The luminescence properties of Dy3+ and Tb3+ single- as well as Dy3+ / Tb3+ double-doped barium borate glasses are investigated for their potential as light-converter. In double-doped barium borate glass an energy transfer from Dy3+ to Tb3+ is observed, i.e., an intense green luminescence from the doped Tb3+ ions results upon excitation at Dy3+-related absorption bands. Ray-tracing simulations allow for an evaluation of singleand double-doped light guides in different length. Here, the luminous flux and luminance values at the rough output face of a luminescent light guide are determined.
Rare-earth doped borate glasses are investigated for their potential as photon down-shifting cover glass for CdTe solar cells. Note, that CdTe solar cells have a poor response in the ultraviolet and blue spectral range due to absorption in the CdS buffer layer having a band gap of 2.4 eV. The following trivalent rare-earth ions are analyzed in detail: Sm3+, Eu3+, and Tb3+. These ions provide strong absorption bands in the ultraviolet / blue spectral range and an intense emission in the red (Sm3+ and Eu3+) or green (Tb3+) spectral range. The gain in short-circuit current density of a CdTe solar cell is calculated for different rare-earth ion concentrations. The calculations are based on the rare-earth’s absorption coefficients as well as their photoluminescence (PL) quantum efficiency. For Sm3+, the PL quantum efficiency depends significantly on the doping concentration. Finally, the potential of double-doped borate glasses, i.e. glasses doped with two different rare-earth ions, is investigated.
Neodymium-doped barium borate glasses are investigated for their potential as fluorescent concentrators for the near
infrared spectral range. Additional doping of the glasses with silver oxide and subsequent heat treatment leads to a reduction
of the doped silver ions and to the formation of metallic silver nanoparticles. The formation of the silver nanoparticles
is indicated by a broad surface plasmon-related extinction band at approximately 410 nm. The influence of the
silver nanoparticles on the fluorescence properties is investigated.
Transparent, rare-earth doped fluorozirconate-based glasses and glass ceramics are attractive systems as up- and downconverters
to increase solar cell efficiency. For down-conversion applications, the efficiency of a silicon solar cell could
be significantly increased in the ultraviolet spectral range by placing a europium-doped glass ceramic on top. High
transparency is a key issue here to avoid scattering losses and to obtain high light output. Transmission spectra of fluorozirconate
glasses, which were additionally doped with chlorine ions to initiate the growth of BaCl2 nanoparticles
therein upon thermal annealing, show that the absorbance in the visible spectral depends significantly on the annealing
conditions. For up-conversion applications, erbium-doped fluorozironate glasses have been investigated. 2-dimensional
intensity mapping of the up-converted fluorescence yielded information on the homogeneity of the glass sample and the
erbium distribution therein. Depth scan experiments showed that the position of the focus of the excitation laser beam
plays a crucial role since saturation of the 2-photon up-conversion occurs for high excitation power.
Transparent glasses as up- or down-converters are attractive systems to increase the efficiency of solar cells. Er-doped
fluorozirconate (FZ) glasses show an intense up-conversion upon excitation at 1540 nm. Transmission spectra show that
the absorbance at 1540 nm grows linearly with the Er-doping level. In Eu-doped FZ glasses, which were additionally
doped with chlorine ions, the growth of BaCl2 nanocrystals can be observed upon thermal annealing. For high annealing
temperatures a phase change from hexagonal to orthorhombic phase BaCl2 can be seen. Upon excitation in the ultraviolet
(UV) spectral range these glass ceramics emit an intense blue emission. A combination of a silicon solar cell and an
Eu-doped FZ glass ceramic as a down-converting top layer shows an increase in the short circuit current in the UV
spectral range compared to a solar cell without a down-converting top layer.
The efficiency of thin film solar cells can be improved with the addition of a photon down-conversion top layer. This
layer converts incident ultraviolet light of the solar spectrum to visible light, which transmits through the glass and is
efficiently absorbed by the active layer of the solar cell. The results of our investigations of thin dielectric films and
fluorozirconate glass, both doped with Tb3+ ions, are presented. Tb3+ has absorption bands between 250 and 380 nm; the
corresponding emission bands are in the spectral range between 400 and 630 nm. Thin SiO2 and Al2O3 films with 0.04 -
10.18 at.% Tb were prepared by co-sputtering. For both as-deposited film systems, the highest fluorescence intensity is
found for a Tb3+ doping level of approximately 1 at.%; the fluorescence intensity of Tb3+ in SiO2 is higher than that in
Al2O3. Thermal treatment leads to an enhancement of the fluorescence intensity by more than one order of magnitude
and the highest fluorescence intensity is found for 2 at.% Tb for annealed thin SiO2 films containing Tb3+. For
comparison, the absorption and emission properties of Tb3+-doped fluorozirconate glass are investigated for a doping
level of 0.3 at.% Tb.
KEYWORDS: Glasses, External quantum efficiency, Luminescence, Solar cells, Upconversion, Photons, Near infrared, Silicon solar cells, Doping, Solar energy
Transparent erbium-doped fluorozirconate (FZ) glasses are attractive systems for upconversion-based solar cells. Upconverted
fluorescence intensity vs. excitation power dependence was investigated for a series of erbium-doped FZ
glasses. It was found that the ratio of the 2-photon upconverted emission in the near infrared at 980 nm to the 3-photon
upconverted emissions in the visible at 530, 550, and 660 nm decreases with increasing excitation power. The integrated
upconverted fluorescence intensity per excitation power shows "saturation" upon increasing the excitation power,
while the point of saturation shifts to lower excitation power with increasing erbium doping level. To demonstrate
the potential of these upconverters for photovoltaic applications, the external quantum efficiency (EQE) of a commercial
monocrystalline silicon solar cell with an Er-doped FZ glass on top of it was measured. For an excitation power of
1 mW at a wavelength of 1540 nm an EQE of 1.6% was found for a 9.1 mol% Er-doped FZ glass. The samples investigated
were not optically coupled to the solar cell and no optical coating was applied to the glass surface.
Thermal processing of as-made fluorozirconate glasses which were additionally doped with neodymium and chlorine
ions leads to enhanced up-conversion fluorescence intensities in these glass ceramics. The samples were annealed between
240°C and 290°C while the optimum value was found for the 270°C sample. We investigated the power dependence
of the infrared fluorescence, the 2-photon up-conversion, and the 3-photon up-conversion fluorescence intensities
as well as the corresponding radiative lifetimes. In analogy to the up-conversion intensity, the radiative lifetime of the
Nd3+ fluorescence at about 880 nm depends significantly on the annealing temperature: the longest lifetime was observed
for the 270°C sample.
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