbed pump light are
quantified.10–16 To our knowledge there are no reports on the
measurement of absolute efficiencies of colloidal upconverting
nanoparticles (NPs).
In response to this lack of data, we have successfully designed
a setup (Fig. 1 and Fig. S1 of the ESI†) using a commercially
available spectrophotometer (Edinburgh Instruments FLS 920), an
integrating sphere, and a 980 nm laser diode to acquire luminescence
efficiency data (pump laser, absorbed pump, and visible emitted
intensities). This method makes use of a relatively basic spectro-
photometer and an inexpensive diode laser. Using these data, we
have successfully measured QYs in the range of 0.005% to 0.3% for
the green emission of several hexagonal-phase NaYF4: 2% Er3+,
20% Yb3+ NPs with particle sizes ranging from 10 to 100 nm. A QY
of 3% was measured for bulk samples with the same dopant levels.
In order to obtain reliable measurements it was essential to calibrate
the responses of the monochromators, detectors and integrating
University of Victoria, Department of Chemistry, P.O. Box 3065, Victoria,
British Columbia, Canada V8W 3V6. E-mail: fvv@uvic.ca; Fax: +1 778-
782-3765; Tel: +1 778-782-8060
† Electronic supplementary information (ESI) available: Experimental
details, powder XRDs and TEM micrographs of the samples. See DOI:
10.1039/c0nr00253d
‡ Current address: 4D Labs, Simon Fraser University, Department of
Chemistry, 8888 University Drive, Burnaby, British Columbia,
Canada, V5A 1S6. E-mail: jboyer@sfu.ca; Fax: +1 778-782-8158,
Tel: +1 778-782-8158.
Fig. 1 Diagram of the integrating sphere setup for luminescence
measurements. Dashed line—excitation light. Solid line—sample emis-
sion.
sphere before any other spectroscopic measurements were per-
formed. The final result is a reliable and straightforward method to
determining QYs of upconverting materials both in powder and
colloid form.
For the absolute QY measurements, we employed a barium sulfate
coated integrating sphere (150 mm in diameter) from Edinburgh
instruments. The integrating sphere was mounted on the fluorimeter
with the entry and output ports of the sphere located in 90 geometry
from each other in the plane of the spectrometer (Fig. S1, ESI†). All
the powder or colloidal samples were held in a quartz cuvette located
in the center of the integrating sphere. Samples were excited with
a JDS uniphase 980 nm laser diode (device type 63-00342) coupled to
a 105 mm (core) fibre. The emission from the fibre tip was collimated
to a beam diameter of 1 mm and directed on the samples using
a Newport F-91-C1-T Multimode Fiber Coupler. Baffles were
employed on both sides of the sample holder to ensure that no
scattered excitation light or emissions would be collected before
scattering off the inside of the sphere. All the spectroscopic data
collected were corrected for the spectral response of both the
fluorimeter and the integrating sphere. The response of the detection
systems in photon flux (sphere, monochromators, detectors) was
determined using a calibrated tungsten lamp (Ocean Optics HL-2000-
CAL). These normalization curves were then applied to all measured
spectra.
The QY is defined as:
# photons emitted Lsample
QY ¼ ¼
# photons absorbed Ereference  Esample

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Fig. 2 Upconversion photoluminescence data for ErYb3 nanoparticles
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(1 wt% colloidal solution in hexanes) excited with a 980 nm laser diode
(power density ¼ 150 W cm2). Laser diode profile for reference (solid
line) and sample (dotted line) is shown on the right. Inset: digital
photograph of the ErYb3 sample under the same excitation conditions.
where QY is the quantum yield, Lsample is the emission intensity,
Ereference and Esample are the intensities of the excitation light not
absorbed by the sample and the reference sample, respectively.17 For
the colloidal samples with smaller particle sizes, a cuvette filled with
the same solvent as the colloid (in our case hexanes) was employed as
reference. We observed no significant difference in the calculated QYs
when employing undoped versions of these materials as reference
materials. Hence, scatter is not an issue in the case of the small NPs
(<50 nm) utilized in this study, as also evident from the lack of scatter
in the inset photograph in Fig. 2. In the case of the largest NP sample
and the micron-sized powder (bulk) sample, undoped versions were
synthesized to act as a reference material in order to mimic sample
scatter. The above equation expresses the number of photons emitted
(numerator) divided by the number of photons absorbed (denomi-
nator), so it runs from 0 to 100% for a one-photon processes and
from 0 to 50% for a two-photon processes.
The excitation light not absorbed by the sample and the reference
was measured using a liquid-nitrogen cooled Hamamatsu R5509
NIR PMT. The difference in the integrated areas of the sample and
reference samples gives the number of absorbed photons. For these
measurements the collected signal was measured across the 976 nm
excitation wavelength (80 cm1). The upconversion photo-
luminescence was measured using a red-sensitive Peltier-cooled
Hamamatsu R955 PMT. The photons emitted were determined by
integrating the area under the photoemission spectra. We neglected
self-absorption of the emitted radiation due to the small absorption
cross-sections of the lanthanide ions which is evident from the photo
in Fig. 2. All spectra were recorded using a 1 nm resolution on the
emission monochromators and were based on an average at least 10
scans. There is a considerable difference in intensity between the
luminescence of the upconverting NPs and the excitation laser line
due to its high power density. In order to obtain accurate data it is
important to ensure that saturation of the photomultiplier tubes of
the fluorimeter does not occur. To avoid saturating the NIR detector
a neutral density filter was employed to attenuate the intensity of the
scattered radiation.
We investigated several NaYF4: Er3+ 2%, Yb3+ 20% samples with
different particle sizes as a demonstration of the validity of this
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Table 1 QYs of the NaYF4: Er3+ 2%, Yb3+ 20% samples
Power
Average particle density/
Sample # size/nm W cm2 QY (%)
ErYb1 [100 20 3.0  0.3
ErYb2 (1 wt%) 100 150 0.30  0.10
ErYb3 (1 wt%) 30 150 0.10  0.05
ErYb4 (1 wt%) 8–10 150 0.005  0.005
ErYb5 core shell (1 wt%) 30 150 0.30  0.10
technique. We choose only to examine samples with a hexagonal
crystal phase as it is widely known that the hexagonal phase of
NaYF4 is one of the best hosts known for the upconversion process.18
A series of micrometre and nanometre particle sized samples were
synthesized using literature methods (see ESI† for synthetic
details).19–22 These samples were given sample codes which are listed
in Table 1. The average particle size of each sample determined by
TEM measurements is also given in Table 1.
The method was first confirmed using a micrometre sized NaYF4
sample whose efficiency has been reported previously in the literature.
A QY of 4% measured through the use of an integrating sphere and
a custom built acquisition system was reported previously for the
green emission in a bulk NaYF4: Er3+, Yb3+ sample.13 Both the
emission of the sample and the laser profile with our doped
and undoped sample were measured employing a power density of
20 W cm2 (within saturation regime of power dependence curve). A
QY of 3.0  0.3% was determined which matches well with literature
results thus validating the accuracy of our technique. The advantage
of our technique is that it employs a commercially available spec-
trometer and an integrating sphere. A relatively inexpensive diode
laser is also used for the measurements meaning this technique is now
accessible for a large number of researchers.
The QYs of several NP samples were measured as well. Three
samples ranging in particles size from 10 to 100 nm were employed to
examine the effect of particles size on the efficiency of this material.
The upconversion emission profile and the laser profile for the 30 nm
sample (ErYb3) are show in Fig. 2. The QYs of the various materials
and the raw data for the calculations are tabulated in Tables 1 and
S1†, respectively. Upconversion is a nonlinear process thus the QYs
of upconverting materials are highly dependent on the power density
of the excitation laser.13 Therefore all measurements on the NPs
samples were performed using a power density of 150 W cm2 which
was at the beginning of the saturation regime of the power depen-
dence curve for all particles examined. Thus the QYs calculated for
the colloidal samples represent the maximum possible QYs attainable
for these materials. The QYs of the NP colloids were also found to be
independent of concentration. Drastic drops in the QYs of the
samples are observed with decreasing particle size as expected from
previous observations on upconverting NPs. Previous studies have
observed decreased upconversion luminescence in smaller NPs. The
drop in quantum yield with decreasing particle size is attributed to the
increase in surface area of the smaller NPs which places a higher
percentage of the dopant lanthanide ions closer to the surface. This
leads to an increase of non-radiative relaxations of the emitting and
intermediate levels by solvent molecules and hence an overall
decrease in the QYs. The higher surface areas of the smaller particles
could also increase the amount of surface defects in close proximity to
This journal is ª The Royal Society of Chemistry 2010

the lanthanide ions which can lead to additional luminescence
quenching.
The unexpected result from our measurements is how sharp the
decrease in QY is with decreasing particle size. When the particle size
decreases from 30 to 10 nm there is a 95% decrease in quantum yield.
This seems to indicate that there is a minimum particle size that is
capable of supporting efficient upconversion luminescence. It should
also be noted that all of the measurements reported here were per-
formed in nonpolar organic solvents. For many of the application
these NPs would have to be rendered dispersible in aqueous
environments which would lead to even greater decreases in QY.22
Optimization of the synthetic procedures to obtain NPs with the
highest possible QYs, such as core/shell structures, is an important
step in realizing the potential of these upconverting NPs.23–25 To
examine this point, we measured the QY of a 30 nm NaYF4: Er3+ 2%,
Yb3+ 20%/NaYF4 core/shell upconverting NP sample (ErYb5). A
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300% increase in the measured QY was observed after the growth of
an undoped NaYF4 shell over the Er3+ doped core NPs. The 30 nm
core/shell material has roughly the same QY as the 100 nm upcon-
verting NP sample (ErYb2) demonstrating the effectiveness of shell
growth at increasing the luminescence efficiency of these materials.
Conclusions
In this communication we have described a technique for measuring
the absolute quantum yields of upconverting nanomaterials based on
the use of a commercially available fluorimeter equipped with an
integrating sphere. Using this setup, we have shown that it is possible
to acquired QYs for lanthanide-doped upconverting nanomaterials.
Quantum yields in the range of 0.005% to 3% were measured for the
green emission of several NaYF4: 2% Er3+, 20% Yb3+ nanoparticles
with different particle sizes and a bulk sample. The beneficial effects
of a core/shell structure were also proven as a significant increase in
QY was observed over a similarly sized uncoated NP sample. The
final result is a reliable and straightforward method to determining
quantum yields of upconverting materials that are now accessible to
a wide range of researchers.
Acknowledgements
Natural Science and Engineering Research Council (NSERC), the
Canada Foundation for Innovation (CFI), and the British Columbia
This journal is ª The Royal Society of Chemistry 2010
View Article Online
Knowledge Development Fund (BCKDF) of Canada are gratefully
acknowledged for support.
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