Klier 2015

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Article
Upconversion Luminescence Properties of
NaYF:Yb:Er Nanoparticles Co-doped with Gd
4 3+
Dennis T Klier, and Michael U. Kumke

J. Phys. Chem. C, Just Accepted Manuscript • DOI: 10.1021/jp5103548 • Publication Date (Web): 21 Jan 2015
Downloaded from http://pubs.acs.org on January 29, 2015
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Page 1 of 34 The Journal of Physical Chemistry
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Upconversion Luminescence Properties of NaYF4:Yb:Er
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9 Nanoparticles Co-doped with Gd3+
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16 Dennis T. Klier and Michael U. Kumke#
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22 University of Potsdam, Department of Chemistry (Physical Chemistry), Karl-Liebknecht-Str. 24-25,
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24 14476 Potsdam, Germany
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27 #
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Kumke@uni-potsdam.de
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31 Abstract: The temperature dependent upconversion luminescence of NaYF4:Yb,Er nanoparticles
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34 (UCNP) containing different contents of Gd3+ as additional dopant was characterized. The UCNP were
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36 synthesized in a hydrothermal synthesis and stabilized with citrate in order to transfer them to the water
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phase. Basic characterization was carried out using TEM and DLS to determine the average size of the
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41 UCNP. The XRD technique was used to investigate the crystal lattice of the UCNP. It was found that
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43 due to the presence of Gd3+ an alteration of the lattice phase from • to β was induced which was also
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46 reflected in the observed upconversion luminescence properties of the UCNP. A detailed analysis of the
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48 upconversion luminescence spectra - especially at ultra low temperatures - revealed the different effects
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of phonon coupling between the host lattice and the sensitizer (Yb3+) as well as the activator (Er3+).
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53 Furthermore, the upconversion luminescence intensity reached a maximum between 15 K and 250 K
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55 depending on Gd3+ content. In comparison to the very complex temperature behavior of the
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upconversion luminescence in the temperature range < 273 K, the luminescence intensity ratio of 2H11/2-
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ACS Paragon Plus Environment
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The Journal of Physical Chemistry Page 2 of 34
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I15/2 to 4S3/2-4I15/2 (R = G1/G2) in a higher temperature range can be described by an Arrhenius type
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3 equation.
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7 Keywords: temperature dependent luminescence, near-infrared, low-temperature, phonon coupling.
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10 Introduction
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12 Upconversion (UC) luminescent materials have attracted great interest in recent decades due to their
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15 outstanding photo physical properties and the resulting application potentials in various fields such as
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17 solid-state laser, solar cells, color displays or life science applications.1-9 Upconversion materials based
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19 on lanthanide-doped fluorides received a lot of attention owing to their high UC efficiency and photo
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22 stability. The most efficient UC materials among various fluoride based UC phosphors are β-phase
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24 NaYF4 doped with Yb3+ and Er3+ or Yb3+ and Tm3+.6,7,10,11 It is well known that the upconversion
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26 luminescence efficiency is highly dependent on dopant concentration, particle size, excitation power
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29 density, crystallite phase and temperature, respectively.8,12,13 The study of their thermal behavior is a
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31 prerequisite for the detailed understanding of intramolecular deactivation processes in order to tailor the
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upconversion luminescence properties and to pave the road for application of multiplexing such as an
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36 optical and magnetic imaging using UC materials.8,14-16
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38 Currently studies on thermal effects have been focused on diverse glass materials or oxide based
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41 materials13 such as ZnO or Y2O3.17-22 As an example for codoped (Er3+, Yb3+) Y2O3 nanocrystals it was
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43 reported that the luminescence intensity decreases with increasing temperature from 10 K to 300
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45 K.13,21,23 This effect was explained by the enhancement of non-radiative multiphonon relaxation rates,
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48 which reduce the radiative transition probabilities at higher temperatures. Van der Ziel et al. reported
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50 that the luminescence intensity of YF3 nanocrystals first increased and then decreased as temperature
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was raised up to room temperature. The depopulation of the higher Stark levels of the 4I11/2 of Er3+ at
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55 lower temperatures and multi phonon deexcitation at higher temperatures were proposed as dominant
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57 factors that governed the temperature dependent behavior.13,21,23
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In the present work, the upconversion luminescence of citrate acid capped NaYF4:Gd3+:Yb3+: Er3+
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3 upconversion nanoparticles (UCNP) with different crystal phases and Y3+ to Gd3+ ratio was studied at
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5 various temperatures from 330 K to 4 K. Both the luminescence intensity and ratio of luminescence
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bands was found to depend on temperature. The crystal phase and thus phonon coupling process plays a
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10 key role for the upconversion luminescence as well as thermal population rates of the emitting energy
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12 levels. The results of this study will show that there is a more complex interplay of different mechanism
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and effect then one dominant effect that governed the special temperature behavior of the UCNP.
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19 Experimental and Theoretical Methods:
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22 Materials: All rare earth oxides RE2O3 (RE: Y, Yb and Er) were purchased from Chem Pur
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24 Feinchemikalien and Forschungsbedarf GmbH. Sodium fluoride (NaF, 99%), gadolinium(III) chloride
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26 hexahydrate (GdCl3 6H2O, 99,9%), sodium nitrate (NaNO3, 99%) and trisodium citrate dehydrate
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29 (Na3C6H5O5 2H2O, 99%) were purchased from Sigma Aldrich. Nitric acid solution (HNO3, 65%) was
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31 purchased from Carl Roth and suprapure nitric acid from Merck. All chemical reagents used in
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experiments were directly used without any further purification. For the experiments double distilled
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36 water was used.
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41 Synthesis of NaYxF4:Yb3+:Gd3+:Er3+ (UCNPx): The UCNP were synthesized according to a
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43 previously reported procedure24-26 in which a hydrothermal method with trisodium citrate as a capping
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45 agent was used. The synthesis was designed to keep an overall constant amount of lattice ions (Y3+,
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48 Yb3+, Er3+, and Gd3+) in different samples to study the effect of gadolinium concentration. The
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50 concentration of the lanthanides (Ln) Er3+ and Yb3+ was constant for all samples whereas the Y3+ was
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52 replaced by Gd3+ ions (see Table 1). The RE(III) nitrates were prepared from the corresponding oxides
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55 in stoichiometric amounts of Y2O3 (1.6 mmol), Yb2O3 (0.36 mmol) and Er2O3 (0.04 mmol) dissolved in
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57 nitric acid (5 mL, 10%) according to the literature method.44 Typically, trisodium citrate (5.8 g) was
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dissolved into (12.4 mL) then a mixture of RE(NO3)3, GdCl3 (0 mmol) and sodium nitrate (6.0 g) were
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added under stirring with additional 5 mL water. After 20 minutes 10 mL of an aqueous solution of
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3 sodium fluoride (0.5 g) was added carefully under stirring. The colloidal solution was heated to 180°C
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5 for 12h. The UCNPs were separated via centrifugation (6000 rpm for 25 min). For further purification,
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the UCNPs were washed using a diluted trisodium citrate solution (6.4 g/L) and again separated via
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10 centrifugation (6000 rpm for 25 min). The procedure was repeated three times. The as-synthesized
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12 UCNPs disperse readily in polar solvents such as in aqueous trisodium citrate solution, forming a clear
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colloidal solution.
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19 Table 1: Different NaY1-xF4: Yb3+: Er3+:Gdx3+ upconversion nanoparticle (UCNPx) used in the study (in
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22 nm).
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25 Sample UCNP0 UCNP15 UCNP30 UCNP45 UCNP60 UCNP80
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27 Gd3+ (x =
0 15 30 45 60 80
28 mol %)
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30 Particle size
274±13 149±7 110±11 80±10 66±9 46±7
31 (TEM)
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33 Particle size
262±36 156±28 128±23 102±21 87±24 68±19
34 (DLS)
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36 Crystallite
37 size
38 58±8 42±4 31±7 10±4 9±3 7±2
(Debye-
39 Sch.)
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43 Structural characterization: X-ray powder diffraction patterns were obtained using a D5005 (Siemens
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46 AG, Munich, Germany) in a range of 3-70° / 2θ with divergence aperture, scattering ray aperture and
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48 graphite monochromatized Cu Kα radiation (λ = 0.15406 nm). The scanning step was 0.02° / 2θ with a
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counting time of 4s per step. The nanocrystalline domain sizes were calculated using the Debye-Scherer
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53 equation (eq. 1):
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55
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57 .
58 =
() (1)
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2 D is the domain size to be determined, λ is the wavelength of the x-ray, B is the FWHM of the
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5 diffraction peak of interest and θ is the angle of the corresponding diffraction peak.
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7 The size and morphology of as-prepared UCNPs were observed on a JEM 1011 transmission electron
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microscope (Jeol Ltd. , Tokio, Japan) (TEM) using a wolfram hairpin cathode, an accelerating voltage
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12 of 80kV and a molybdenum panel. The measurements were recorded using a side-mounted Olympus
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14 Mega View G2 (Olympus Germany GmbH, Hamburg, Germany). Particle size characterizations were
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17 also carried out with dynamic light scattering (DLS) by using a ZETASIZER Nano ZS (Malvern
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19 Instruments Ltd., Herrenberg, Germany) as well. As lightsource a He-Ne laser at λ = 633nm was used.
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21 The samples were prepared as a thin droplet on the substrate and were further investigated by Raman
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24 spectroscopy. Here, a Raman Microscope (ALPHA 300 RA, WITec, Ulm, Germany) coupled with an
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26 intensified CCD camera (DU401A-BR-DD-352, WITec, Ulm, Germany) was used.
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28 The elemental composition of the as-prepared UCNP was confirmed by ICP-OES (for more details see
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31 Supporting Information (SI.Table 1)).
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33 Room temperature steady state and time resolved upconversion luminescence: Room temperature
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steady state and time resolved upconversion emission spectra were obtained using a wavelength tunable
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38 pulsed Nd:YAG/OPO laser system (laser: Quanta Ray, Spectra--Physics, Mountain View, CA, USA;
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40 OPO: GWU-Lasertechnik Vertriebsges. mbH, Erftstadt, Germany) operating at 20 Hz as excitation light
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43 source (at 26 mJ / 130 mW) and recorded using an intensified CCD-camera (iStar DH720-18H-13,
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45 Andor Technology, Belfast, Great Britain) coupled to a spectrograph (MS257 Modell 77700A, Oriel
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47 Instruments) equipped with a 300 l/mm grating. The ''box car'' technique was applied for these sets of
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50 measurements. The initial gate delay was set to ∆t = 500 ns and the gate width was adjusted between δt
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52 = 10-100 µs. The luminescence decay kinetics were evaluated by equation 2:
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57 () = + ∗ (− ∗ ) + ∗ (− ∗ ) (2)
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5
From the coefficients B1 and B2 the relative fractions •1 and • 2 were calculated according to equation 3:
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3
4
5 ∗
6 α = ( (3)
∗ !" ∗ " )
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12 For the temperature range of 303 K > T > 328 K the samples were measured as colloidal solutions in
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14 PMMA (Polymethylmethacrylate) cuvettes sealed with Parafilm®. Prior to measurement the samples
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16 were heated in a water bath to the chosen temperature and measured in a temperature controlled sample
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19 holder.
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24 Low temperature upconversion measurements: The temperature dependent steady state
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26 upconversion luminescence measurements were recorded using a continuous wave, fiber coupled laser
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diode working at 1000 mW (SHE-SP-975-160-FS-SMA, Laser 2000 GmbH, Wessling, Germany),
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31 coupled to a shutter in order to avoid heating up the sample. In order to perform low temperature
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33 luminescence measurements in a range of 4 K to room temperature, the UCNP colloidal solutions or
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36 powders were sealed inside glass tubes and placed on a copper sample holder in a vacuum chamber
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38 attached to the cold plate of a closed cycle liquid Helium cryostat. The cryostat system consist of a
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40 Helium compressor unit (Sumitomo Heavy Industries Ltd., Markt Indersdorf, Germany), a vacuum
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43 pump (Leybold vacuum Turbolab 80, Oerlikon, Köln, Germany) for the sample chamber and a
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45 temperature controller (331 Temperature Controller, Lakeshore, Westerville, USA). The excitation light
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47 was focused on the samples at an angle of 90°. The upconversion luminescence emission was recorded
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50 using a lens system mounted in front of a fiber connected spectrograph (Shamrock SR-303i, Andor
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52 Technology, Belfast, Great Britain) equipped with an intensified CCD camera (iStar DH 720 18V 73,
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Andor Technology, Belfast, Great Britain).
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59 Results and Discussion
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Structural Investigations: UCNPx based on the NaYF4 host lattice were synthesized with varying
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3 content of Gd3+ (x = 0 – 80 mol%, see Table 1, and SI-Tab. 1 for elemental analysis). The samples were
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5 first examined by X-ray powder diffraction. For the NaYF4 host lattice two different thermodynamically
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stable phases, the cubic (isotropic) α-phase and the hexagonal (anisotropic) β-phase, are known.27 In
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10 Figure 1 diffraction patterns of UCNPx with x = 0, 30 and 80 are compared. In the absence of Gd3+ ions
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12 the X-ray diffractions pattern can be assigned to a pure cubic α-phase, as expected for this type of
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15 UCNP synthesized under mild conditions.24-26 The gradually decrease of the diffraction peak intensities
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17 of the cubic α-phase is correlated with an increasing Gd3+ dopand concentration and the rise of the
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19 diffraction peak intensity of the hexagonal phase, whereby a gradual phase transition from cubic- to the
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22 hexagonal phase is obvious. The pure β-phase was obtained at Gd3+ concentration of 80 mol%, which is
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24 consistent with the studies of Song et al. (see Figure 1).28 Remarkably, the cubic to hexagonal β-phase
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26 transition is complete after heating at 160-200°C for 12 h, whereas a complete phase transition without
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29 any Gd3+ is typically achieved at distinctly higher temperatures (T >300°C) or longer reactions times of
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31 16 h or more.24-26
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Figure 1: X-ray diffraction patterns of UCNPx (x = 0, 30, 80) with the Millerschen Indices of the
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3 corresponding lattice plane are shown.
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8 The lattices of NaGdF4 and NaYF4 belong to the same space group (P63/m) and show nearly similar
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10 unit cell parameters.10,27 Therefore, the observed transition between cubic and hexagonal phase for the
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UCNPx materials could be a consequence of the good similarity of the hexagonal phases of NaGdF4 and
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15 NaYF4 which is also indicated by the diffraction patterns of both (NaGdF4 (ICDD no: 28-0699) and
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17 NaYF4 (ICDD no: 28-1192)).10,27 The crystallite size of the as-prepared UCNPs was calculated using the
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Debye-Scherrer equation (Equation 1). It is obvious, see also Table 1, that the crystallite size decreases
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22 with increasing amount of Gd3+ ion dopand concentration and is nearly constant at Gd3+ concentrations
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24 of at least 45 mol%. Based on XRD measurements only the crystallite size is determined, which can be
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27 significantly different from the particle size determined from other techniques such as TEM and DLS
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29 (vide infra and see Table 1). The XRD data for the size dependence on the Gd3+ content are in good
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31 agreement with the general trend observed with DLS and TEM (see Table 1). The large difference is
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34 also an indication that the particles are containing more than one crystalline domain (or some amorphes
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36 parts, which is not supported by the good luminescence upconversion properties of the particles, vide
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supra).
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43 The particle size and morphology of UCNPx at different Gd3+ dopand concentration was further studied
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46 using TEM and DLS. The TEM images of the different UCNPx showed that the particles were irregular
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48 spherical in shape (SI Figure 1).28 In order to determine the average particle size from TEM images
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50 approximately 200 particles were included in the statistical analysis which showed that with increasing
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53 Gd3+ dopand concentration the diameter of the nanoparticles gradually decreased (see Table 1). In
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55 comparison to the shown results (similar to Liu et al.), Song et al. observed no effect of Gd3+ ion doping
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57 concentration on particle size evolution, which is related to different solvent mixtures.10,28
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In addition, DLS was used as a complementary method for particle size determination. The results of the
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3 DLS measurements are also shown in Table 1. Corroborating the results of the TEM images, DLS
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5 showed as well a decreasing particle size evolution with increasing Gd3+ concentration. In comparison
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to the TEM investigations the particle size obtained from the DLS measurements are slightly larger. In
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10 DLS the hydrodynamic radius is determined which includes also contribution of a solvent shell. The
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12 latter is not observed in the TEM images, which subsequently yield slightly smaller particle sizes when
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compared to DLS.
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19 In the synthesis of the UCNPx the particle size control is defined by the combination of the capping
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22 agent (here sodium citrate) and by the Gd3+ concentration. The significant particle size reduction
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24 (according to the TEM image analysis about factor of 6 between 0 mol% and 80 mol% Gd3+) can be
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26 attributed to effects of the Gd3+ ions on the effective surface charge, which is a key factor for the crystal
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29 growth rate. This explanation is supported by DFT calculations which showed that the electron charge
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31 density of the crystal surface increases when small Ln3+ ions (e.g., Nd3+, Gd3+ and Sm3+ ion) substitute
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the Y3+ ions in the crystal lattice.10
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36 From Raman spectra (see Figure 2) shows the vibrational modes of UCNPx nanoparticles displaying
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38 five obvious Raman peaks at ν = 249.6 cm-1, 422.1 cm-1, 536.8 cm-1, 739.5 cm-1 and 1062 cm-1,
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41 respectively. The most intense vibrational bands are found at low phonon energies between 200-500 cm-
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1
43 , which is consistent with reported low phonon energies for this kind of materials.10,29-31 The gradually
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45 decrease of the first Raman peak (249.6 cm-1) intensity and increase of the second Raman peak (422.1
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48 cm-1) is correlated with an increasing amount of Gd3+ dopand.
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22 Figure 2: Raman spectra of different UCNPx (x = 0, 15, and 30 mol %, λex = 532 nm).
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All vibrational bands at wavenumbers larger than 500 cm-1 are attributed to the vibrations from the
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28 organic capping agent citrate except for the band located at 1062 cm-1. The presence of citrate on the
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30 surface of the UCNP is indicated by strong COOH out-of-plane deformation modes in the 786-908 cm-1
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33 region and the C-O stretching modes in the 998-1112 cm-1.
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37 Upconversion Luminescence Spectroscopy Studies: In Figure 3 the luminescence spectra of the
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39 UCNPx containing different mol% Gd3+ are shown.
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26 Scheme 1: Schematic energy level diagram of the upconversion mechanism of a Er3+ and Yb3+ dopand
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28 ion system following an excitation with 976 nm. The full lines pointing upwards represent energy
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30
31 absorption, the dotted lines represent energy transfer, the waved lines represents non radiative relaxation
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33 processes and the colored full lines pointing downwards represents the visible emission. The cross-
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35 relaxation between different excited Er3+ ions is represented by “CR”.
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41 The spectra were recorded in water with λex = 976 nm and are the result of energy upconversion
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43 processes (see Scheme 1).32 The three most intense emission bands can be observed in the green spectral
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45 region centered at λem = 525 nm (2H11/24I15/2 transition, G1), 545 nm (4S3/24I15/2 transition, G2) and
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48 the red spectral region centered at 660 nm (4F9/24I15/2 transition, R) accompanied by the albeit very
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50 weak blue band centered at 505 nm (4F7/24I15/2 transition) and a second weak red band at 700 nm as a
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result of the 4F7/2 4I13/2 transition.11,13,33-35 The observed fine structure (Stark splitting) is induced by
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55 changes of the crystal field splitting due to small differences in the coordination environment.33,36,37
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11
The upconversion emission spectra shown in Figure 3 reveal significant differences between the
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2
3 UCNPx investigated. For the absolute intensities of the upconversion emission, a strong dependence on
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5 the Gd3+ concentration was found.38 The emission intensity of the UCNPx increased with an increase in
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7
the Gd3+ concentration up to 15 mol% and then showed a gradual decrease upon further increase of the
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10 Gd3+ content.28 Since the 6P7/2 level, which represents the next electronic state above the ground state of
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12 Gd3+, is spectroscopically found in the ultra violet region and is therefore much higher in energy than
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15
the excited state levels of Er3+ and Yb3+, any luminescence quenching by energy transfer between these
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17 ions can be ruled out. The effect is more probably related to alterations of the crystal lattice induced by
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19 the addition of Gd3+ ions: (i) change from •- to β-phase of the nanoparticle lattice and (ii) variation of
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22 the energy gap between Stark levels of Yb3+ (2F5/2) and Er3+ (4I11/2), respectively, subsequently leading
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24 to a more effective upconversion. Variations in the relative position of the Stark levels of lanthanides in
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26
27
different host lattice are well known.37,39 For higher Gd3+ contents (x > 15) as a third parameter the
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29 particle size affecting the luminescence yield of the nanoparticles comes into play. Smaller
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31 nanoparticles exhibit a higher surface to volume ratio (SA/Vol.) leading to a relative higher
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34 concentration of dopands ions located at the surface nearby region or on surface. Thus, the observed
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36 upconversion luminescence is quenched by enhancement of non radiative relaxations processes in the
37
38 surface region.
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41 At room temperature no change in the Yb3+-related absorption is found. Here, the splitting of the
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43 involved Stark levels of the 2F7/2 state is small and thermal equilibration is reached at room temperature
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45
masking any possible influence of the Gd3+ content. Here, high-resolution ultra-low temperature
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47
48 experiments are required to get a deeper insight (vide infra).
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50 In Figure 4 typical luminescence decay kinetics of the UCNPx for the green (λem = 545 nm, G2) and
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red (λem = 660 nm, R) emission are shown. From the raw data it is evident that the underlying decay
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55 kinetics are complex, because erbium ions located in the bulk phase of the particles and on the surface
56
57 are influenced by their environment to a different extent (e.g., quenching by water molecules). Hence, a
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60 bi-exponential decay law was chosen for the data analysis (see equation 2).
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28 Figure 3: Upconversion emission spectra of UCNPx showing the Er3+-luminescence bands G1, G2, and
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31 R for increasing Gd3+ content (λex = 976 nm).
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37 Moreover, in the analysis it was assumed that due to the decreasing size of the UCNPx with increasing
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39 Gd3+ content only the relative fraction of bulk-to-surface luminescence is changing. Consequently, the
40
41 experimental data were evaluated in a global analysis with two common decay times τ1 and τ2 only
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44 leaving the coefficients B1 and B2 as individual fit parameters. The relative fractions •1 and •2 were
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46 calculated according to equation 3 (see Table 2). From Figure 4 and Table 2 it is evident that above a
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48
49
certain Gd3+ content the luminescence kinetics distinctly changed. UCNPx with x = 0 - 30 showed a
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51 larger contribution from a short luminescence decay with a corresponding luminescence decay time τ1
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53 of about 10 µs. For UCNPx with x = 45 - 80 contributions from this short decay component were less
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56 than 5%. This was found for the decay kinetics of the G2 and R luminescence of erbium (see Table 2).
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13
For R luminescence, the second decay time τ2 ~ 200 µs was determined, which is distinctly longer than
1
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3 the time decay τ2 of ~ 100 µs found for the corresponding emission decay of G2.
4
5
6
7
Table 2: Luminescence decay parameters of UCNPx
8
9
10
11 Sample UCNP0 UCNP15 UCNP30 UCNP45 UCNP60 UCNP80
12
13 G2 Fraction (in %)
14
15 •1
16 58 63 42 4 5 4
17 τ1 = 10 µs)
18
19 •2
20 42 37 58 96 95 96
21 τ2 = 113 µs)
22
23 R Fraction (in %)
24
25 •1
26 30 30 30 2 3 3
27 τ1 = 11 µs)
28
29 •2
30
70 70 70 98 97 97
31 τ2 = 209 µs)
32
33
34
35 The observed short luminescence decay time τ1 may be related to erbium ions located near the surface
36
37
38 of the nanoparticles, while long luminescence decay time τ2 could be attributed to erbium ions located in
39
40 the bulk phase of the nanoparticles. In that case the short luminescence decay time τ1 could be a
41
42 consequence of an efficient quenching process due to water molecules interacting with the surface of the
43
44
45 UCNPx. It can be hypothesized that i) with decreasing size of the nanoparticle the average number of
46
47 water molecules possibly interacting with the surface of the nanoparticle is also decreasing, which
48
49
50
would subsequently reduce the relative fraction of τ1 or ii) the quenching becomes extremely efficient
51
52 (“quasi static”) and the major part of the surface-located erbium ions is completely quenched leaving
53
54 only a small portion to be present in the overall luminescence decay.
55
56
57
58
59
60
14
1
2
3
4
5
6
7
8
9
10
11
12
13
14
15 Figure 4: Luminescence decay kinetics of UCNPx for the green emission G2 (λem = 545 nm, left) and the
16
17
18 red emission R (λem = 660 nm, right) (λex = 980 nm, initial delay δt = 500 ns).
19
20
21 The τ2 of the red emission R was found to be longer than τ2 of the corresponding green emission G2,
22
23 which is related to the differences in the rate constants of deactivation processes of the 4S3/2- and 4F9/2-
24
25
26
level in erbium (see Scheme 1).
27
28
29
30
31
Low-temperature Upconversion Luminescence Studies: In Figure 5 emission spectra as well as the
32
33 integrated luminescence band intensities of UCNP80 (λex = 976 nm) for the temperature range of 4 K < T
34
35 < 209 K are shown, which are representative for the observed temperature dependence of all UCNPx
36
37
38 investigated. The following trends were observed for the different luminescence bands of Er3+: (i) The
39
40 luminescence intensity of the 2H11/24I15/2 transition (G1) gradually decreased with decreasing
41
42 temperature and disappeared completely at temperatures below 120 K. (ii) In contrast to the G1
43
44
45 emission band, the intensity of the G2- and R–related emission bands initially increased with decreasing
46
47 temperature. However, after passing T = 210 K, the emission intensity decreased again upon further
48
49
lowering the temperature (see Figure 5). When temperature drops below 100 K an additional increase in
50
51
52 upconversion luminescence intensity was found for band R, whereas in case of band G2 the intensity
53
54 did not change significantly.
55
56
57
58
59
60
15
1
2
3
4
5
6
7
8
9
10
11
12
13
14
15
16
17
18
19
20
21
22
23 Figure 5: Left: Temperature dependent upconversion emission of UCNP80 (λex = 976 nm). Inset or
24
25 Right: Temperature dependent upconversion emission (integrated intensities and normalized) of UCNPx
26
27
28 nanoparticles (80 mol% Gd3+).
29
30
31 The difference in the temperature dependence of the G1 and G2 emission bands is connected to the
32
33 population pathways of the related energy levels 2H11/2 and 4S3/2, respectively. In Scheme 2 a detail view
34
35
36 of the respective Stark levels of 2H11/2 and 4S3/2 is shown. The Stark levels are calculated from the
37
38 excitation and emission spectra of the UCNPx under investigation. The population of the green emitting
39
40 levels G1 and G2 (2H11/2 and 4S3/2) usually occurs by successive energy transfer processes from the
41
42
43 excited 2F5/2 state of Yb3+ ions to the Er3+ ions exciting it first to the 4I11/2 state and in a second step to
44
45 the 4F7/2 excited state. Followed by a non-radiative relaxation process the Er3+ ion deactivates to the
46
47 2
H11/2 and - due to the moderate energy gap between 2H11/2 and 4S3/2 states (about 700 cm-1) - the Er3+
48
49
50 ions can relax fast to the 4S3/2 state. Finally, the 2H11/2 level is thermally re-populated via thermal
51
52 agitation (see Scheme 2) resulting in the observed two Er3+-emission bands G1 and G2 as shown in
53
54
55
Figure 3 (see also Scheme 1).13,33,34,39
56
57
58
59
60
16
1
2
3
4
5
6
7
8
9
10
11
12
13
14
15
16
17
18
19
20
21
22
23
24
25
26
27
28
29
30
31
32
33
34
35 Scheme 2: Close-up of energy levels related to G1 and G2 emission in erbium.
36
37
38 The thermal equilibration of the two levels is fast, hence the observed intensity ration of G1 and G2
39
40 will be dependent on the temperature. Alternatively, the ions can relax non-radiative to the 4F9/2 level
41
42
43 leading to red emission (centered at 660 nm). Further, the 4F9/2 level can be populated after non-
44
45 radiative relaxation from the 4I11/2- to 4I13/2 level followed by an energy transfer from the sensitizer Yb3+
46
47 to the Er3+, leading also to the red emission R. Typically cross relaxation processes between two excited
48
49
50 Er3+ ions can be neglected in the UCNPx investigated because of the low Er3+ content used.35,40
51
52
53
54
55
In Figure 6 the temperature dependent upconversion luminescence intensity of UCNPx are compared.
56
57 In general, a similar temperature dependence was found for all UCNPx investigated. Upon lowering the
58
59 temperature, the intensities of the G2 and R bands increased and then dropped again after passing a
60
17
certain temperature. However, the temperature of maximum luminescence intensity was found to be
1
2
3 specific for the Gd3+ content of the UCNPx.
4
5 For the temperature dependence of the R band it was found that for concentration of Gd3+ above 60
6
7
mol% luminescence intensity increased again at very low temperatures (see Figure 6). The observed
8
9
10 differences of the temperature dependency are due to the different population mechanisms of band R
11
12 and G1. Within the different cascades of energy transfers from the Yb3+ to the Er3+ and the non-radiative
13
14
15 relaxation steps (see Scheme 1) phonon coupling is very important in order to bridge little energy
16
17 difference between the sensitizer and the activator involved. From the XRD and Raman measurements
18
19 (see Figure 1 and 2) a change in the host lattice properties (transition between •- and β-phase) with
20
21
22 increasing Gd3+ content was concluded.
23
24
25
26
27
28
29
30
31
32
33
34
35
36
37
38
39
40
41
42
43 Figure 6: Normalized upconversion luminescence intensities of UCNPx as function of temperature for
44
45 G2 (left) and R (right) (τex = 976 nm).
46
47
48 In a control experiment UCNP0 was tempered at different temperatures to induce the phase transfer
49
50
51 from •-phase to β-phase.42,44 In Figure 7 (left) the41 corresponding XRD data are presented.
52
53 Comparison with reference data and with Figure 1 shows that in the material a phase transfer from •-
54
55
56 Phase (300°C) to β-Phase (400°C), and back to •-Phase (700°C) is induced due to different
57
58 thermodynamic stabilities.40 The corresponding integrated luminescence intensities of these three
59
60
18
tempered materials are shown in Figure 7 (right) for the emission band G2. The maximum of
1
2
3 upconversion luminescence shifts to higher temperatures with increasing amount of β-phase (sample
4
5 tempered at 400°C) and then back to lower temperatures because of the back transfer from β-phase to •-
6
7
8 phase (sample tempered at 700°C). This experiment underlines the importance of the host lattice for the
9
10 temperature dependence of the luminescence properties of UCNP and it further shows that with the
11
12 adjustment of the Gd3+ content temperature sensitivity range of the UCNP can be tailored.
13
14
15
16
17
18
19
20
21
22
23
24
25
26
27
28
29
30
31
32
33
34
35
36
37
38
39
40
41
42
43
44
45
46
47 Figure 7: UCNP0 at three different temperatures are shown. Left: X-ray diffraction patterns. The blue
48
49 dotted lines represents die •-phase und the red one the β-phase. Right: Normalized upconversion
50
51
52 luminescence intensity of band G2 and R after different thermal treatments as function of temperature.
53
54
55 A similar temperature dependence has been reported by Zhang et al. for NaYF4:Yb3+/Er3+
56
57 nanoparticles.14,41 They found that the temperature, at which the maximum luminescence intensity was
58
59
60 observed, was dependent on the size of the nanoparticles. On the other hand, for bulk NaYF4:Yb3+/Er3+
19
powders a different temperature effect was observed. For bulk powders of Yb3+/Er3+ co-doped NaYF4,
1
2
3 barium-thorium fluoride or chalcogenide glasses after an initial increase the luminescence intensity is
4
5 reaching a plateau and stays constant when further lowering the temperature.13,33 The difference in the
6
7
temperature dependence of bulk materials and nanoparticles is related to the extent of electron-phonon
8
9
10 coupling, which is stronger in nanoparticles.13,18
11
12 In Yb3+ the two lowest energy crystal field components of the 2F5/2 multiplet are 2F5/2|0> (~10281 cm-
13
14 1
15 ) and 2F5/2|1> (~10242 cm-1).39 The temperature dependent emission is determined by population as
16
17 well as the excitation cross-section of the 2F5/2|0> and 2F5/2|1> levels of Yb3+, since both parameters are
18
19 temperature dependent. For thermal equilibrium the Boltzmann coefficient N1/N0 = 0.84 at room
20
21
22 temperature is very high, which is a consequence of the very low energy difference of 39 cm-1 between
23
24 the two Stark levels.
25
26
27
28
29
30
31
32
33
34
35
36
37
38
39
40
41
42
43
44
45
46 Figure 8: Excitation emission spectra of UCNP15 at T = 295 K and T = 85 K. (λem = 540 nm).
47
48
49
50
51
52
In Figure 8 the excitation spectra of UCNP15 at room temperature and at 80 K are shown. Due to
53
54 thermal equilibration only one broad emission band at λex = 976 nm is found at room temperature.
55
56 However, at T = 80 K the broad emission is split into two emission bands and the energy difference of
57
58
59 39 cm-1 fits very to the energy difference of the Stark levels 2F5/2|0> and 2F5/2|1> of Yb3+. Figure 8
60
20
further shows that the intensity of the 2F5/2|0>-related peak is approx. ten-times higher compared to the
1
2 2
3 F5/2|1> related emission. Since the excitation spectra were constructed based on the Er3+ emission
4
5 intensity under variation of the excitation wavelengths, the intensity distribution could be due to
6
7
differences (i) in the transfer efficiency from Yb3+ to Er3+ and/or (ii) in the absorption cross section of
8
9
10 the Yb3+ Stark levels involved. It is known that the excitation cross section of the 2F5/2|0> Stark level is
11
12 larger, but on the other hand with respect to energy matching between Yb3+ and Er3+ the transfer from
13
14
15
the 2F5/2|1> Stark level is more efficient. A nearly perfect resonance is given for level 2F5/2|1> of Yb3+
16
17 and 4I11/2|0> of Er3+. For the overall process of generating upconversion luminescence thermal
18
19 2
population of the F5/2|1> Stark level is important. Consequently the temperature dependent
20
21
22 luminescence is defined by the Boltzmann fraction in the 2F5/2|0> state and the excitation cross-section
23
24 of Yb3+, which is also temperature dependent. Therefore the upconversion luminescence intensity Ii can
25
26 be written as:13,33,46,47
27
28
( ∆+
29 # = $#,& '− ,) / 0123 (4)5() (4)
- .
30
31
32 Ni,∞ the population of the emission band in the high energy limit and ∆E denotes the energy
33
34
35 difference between the 2F5/2|0> and 2F5/2|1> states of Yb3+. Further, kB is the Boltzmann constant and pi
36
37 is the number of photons required for the excitation of band i. Finally σYb(T) describes the temperature
38
39
40 dependence of the (Lorentzian) excitation cross-section of Yb3+ and can be written as;
41
,- .
42 123 (4) ∝ exp (− +:
) (5)
43
44
45 The fitting parameter Eq is an empirical quenching energy. This equation is restricted to resonant
46
47 energy transfers from 2F5/2|1> of Yb3+ to 4I11/2|0> of Er3+. Hence, no phonon mediated energy transfer
48
49
50
step is considered in this approximation.
51
52
53
54
55
56
57
58
59
60
21
1
2
3
4
5
6
7
8
9
10
11
12
13
14
15
16
17
18
19
Figure 9: Integrated upconversion luminescence intensities (dots) of UCNP60 for G2 as a function of
20
21 temperature. The solid line represents the data analysis of the experimental data according to equation 4.
22
23
24 As an example in Figure 9 the analysis of the experimental data of UCNP60 using equation 4 for the
25
26
27
luminescence band G2 as a function of temperature is shown. The low temperature regime was
28
29 reasonable fit be equation 4. For higher temperatures, larger deviations between the model and the
30
31 experimental data were found. This indicates that at low temperatures the influence of the Stark
32
33
34 splitting, the energy match between activator and sensitizer, and the absorption cross section are the
35
36 determining parameters in the upconversion process, but at higher temperature another factor has to be
37
38 considered. Here, the electron phonon coupling needs to be considered.
39
40
41
42
43 Temperature dependent Upconversion Luminescence for T > 273 K: Not only the Yb3+- and
44
45 subsequent energy transfer related processes are temperature dependent, but also the population of
46
47
48 different energy levels of Er3+ are influence by the temperature (e.g., the 2H11/2 and the 4S3/2 level from
49
50 which the G1 and G2 luminescence originates).41
51
52
53
For T > 273 K the correlation of the luminescence intensity ratio (R = G1/G2) and the temperature T
54
55 can be described by an Arrhenius type equation.16,45
56
57 < ∆+=/="
58 ; = <= = exp >− ,- .
@ (6)
="
59
60
22
R is the ratio of integrated luminescence intensity originating from band G1 and G2 which are
1
2
3 separated by the energy gap ∆EG1/G2, kB is the Boltzmann constant, T is the temperature and A is a
4
5 constant which depends on the spontaneous emission rate and the energies of the emitting states in the
6
7
host material.
8
9
10 For the higher temperature range (T>273 K) the data were evaluated according to equation 6. From
11
12 Figure 10 (left) it can be seen that R is changing with temperature, because the relative intensity of the
13
14
15 G1-related luminescence is increasing. This is a consequence of the thermally induced re-distribution in
16
17 population between the energy levels 2H11/2 and 4S3/2 (see Scheme 1). Especially for higher temperatures
18
19 (T > 273 K) a distinct change with temperature was found, which is connected to the fact that the energy
20
21
22 gap ∆EG1/G2 is in the order of a few hundred wavenumbers depending on the host lattice.
23
24
25
26
27
28
29
30
31
32
33
34
35
36
37
38
39
40
41
42 Figure 10: Left: Analysis of UCNP0 sample data temperature dependence of the logarithm of the
43
44
45 integrated emission intensity ratio of band G1 and G2. Right: Energy gap ∆EG1/G2 as a function of Gd3+
46
47 concentration.
48
49
50
51
52
53 For UCNP0 an energy gap ∆EG1/G2 = 812 ± 8 cm-1 was determined, which correlates very well with the
54
55 data of Carnall et al. who studied the energy level assignments for Er3+ in several host lattices.39,49
56
57
58 Figure 10 (right) shows the calculated energy gaps ∆EG1/G2 of the UCNPx. A distinct impact of the Gd3+
59
60
23
concentration on the ∆EG1/G2 in the different UCNPx was found. ∆EG1/G2 decreases with increasing Gd3+
1
2
3 concentration and finally reached a minimum value of 680 cm-1 for Gd3+ concentration of 45 mol%.
4
5 Higher concentration of Gd3+ ions showed no further decrease of ∆EG1/G2. These results further
6
7
corroborate the results of the XRD and luminescence decay time measurements, in which the strong
8
9
10 influence of the Gd3+ on the host lattice and subsequently on the luminescence properties was observed
11
12 too (vide supra). Due to the Gd3+ ions the Stark splitting of the 4S3/2 level is increased resulting in a
13
14
15
smaller energy gap ∆EG1/G2 because the lowest Stark level of 2H11/2 and the highest Stark level of 4S3/2
16
17 moved closer together. Associated with the decreasing ∆EG1/G2 is an enhanced population of the energy
18
19 level 2H11/2 due to thermal equilibration (Boltzmann distribution) leading to an increasing luminescence
20
21
22 intensity of G1 relative to G2. A selection of the upconversion emission ratios of band G1 and G2 in
23
24 dependence of Gd3+ concentration are shown in Table 3. The increasing ratio RG1/G2 with the gradually
25
26 increasing amount of Gd3+ in the host lattice is caused by the decreasing energy gap ∆EG1/G2 showing a
27
28
29 very good correlation to the initial results.
30
31
32
33
34 Tab.3: Ratio RG1/G2 of the upconversion luminescence of G1 and G2 for different UCNPx at different
35
36 temperatures.
37
38
39 Temperature [K] UCNP0 UCNP30 UCNP80
40
41 120 - - 0.09
42
43 160 0.07 0.12 0.14
44
45 209 0.11 0.17 0.22
46
47 303 0.26 0.27 0.37
48
49 313 0.30 0.31 0.38
50
51 323 0.33 0.35 0.46
52
53 328 0.35 0.37 0.49
54
55
56
57
58 Based on equation 6 the absolute Sa and relative sensor sensitivity Sr can be obtained. 49-52
59
60
24
1
2
EF ∆+=/="
3 AB ~ D D ~ ; (7)
E. ,. "
4
5
6
7
8 EF ∆+=/="
9 AG ~ 100% D D ~ 100% (8)
F E. ,. "
10
11
12 The temperature sensitive calculated value of Sa and Sr are shown in Figure 11. The maximum value of
13
14 Sr of 1.35 % K-1 was found at 303 K which is slidely higher (among the highest Sr which can be found
15
16
in the literature) to typical values of NaYF4:Yb3+:Er3+ or other new host lattices of upconverters like
17
18
19 GdVO4:Yb3+:Er3+.49 The temperature resolution of ~ 0.37 K was obtained from δR/Sa where δR is the
20
21 standard deviation of the residuals in the polynomial interpolation of the experimental data points
22
23
24 (temperature vs R = IG1/IG2).
25
26
27
28
29
30
31
32
33
34
35
36
37
38
39
40
41
42
43
44
45
46
47 Figure 11: Absolute (black line) and relative (red line) sensitivity of the temperature sensor based on R
48
49 of the upconversion luminescence of UCNPs.
50
51
52
53
54 Conclusion:
55
56
The upconversion luminescence properties of citrate stabilized nanoparticles (UCNP) based on a NYF4
57
58
59 host matrix, which was doped with Yb3+ and Er3+ as sensitizer and activator, respectively, were studied.
60
25
In order to tailor the UCNP properties different amounts of Gd3+ were co-doped. The luminescence
1
2
3 properties UCNP were characterized and the temperature dependence of different luminescence
4
5 parameters (spectral intensity distribution, decay kinetics) were analyzed for the temperature range of 4
6
7
K < T < 328 K. In complementary measurements using XRD, TEM, and DLS the distinct alteration of
8
9
10 fundamental properties such as particle size and crystal phase depending on the Gd3+ content were
11
12 found. With increasing Gd3+ content the particle size obtained decreased from 274 nm to 46 nm for the
13
14
15
highest Gd3+ content tested. Here, the Gd3+ ions increase the effective surface charge which is a key
16
17 factor for the crystal growth rate. In addition, also the type of crystal phase was shifted from the cubic
18
19 •-phase to the hexagonal β-phase. Both, decreasing particle size and crystal phase change were reflected
20
21
22 in the upconversion luminescence properties of the particles. The overall luminescence intensity first
23
24 increased with increasing Gd3+ concentration due to the change of the host lattice to the β-phase, which
25
26
27
is known to improve the luminescence. On the other hand the volume to surface ratio was also changed
28
29 and the higher relative surface area lead to an enhanced luminescence quenching due to interactions
30
31 (e.g., with solvent molecules like water) at the particle surface. This effect became dominant for high
32
33
34 Gd3+ concentrations. This was also supported by the luminescence decay kinetics. Not only the overall
35
36 luminescence intensity was dependent on the degree of Gd3+ doping but also the spectral distribution
37
38 which gives a unique opportunity for multiparameter sensing or labeling applications. Here, the
39
40
41 particles, which are identical with respect to their fundamental chemical reactivities (e.g., surface
42
43 functionalization), may be used as multicolor labels which can be identified by their emission pattern.
44
45
The interplay between intensity as well as spectral distribution and the Gd3+ content was further
46
47
48 investigated by recording the temperature dependence of different photophysical parameters. Especially
49
50 the application of high-resolution luminescence spectroscopy at ultra-low temperature in combination
51
52
53
with narrow banded excitation proved to be a valuable tool to shed light on the different population
54
55 processes involved for the sensitizer (Yb3+) and activator (Er3+). The temperature profile of the
56
57 luminescence intensity as well as the intensity distribution (e.g., ratio of the green and red emission) was
58
59
60 strongly depending on the Gd3+-content. The intensity ration of the different Er3+ luminescence bands
26
can be envisioned to be used as a nanothermometer, e.g., to measure the temperature spatially resolved
1
2
3 in tissues.
4
5
6 Acknowledgment: We are thankful to Dr. C. Günter and Dr. C. Prietzel (work group of Prof. J. Kötz)
7
8 who performed the structural studies (XRD- and TEM-studies) of the samples. We further thank Prof. E.
9
10
11 Rühl for fruitful discussions as well as Dr. J. Traeger and Prof. H.-J. Holdt who performed the ICP-OES
12
13 analysis for us.
14
15
16 Supporting Information Available: TEM image of UCNP NaYF4: Yb/Er (18/2 mol %) with a Gd3+
17
18
19 dopand concentration of 45 mol %. Upconversion luminescence spectra of NaYF4: Yb/Er (18/2 mol %)
20
21 with various Gd3+ dopand concentration and various temperatures. Excitation spectra and results of ICP-
22
23 OES studies of the as-prepared UCNP at various Gd3+ dopand concentration. This material is available
24
25
26 free of charge via the Internet at http://pubs.asc.org.
27
28
29
30
31
32 References:
33
34
35 1. Kuningas, K.; Ukonaho, T.; Päkkilä, H.; Rantanen, T.; Rosenberg, J.; Lövgren, T. & Soukka, T.
36
37 Upconversion Fluorescence Resonance Energy Transfer in a Homogeneous Immunoassay for Estradiol.
38
39
40
Anal. Chem. 2006, 78, 4690 – 4696.
41
42
43 2. Soukka, T.; Rantanen, T. & Kuningas, K. Photon Upconversion in Homogeneous Fluorescence-
44
45 based Bioanalytical Assays. Ann. NY. Acad Sci. 2008, 1130, 188 - 200.
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47
48 3. Chen, N.-T.; Cheng, S.-H.; Liu, C.-P.; Souris, J. S.; Chen, C.-T.; Mou, C.-Y. & Lo, L.-W. Recent
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50
51 Advances in Nanoparticle-Based Förster Resonance Energy Transfer for Biosensing, Molecular
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53 Imaging and Drug Release Profiling. Int. J. Mol. Sci. 2012, 13, 16598 - 16623.
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55
56 4. Lee, D.-E.; Koo, H.; Sun, I.-C.; Ryu, J. H.; Kim, K. & Kwon, I. C. Multifunctional nanoparticles
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58
59 for multimodal imaging and theragnosis Chem. Soc. Rev. 2012, 41, 2656 - 2672.
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5. Liu, Y.; Tu, D.; Zhu, H. & Chen, X. Lanthanide-doped luminescent nanoprobes: controlled
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3 synthesis, optical spectroscopy, and bioapplications. Chem. Soc. Rev. 2013, 42, 6924 - 6958.
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5
6 6. Min, Y.; Li, J.; Liu, F.; Padmanabhan, P.; Yeow, E. K. L. & Xing, B.
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8 Recent Advance of Biological Molecular Imaging Based on Lanthanide-Doped Upconversion-
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11 Luminescent Nanomaterials. Nano.Mat. 2014, 4, 129 - 154.
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14 7. Sun, L.-D.; Wang, Y.-F. & Yan, C.-H. Paradigms and Challenges for Bioapplication of Rare Earth
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16 Upconversion Luminescent Nanoparticles: Small Size and Tunable Emission/Excitation Spectra.
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18
19 Accounts Chem. Res. 2014, 47, 1001 - 1009.
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22 8. Gorris, H. H. & Wolfbeis, O. S. Photonen aufkonvertierende Nanopartikel zur optischen Codierung
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24 und zum Multiplexing von Zellen, Biomolekülen und Mikrosphären
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27 Angew. Chem. 2013, 125, 3668 - 3686.
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30 9. Zhou, J.; Liu, Z. & Li, F. Upconversion nanophosphors for small-animal imaging. Chem. Soc. Rev.
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32 2012, 41, 1323 - 1349.
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34
35 10. Wang, F.; Han, Y.; Lim, C. S.; Lu, Y.; Wang, J.; Xu, J.; Chen, H.; Zhang, C.; Hong, M. & Liu, X.
36
37
38 Simultaneous phase and size control of upconversion nanocrystals through lanthanide doping Nature
39
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Dennis T Klier, and Michael U. Kumke

The Journal of Physical Chemistry C is published by the American Chemical Society.

21. van der Ziel, J. P.; Ostermayer, F. W. & Van Uitert, L. G.

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