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

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 View Article Online

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
Fig. 2 Upconversion photoluminescence data for ErYb3 nanoparticles A series of micrometre and nanometre particle sized samples were
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(1 wt% colloidal solution in hexanes) excited with a 980 nm laser diode synthesized using literature methods (see ESI† for synthetic
(power density ¼ 150 W cm2). Laser diode profile for reference (solid details).19–22 These samples were given sample codes which are listed
line) and sample (dotted line) is shown on the right. Inset: digital in Table 1. The average particle size of each sample determined by
photograph of the ErYb3 sample under the same excitation conditions. TEM measurements is also given in Table 1.
The method was first confirmed using a micrometre sized NaYF4
where QY is the quantum yield, Lsample is the emission intensity, sample whose efficiency has been reported previously in the literature.
Ereference and Esample are the intensities of the excitation light not A QY of 4% measured through the use of an integrating sphere and
absorbed by the sample and the reference sample, respectively.17 For a custom built acquisition system was reported previously for the
the colloidal samples with smaller particle sizes, a cuvette filled with green emission in a bulk NaYF4: Er3+, Yb3+ sample.13 Both the
the same solvent as the colloid (in our case hexanes) was employed as emission of the sample and the laser profile with our doped
reference. We observed no significant difference in the calculated QYs and undoped sample were measured employing a power density of
when employing undoped versions of these materials as reference 20 W cm2 (within saturation regime of power dependence curve). A
materials. Hence, scatter is not an issue in the case of the small NPs QY of 3.0  0.3% was determined which matches well with literature
(<50 nm) utilized in this study, as also evident from the lack of scatter results thus validating the accuracy of our technique. The advantage
in the inset photograph in Fig. 2. In the case of the largest NP sample of our technique is that it employs a commercially available spec-
and the micron-sized powder (bulk) sample, undoped versions were trometer and an integrating sphere. A relatively inexpensive diode
synthesized to act as a reference material in order to mimic sample laser is also used for the measurements meaning this technique is now
scatter. The above equation expresses the number of photons emitted accessible for a large number of researchers.
(numerator) divided by the number of photons absorbed (denomi- The QYs of several NP samples were measured as well. Three
nator), so it runs from 0 to 100% for a one-photon processes and samples ranging in particles size from 10 to 100 nm were employed to
from 0 to 50% for a two-photon processes. examine the effect of particles size on the efficiency of this material.
The excitation light not absorbed by the sample and the reference The upconversion emission profile and the laser profile for the 30 nm
was measured using a liquid-nitrogen cooled Hamamatsu R5509 sample (ErYb3) are show in Fig. 2. The QYs of the various materials
NIR PMT. The difference in the integrated areas of the sample and and the raw data for the calculations are tabulated in Tables 1 and
reference samples gives the number of absorbed photons. For these S1†, respectively. Upconversion is a nonlinear process thus the QYs
measurements the collected signal was measured across the 976 nm of upconverting materials are highly dependent on the power density
excitation wavelength (80 cm1). The upconversion photo- of the excitation laser.13 Therefore all measurements on the NPs
luminescence was measured using a red-sensitive Peltier-cooled samples were performed using a power density of 150 W cm2 which
Hamamatsu R955 PMT. The photons emitted were determined by was at the beginning of the saturation regime of the power depen-
integrating the area under the photoemission spectra. We neglected dence curve for all particles examined. Thus the QYs calculated for
self-absorption of the emitted radiation due to the small absorption the colloidal samples represent the maximum possible QYs attainable
cross-sections of the lanthanide ions which is evident from the photo for these materials. The QYs of the NP colloids were also found to be
in Fig. 2. All spectra were recorded using a 1 nm resolution on the independent of concentration. Drastic drops in the QYs of the
emission monochromators and were based on an average at least 10 samples are observed with decreasing particle size as expected from
scans. There is a considerable difference in intensity between the previous observations on upconverting NPs. Previous studies have
luminescence of the upconverting NPs and the excitation laser line observed decreased upconversion luminescence in smaller NPs. The
due to its high power density. In order to obtain accurate data it is drop in quantum yield with decreasing particle size is attributed to the
important to ensure that saturation of the photomultiplier tubes of increase in surface area of the smaller NPs which places a higher
the fluorimeter does not occur. To avoid saturating the NIR detector percentage of the dopant lanthanide ions closer to the surface. This
a neutral density filter was employed to attenuate the intensity of the leads to an increase of non-radiative relaxations of the emitting and
scattered radiation. intermediate levels by solvent molecules and hence an overall
We investigated several NaYF4: Er3+ 2%, Yb3+ 20% samples with decrease in the QYs. The higher surface areas of the smaller particles
different particle sizes as a demonstration of the validity of this could also increase the amount of surface defects in close proximity to

1418 | Nanoscale, 2010, 2, 1417–1419 This journal is ª The Royal Society of Chemistry 2010
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the lanthanide ions which can lead to additional luminescence Knowledge Development Fund (BCKDF) of Canada are gratefully
quenching. acknowledged for support.
The unexpected result from our measurements is how sharp the
decrease in QY is with decreasing particle size. When the particle size Notes and references
decreases from 30 to 10 nm there is a 95% decrease in quantum yield.
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This journal is ª The Royal Society of Chemistry 2010 Nanoscale, 2010, 2, 1417–1419 | 1419