In this paper, the upconversion luminescent properties of Y2O3:Er3+(1%)/Yb3+(4%) nanoparticles with different sizes (13−55 nm) and its corresponding bulk material as a function of excitation power were studied under 978-nm excitation. Red (4F9/2 → 4I15/2), green (2H11/2, 4S3/2 → 4I15/2), and blue (2H9/2 → 4I15/2) transitions were observed. The results indicated that the relative intensity of the blue as well as the red to the green increased gradually with decreasing particle size. As a function of excitation power, the slope in the ln−ln plot for the red emission changed between 2.0 and 1.0 and gradually decreased with increasing particle size, which was attributed to competition between linear decay and upconversion processes for the depletion of the intermediate excited states. As the particle size decreased to 13 nm, a three-photon populating process occurred for the green emission. As the excitation power varied in different paths, gradually increasing or gradually decreasing, a hysteresis loop appeared in the power dependence of emission intensity, which was mainly caused by a local thermal effect induced by laser irradiation. The intensity ratio of 2H11/2 → 4I15/2 to 4S3/2 → 4I15/2 (R HS ) varied complicatedly with excitation power, which was theoretically explained considering the thermal distribution and relaxation processes. Two novel cross-relaxation paths were proposed on the basis of the variation of R HS under excitation at different wavelengths, 488 and 978 nm.
Broadband near‐infrared (NIR) phosphor‐converted light emitting diode (pc‐LED) is demanded for wearable biosensing devices, but it suffers from low efficiency and low radiance. This study reports a broadband NIR Ca3‐xLuxHf2Al2+xSi1−xO12:Cr3+ garnet phosphor with emission intensity enhanced by 81.5 times. Chemical unit co‐substitution of [Lu3+−Al3+] for [Ca2+−Si4+] is responsible for the luminescence enhancement and further alters the crystal structure and electronic properties of the garnet. Using the optimized phosphor, a NIR pc‐LED with photoelectric efficiencies of 21.28%@10 mA, 15.75%@100 mA and NIR output powers of 46.09 mW@100 mA, 54.29 mW@130 mA is fabricated. The high power NIR light is observed to penetrate upper arms (≈8 cm). For application in NIR spectroscopy, the NIR pc‐LED is used as light source to measure transmission spectra of water, alcohol, and bovine hemoglobin solution. These results indicate the NIR garnet phosphor to be a promising candidate for NIR pc‐LED.
The garnet Ca2LuZr2Al3O12 (CLZA) is a promising broad-band NIR phosphor for blue LED chips when it is doped with Cr3+.
In this paper, the upconversion luminescent properties of Gd2O3:Er3+,Yb3+ nanowires as a function of Yb concentration and excitation power were studied under 978-nm excitation. The results indicated that the relative intensity of the red emission (4F(9/2)-4I(15/2)) increased with increasing the Yb3+ concentration, while that of the green emission (4S(3/2)/2H(11/2)-4I(15/2)) decreased. As a function of excitation power in ln-ln plot, the green emission of 4S(3/2)-4I(15/2) yielded a slope of approximately 2, while the red emission of 4F(9/2)-4I(15/2) yielded a slope of approximately 1. Moreover, the slope decreased with increasing the Yb3+ concentration. This was well explained by the expanded theory of competition between linear decay and upconversion processes for the depletion of the intermediate excited states. As the excitation power density was high enough, the emission intensity of upconversion decreased due to thermal quenching. The thermal effect caused by the exposure of the 978-nm laser was studied according to the intensity ratio of 2H(11/2)-4I(15/2) to 4S(3/2)-4I(15/2). The practical sample temperature at the exposed spot as a function of excitation power and Yb3+ concentration was deduced. The result indicated that at the irradiated spot (0.5 x 0.5 mm2) the practical temperature considerably increased.
The rare earth Er 31 and Yb 31 codoped system is the most attractive for showcasing energy transfer upconversion. This system can generate green and red emissions from Er 31 under infrared excitation of the sensitizer Yb 31 . It is well known that the red-emitting state can be populated from the upper green-emitting state. The contribution of multiphonon relaxation to this population is generally considered important at low excitation densities. Here, we demonstrate for the first time the importance of a previously proposed but neglected mechanism described as a cross relaxation energy transfer from Er 31 to Yb 31 , followed by an energy back transfer within the same Er 31 -Yb 31 pair. A luminescence spectroscopy study of cubic Y 2 O 3 :Er 31 , Yb 31 indicates that this mechanism can be more efficient than multiphonon relaxation, and it can even make a major contribution to the red upconversion. The study also revealed that the energy transfers involved in this mechanism take place only in the nearest Er 31 -Yb 31 pairs, and thus, it is fast and efficient at low excitation densities. Our results enable a better understanding of upconversion processes and properties in the Er 31 -Yb 31 system. Light: Science & Applications (2015) 4, e239; doi:10.1038/lsa.2015.12; published online 16 January 2015 Keywords: energy transfer; erbium-ytterbium system; upconversion luminescence INTRODUCTION Infrared to visible upconversion luminescence has been extensively studied for its fundamental value 1-3 and its various potential applications in upconversion lasers, 4 bioimaging, 5 etc. The codoping of Er 31 and a high concentration of sensitizer Yb 31 forms the most attractive energy transfer upconversion (ETU) system. Under infrared (980 nm) excitation of the sensitizer Yb 31 , this system can generate green and red upconversions originating from the 4 S 3/2 R 4 I 15/2 and 4 F 9/2 R 4 I 15/2 transitions of Er 31 , respectively. Unlike the green upconversion, the red upconversion benefits from several possible excitation mechanisms. 6,7 Multiphonon relaxation (MPR) from the upper 4 S 3/2 state and ETU from the lower intermediate 4 I 13/2 state are generally considered dominant at low infrared excitation densities because other mechanisms involving three photon processes 6,7 become important only at high infrared excitation densities, 8 which is not the topic of this work.The MPR is not the only mechanism for populating the 4 F 9/2 from the 4 S 3/2 ; a non-MPR mechanism was proposed earlier, 8 but it has not been considered important since then. This mechanism involves two sequential energy transfers between Er 31 and Yb 31 . The first step is a well-known cross-relaxation (CR) energy transfer from Er 31 in the
One-dimensional pure cubic Y(2)O(3)/Eu(3+) nanocrystals (NCs) were synthesized by a hydrothermal method at various temperatures. The NCs prepared at 130 degrees C yielded nanotubes (NTs) with wall thickness of 5-10 nm and outer diameter of 20-40 nm. The NCs prepared at 170 and 180 degrees C yielded nanowires (NWs) with diameters of approximately 100 and approximately 300 nm, respectively. Their luminescent properties, including electronic transition processes, local environments surrounding Eu(3+) ions, electron-phonon coupling, and UV light irradiation induced spectral changes have been systematically studied and compared. The results indicate that the Y(2)O(3)/Eu(3+) NTs and NWs have strong red (5)D(0)-(7)F(2) transitions. The fluorescence lifetime of (5)D(1)-(7)F(1) hardly changes in different samples, while that of (5)D(0)-(7)F(2) decreases a small amount in Y(2)O(3)/Eu(3+) NTs. The (5)D(0)-(7)F(2) lines originate from the emissions of Eu(3+) ions occupying one C(2) site, like that in the bulk powders. The phonon sideline with a frequency shift of 40-50 cm(-1) appears at the low-energy side of the (7)F(0)-(5)D(0) zero phonon line. The relative intensity of the sideline to zero phonon line increases by varying from NTs to NWs, and the spectral position of the phonon sideline shifts red. The UV light irradiation induced spectral change in the charge-transfer band was studied. The results indicate that the spectral change is dependent on sample size and is wavelength selective. A detailed model was proposed to explain the light-induced spectral change.
A single-layer polymer stabilized liquid crystal (PSLC) film reflecting both right- and left-circularly polarized light has been developed by a wash-out/refill method. The PSLC film was achieved by prefabricating the polymer network with a left-handed helical structure and then refilling a cholesteric liquid crystal with a right-handed helical structure into the network. The reflection intensity of the PSLC film is close to 100% when the pitch lengths of the two opposite helical structures are the same. It was demonstrated that the memory effect of the polymer network is an important mechanism for the resulting film properties.
A blue phase with a broad temperature range of about 23.0 °C is easily achieved in a hydrogen‐bonded self‐assembled complex of chiral fluoro‐substituted benzoic acid and pyridine derivative. The success in extending the temperature of blue phase indicates that the hydrogen‐bonded self‐assembly is a promising new approach to broaden the temperature range of blue phases and to investigate the mystery of blue phases.
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