High Resolution Image Download MS PowerPoint Slide Spectral conversion of sunlight can enhance solar cell efficiencies by shifting short-wavelength photons to longer wavelengths, where the photovoltaic response is stronger. This can be realized with near 100% energy efficiency by materials capable of quantum cutting . These emit two longer-wavelength photons, following the absorption of one shorter-wavelength photon. Although various quantum-cutting materials have been reported, follow-up research has often disproved initial claims. Here, we demonstrate that photon correlation analysis is a universal strategy to unambiguously identify quantum cutting. We investigate two materials, YPO 4 codoped with Tb 3+ and Yb 3+ and yttrium aluminum garnet (YAG) codoped with Ce 3+ and Yb 3+ . Both are reported to perform quantum cutting via blue light absorption followed by cooperative energy transfer to near-infrared-emitting Yb 3+, but some studies have cast doubts for YAG:Ce 3+,Yb 3+ . Our correlation analysis demonstrates bunched emission for YPO 4:Tb 3+,Yb 3+, confirming quantum cutting. In contrast, YAG:Ce 3+,Yb 3+ shows Poissonian emission statistics, disproving its quantum-cutting capability, despite previous claims.
Abstract Quantum cutting (QC) is a process that can split one high-energy photon into two or more low-energy photons.1-4 As an attractive mechanism, it has been extensively explored for acquiring high quantum efficiency (QE) of more than 100%.5-8 Here, we report the first experimental observation of multiphoton QC with ultrahigh QEs in CaF2:Yb polycrystalline. Under 266 nm excitation, an internal quantum efficiency as high as ~285% was achieved, indicating that one ultraviolet (UV) photon was split into more than two ~1000 nm near infrared (NIR) photons. Photovoltaic experiments demonstrated that the polycrystalline increased the output power of a polycrystalline silicon solar cell by more than 200% in the case of 266 nm irradiation. Spectral analysis confirmed that the ultrahigh QE originated from efficient cooperative absorptions of Yb-tetramers and Yb-trimers and individual emission of single Yb3+ ions. This study provides a promising approach for improving spectral response of silicon solar cells and detectors in the UV region.
The deposition of a thin layer of a quantum-cutter material on top of silicon-based solar cells seems to be a promising solution to reduce the thermalization losses. This mechanism has been reported in materials codoped with Pr3+-Yb3+, where Pr3+ can sensitize two Yb3+ ions for one absorbed blue photon. In the present Letter, we analyze precisely energy transfers between Pr3+ and Yb3+ in CaYAlO4, and we measure a quantum-cutting rate of 145%. We show that a very efficient back transfer from Yb3+ toward the (1)G4 level of Pr3+ ion leads to a strong reduction of the quantum yield.
Abstract In optical materials energy is usually extracted only from the lowest excited state, resulting in fundamental energy-efficiency limits such as the Shockley–Queisser limit for single-junction solar cells. Photon-cutting materials provide a way around such limits by absorbing high-energy photons and ‘cutting’ them into multiple low-energy excitations that can subsequently be extracted. The occurrence of photon cutting or quantum cutting has been demonstrated in a variety of materials, including semiconductor quantum dots, lanthanides and organic dyes. Here we show that photon cutting results in bunched photon emission on the timescale of the excited-state lifetime, even when observing a macroscopic number of optical centres. Our theoretical derivation matches well with experimental data on NaLaF4:Pr3+, a material that can cut deep-ultraviolet photons into two visible photons. This signature of photon cutting can be used to identify and characterize new photon-cutting materials unambiguously.
The efficiency of single-junction solar cells is limited to about 30% (the Shockley-Queisser limit). Spectral mismatch losses (transparency to low-energy photons, thermalization of high-energy photons) strongly contribute to lowering the maximum efficiency. To reduce thermalization losses, photon splitting is proposed and observed for a variety of lanthanide-doped materials. For
Er3+, even a one-to-three photon-splitting process has been reported, yielding three IR photons at around 1530 nm following absorption of one blue-green photon. This is especially beneficial for narrow band gap solar cells, such as crystalline
Ge. Here, we report on photon splitting for
Er3+ in
YVO4. Following absorption in the
2H11/2 and
4S3/2 levels (520--550 nm), efficient cross-relaxation (CR) yields two excited
Er3+ ions: one in the
4I9/2 state and one in the
4I13/2 state (CR1). A second CR step from the
4I9/2 state, leaving both
Er3+ ions in the
4I13/2 excited state (CR2), is crucial in realizing efficient three IR photon splitting. It is demonstrated here that the second step has a low efficiency, as a result of competing fast multiphonon relaxation, ${}^{4}{\mathrm{I}}_{9/2}{\ensuremath{\rightarrow}}^{4}{\mathrm{I}}_{11/2}$, and a large energy mismatch, which makes the CR2 step thermally activated. Based on experiments and theory, a maximum quantum efficiency of 170% is calculated for IR emission, following blue-green excitation in
YVO4:Er3+. An outlook is presented for three-photon splitting in low-phonon-energy hosts, where nonradiative multiphonon relaxation is suppressed. The anti-Stokes nature of the second CR step makes three-photon splitting unlikely and prevents the realization of IR quantum yields above 200%.
The infrared quantum cutting phenomena, which is an international hot research field, of Er1.0P5O14 noncrystalline glass are studied by the present paper for the first time. The 1537.0nm infrared fluorescence of Er1.0P5O14 noncrystalline glass is confirmed to be the multi-photon quantum cutting fluorescence by computation and comparison between absorption and excitation spectra. It is found that the 4I13/2→4I15/2 quantum cutting fluorescence is very strong, induced by the excited 2H11/2, 4G11/2, and 4G9/2 energy levels. Its mechanism is thoroughly analyzed based on the calculation of spontaneous emission rates, nonradiative multiphonon relaxation rates and energy transfer rates. It is found the strong downconversion energy transfers {2H11/2→4I9/2,4I15/2→4I13/2},{4G11/2→4I13/2, 4I15/2→2H11/2},{4G9/2→4F7/2,4I15/2→4I13/2} 和 {4G9/2→4I13/2, 4I15/2→2H11/2} are responsible for the strong infrared three-photon and four-photon quantum cutting fluorescence of Er1.0P5O14 noncrystalline glass. The present research is significant for enhancing solar cell efficiency.
Efficient three-step sequential three-photon near-infrared (NIR) quantum cutting in Tm3+-doped transparent oxyfluoride glass ceramics has been demonstrated, where an absorbed blue photon could be cut into three NIR photons at 1190, 1460, and 1800 nm with quantum yield greater than unity. On the basis of static and dynamic photoemission, monitored excitation, and time-resolved fluorescence spectra, we investigate in detail the underlying optoelectronic mechanism. Further development of an efficient triply-cutting material might open up a path towards ultra-efficient photonic devices, which enables more photons emitted than absorbed in the excitation process.