Photon Upconversion through a Cascade Process of Two-Photon

This sequential energy transfer enables upconversion from four photons from a ... (38) Notably, LHP shows not only giant TPA cross sections of 105–1...
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Photon Upconversion through a Cascade Process of Two-Photon Absorption in CsPbBr3 and Triplet−Triplet Annihilation in Porphyrin/Diphenylanthracene Shogo Izakura,† Wenting Gu,† Ryosuke Nishikubo,† and Akinori Saeki*,†,‡ †

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Department of Applied Chemistry, Graduate School of Engineering, Osaka University, 2-1 Yamadaoka, Suita, Osaka 565-0871, Japan ‡ Precursory Research for Embryonic Science and Technology (PRESTO), Japan Science and Technology Agency, 4-1-8 Honcho, Kawaguchi, Saitama 332-0012, Japan S Supporting Information *

ABSTRACT: Photon upconversion constitutes an exceptionally rich area of research in photonics and electronics, where low-energy light is converted to high-energy light through nonlinear processes represented by two-photon absorption (TPA) and triplet−triplet annihilation (TTA). Here, we report a cascade process of TPA in inorganic perovskite quantum dots (PQDs) of CsPbBr3 and TTA in an organic molecule (9,10-diphenylanthracene) mediated by an octaethylporphyrinatoplatinum(II) (PtOEP) sensitizer. This sequential energy transfer enables upconversion from four photons from a near-infrared femtosecond laser at 800 nm to one photon at 430 nm with a large anti-Stokes shift of ∼1.3 eV. We characterize the energy transfer from PQDs to PtOEP by picosecond lifetime spectroscopy and a Stern−Volmer plot of the steady-state photoluminescence while considering dynamic and static quenching as well as trivial absorption and Förster (fluorescence) resonance energy transfer. The serial connection of TPA and TTA achieved in a simple system opens up an attractive avenue in nonlinear photonics and harvesting of low-energy photons.

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excitation photons.21,22 The efficiency of TPA is accordingly governed by its cross section in Goeppert-Mayer (GM) units (1 GM = 10−50 cm4 s photon−1), where the typical cross sections of organic molecules are on the order of 102−103 GM.2 Meanwhile, interest in organic−inorganic lead halide perovskites (LHP) was triggered by the discovery of their prominent optoelectronic properties suitable for use in solar cells,23−26 light-emitting diodes,27−30 and other functional systems such as water photolysis,31 lasing,32,33 electro-34 and thermo-chromic switching,35−37 and X-ray imaging.38 Notably, LHP shows not only giant TPA cross sections of 105−106 GM39,40 depending on the size of nanoparticles,41 but also multiphoton (three, four, and five) absorption at high intensity excitation, which provides an extremely large anti-Stokes shift from infrared (e.g., 2000 nm) to green (∼514 nm).42 Encouraged by the large TPA cross section of LHP, here, we report a cascade process of TPA and TTA, which has remained challenging so far due to the low efficiency of each process. However, the process could afford photon upconversion from

INTRODUCTION Photon upconversion is an interesting nonlinear process that converts low-energy photons to high-energy photons, contrary to the normal energy relaxation process.1−4 This unique phenomenon has been utilized in bio-imaging 5−7 and fabrication of nano-/micro-structures,8−11 and is potentially applicable in enhancing power conversion efficiency in a solar cell by converting inaccessible near-infrared (IR) sunlight to a photon energy above the bandgap energy.12−14 Two-photon absorption (TPA) and triplet−triplet annihilation (TTA) are the major processes, and many organic molecules and metal complexes have reportedly exhibited photon upconversion processes, such as green to blue15−17 and red to yellow.18−20 Emission through TTA results from a sequential process beginning with initial photoabsorption in a sensitizer and ending with emission from an acceptor. A typical molecular system is a combination of octaethyl-porphyrinatopalladium(II) (PdOEP) or octaethylporphyrinatoplatinum(II) (PtOEP) sensitizer and 9,10-diphenylanthracene (DPA) or pyrene (Py) acceptor, which allows green-to-blue upconversion with an anti-Stokes shift of ∼0.4 eV.1−3 In contrast, TPA requires a stronger excitation intensity than TTA, because TPA takes place through a virtual state with spatiotemporally confined © XXXX American Chemical Society

Received: June 8, 2018 Revised: June 14, 2018

A

DOI: 10.1021/acs.jpcc.8b05508 J. Phys. Chem. C XXXX, XXX, XXX−XXX

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The Journal of Physical Chemistry C

with/without focusing (a convex lens with a 10 cm focal length, where a quartz cell was placed 5 cm away from the lens). The photoluminescence spectrum was recorded through IR cutting filters (>800 nm) using an Ocean Optics Inc. model HR4000GG-UV-NIR spectrometer.

near-IR to near-ultraviolet without multiphotoabsorption under intense excitation. Perovskite quantum dots (PQDs) consisting of CsPbBr3 were chosen as the energy donor, owing to their high photoluminescence (PL) quantum yield (∼0.9),43−45 aforementioned large TPA cross section,39−42 and facile applicability in a colloidal solution.43 The energy in PQDs produced by TPA is designed to lead to emission from the singlet excited state (S1) of DPA formed via TTA. PtOEP acts as the sensitizer of the triplet excited state (T1), since the emission spectrum of CsPbBr3 PQDs overlaps with the Qband in PtOEP to a higher degree than PdOEP (Figure S1). Methylammonium (MA) lead bromide (MAPbBr3) is also TPA-compatible,46 but its emission peak does not match well with the porphyrin-based sensitizer. In addition, the photoluminescence quantum yield47−49 and TPA cross section42 of MAPbBr3 in its colloidal form are sensitive to size and surface modification. Thus, we characterize the energy transfer (ET) from CsPbBr3 PQDs to PtOEP and triplet transfer from PtOEP to DPA by photoluminescence and picosecond lifetime spectroscopies. The overall process is examined under excitation with nanosecond and femtosecond lasers.

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RESULTS AND DISCUSSION Energetics of Involved Chemicals. Figure 1 shows schematic illustration of the energetic scheme involved in the

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EXPERIMENTAL SECTION A deoxidized toluene solution of colloidal PQDs was prepared through ligand-assisted reprecipitation (LARP), according to a previous report.50 CsBr, PbBr2, DPA, and n-octylamine were purchased from Tokyo Chemical Industry (TCI) Co., Ltd. and PtOEP was purchased from Sigma-Aldrich Co., Llc. N,Ndimethylformamide (DMF), toluene, and oleic acid were purchased from Wako Pure Chemical Industry, Ltd. All chemicals were used without further purification. A precursor solution consisting of 5 mL of DMF, CsBr (0.16 mmol), PbBr2 (0.20 mmol), oleic acid (1 mL), and n-octylamine (50 μL) was prepared. A 0.5 mL of precursor solution was added dropwise into toluene (10 mL) under vigorous stirring, affording a green-emissive PQD colloidal solution. After removing precipitates by centrifuging at 10 000 rpm for 10 min, the PQD solution was bubbled with N2 gas for 1 h and stored in a glovebox (O2 < 0 ppm, H2O < 0 ppm). A colloidal PQD solution of toluene with 0−0.5 mM PtOEP and 0−50 mM DPA was prepared in the glovebox, accordingly. A diluted solution of each compound was prepared for UV−vis and fluorescence spectral evaluation. UV−vis and fluorescence spectroscopies were performed using a Jasco V-730 UV−vis spectrophotometer and a Jasco FP-8300 spectrometer, respectively. Photoelectron yield spectroscopy (PYS) on indium-tin-oxide glass was performed using a Bunko Keiki BIP-KV2016K instrument. Picosecond fluorescence lifetime measurements based on the time-correlated single-photon counting technique were performed using a HORIBA model FluoroCube 3000U-UltraFast-SP spectrophotometer (λex = 377 nm). A 900 nm nanosecond pulse (10 Hz, 5−8 ns duration, 7 mW) from an optical parametric oscillator (Continuum Inc., Panther) seeded by a Nd:YAG laser (Continuum Inc., Surelite II) was focused into a 1 mm diameter spot with a convex lens and was used for TPA−TTA experiments. The photoluminescence spectrum was monitored through IR cutting filters (>800 nm) using an Andor model iStar image-intensifier ICCD camera equipped with a Solar TII model MS2004 monochromator. A femtosecond pulse (1 kHz, 106 W cm−2). Thus, the total yield in PQDs is insufficient for the downstream nonlinear TTA process, whereas a partial ET from PQDs to PtOEP occurs as confirmed from the quenched emission of PQDs by about half. The serial TPA−TTA process was then examined using an 800 nm femtosecond laser with focusing. ρex was increased to 1011 W cm−2 (∼1030 photons cm−2 s−1) by 4 orders of magnitude compared with that of the nanosecond laser. Neither degradation nor ablation of the PQD suspension were observed at this ρex. The difference in the TPA cross sections at 900 and 800 nm is only a small factor.42 Thus, the change is readily attributed to the value of ρex. Figure 5b exhibits the photoluminescence spectra of PQD with PtOEP and DPA, which involves a blue-colored region centered at ∼430 nm due to the fluorescence from the DPA S1 state and a decrease in the green (500−550 nm) region due to the ET. The PQD + PtOEP solution without DPA showed the quenching of PQD photoluminescence along with the emergence of phosphorescence from the PtOEP T1 state at 646 nm generated by the TPA−ET−ISC process, whereas the emission at 400−450 nm was not observed. The PtOEP + DPA solution without PQDs showed a weak fluorescence from the DPA S1 state, possibly generated by multiphoton absorption of DPA molecule. On the basis of these comparative measurements, the cascade TPA−TTA process was demonstrated for the first time, where the anti-Stokes shift in the present TPA−TTA process was calculated to be 1.3 eV (800 and 430 nm), which can be increased up to ∼1.6 eV if a high-power IR pulse at 1038 nm is available. The appearance of the enhanced fluorescence from

the DPA S1 state in the presence of PQDs indicates the indispensable role of PQDs for initiating TPA and beginning the resulting cascade process. As shown in Figure 6a, the intensities of the green photoluminescence from PQDs increased with the excitation intensity (Iex = 1.3−24 mJ cm−2 pulse−1). The slope of the logarithmic plot (PL intensity at 514 nm vs Iex) was 1.5, which is smaller than the theoretical value of the second-order TPA process (Figure 6b). This is probably due to the undesired energy loss at the high Iex such as nonlinear optical interaction with the solvent, because the logarithmic slopes were 1.99 and 1.94 for the PQDs and PQDs with PtOEP and DPA solutions at the reduced Iex without focusing (Iex = 0.11−3.6 mJ cm−2 pulse−1, Figure S10). The phosphorescence peak of the PtOEP T1 state at 646 nm observed in the PQD + PtOEP solution exhibited the slope of 1.4, indicating that the PtOEP T1 was generated as a result of ET from the excited state of PQDs generated by the TPA process (the spectra are shown in Figure S11). The slope of the PL peak at 480−510 nm in PQD + PtOEP + DPA solution was 1.4. Notably, the 2-fold slope (2.9) was observed in the fluorescence peak of the DPA S1 state at 430 nm, supporting the total four-photon process of the TPA− TTA cascade. The quantum yield of TPA (φTPA) at the optimal condition was calculated to be 0.21 (the maximum is 0.5) by measuring ΔI/(2I), where ΔI and I are the absorbed and incident light intensities, respectively.2 This φTPA is reasonably consistent with the calculated φTPA (0.30) from the light intensity, TPA cross section of CsPbBr3 and PQD concentration (see the E

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decrease in the emission intensity at 400−500 nm with the increase in the depth of the excitation light path (Figure S12). Nonetheless, efficient TPA in single crystal LHP46 may cause a cascade process in a solid film. Thus, we envision that the present system offers plenty of room for exploring organic and hybrid upconversion systems with large anti-Stokes shifts.

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CONCLUSIONS We demonstrated a cascade process of TPA and TTA in a ternary solution of colloidal PQDs, PtOEP, and DPA. Fluorescence from the S1 in the DPA state at 430 nm was observed with a large anti-Stokes shift of 1.3 eV under femtosecond laser excitation at 800 nm (1011 W cm−2). The six serial steps (TPA, ET, ISC, TET, TTA, and RD) were comparatively examined, suggesting that the nonlinear processes (TPA and TTA) are rate-limiting for the overall yield. The large FRET radius (35.4 Å), efficient reabsorption by PtOEP, and the relatively large SQ rate constant (8.1 × 103 M−1) were found to contribute to the ET process. The use of LHP along with a rational design of organic molecules is suggested to broaden the application of upconversion, leveraged on the excellent TPA properties of LHP in its colloidal solution and in a single crystal form.

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Figure 6. (a) Photoluminescence spectra of PQDs (left panel) and PQDs with 0.2 mM PtOEP and 10 mM DPA (all, right panel) in toluene (λex = 800 nm, a focused femtosecond laser) with changing the excitation intensity (Iex). (b) Logarithmic plots of photoluminescence intensities vs Iex. The solid lines are the least-meansquares fits of B(Iex)α, where, B and α are the scaling factor and the power factor, respectively. α corresponds to the slope of the plot. The values in the brackets are the PL wavelengths.

S Supporting Information *

The Supporting Information is available free of charge on the ACS Publications website at DOI: 10.1021/acs.jpcc.8b05508. Quenching analysis and estimation of TPA quantum yield; normalized photoabsorption spectra of PtOEP and PdOEP (Figure S1); PYS and onset of photoabsorption spectra (Figure S2); picosecond lifetime spectroscopy of DPA and PQD with PtOEP, respectively (Figure S3 and Table S1); nanosecond transient photoluminescence spectra of PtOEP (Figure S4); extinction coefficient of photoabsorption spectrum of PtOEP (Figure S5); overlap integral (Figure S6); analytical fit of concentration dependence of PtOEP on the PL intensity (Figure S7); picosecond lifetime spectroscopies of PQD at different excitation intensities (Figure S8 and Table S2); photoluminescence spectra of PtOEP + DPA, PQD, and PQD + PtOEP respectively (Figures S9− S11); photoluminescence spectra of PQD + PtOEP with optical path depth (Figure S12) (PDF)

Supporting Information). Note that the photoluminescence quantum yield of PQD (∼0.9 at the maximum)43−45 is not included in φTPA. The quantum yield of TTA upconversion (φTTA) in a deoxygenated DMF solution of PtOEP−DPA has been reported to be 2.3 × 10−2 (the maximum is 0.5).54 Accordingly, the overall efficiency of the TPA−TTA cascade process is approximately 0.2% (Table 1). Among the serial Table 1. Summary of the Quantum Yields (φ) under Optimal Conditions φ

value

refs

TPA ET ISC TET TTA RD overall

0.21a 0.5 1.0 1.0 2.3 × 10−2a,b 0.87 2.1 × 10−3 c

this work this work 65 64 54 54 this work

ASSOCIATED CONTENT

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AUTHOR INFORMATION

Corresponding Author

*E-mail: [email protected]. Tel: +81-6-6879-4587. ORCID

a

The maximum is 0.5 (a two-photon process). bA deoxygenated DMF solution with 0.025 mM PtOEP and 7 mM DPA (λex = 532 nm, ref 54). cφTPAφETφISCφTETφTTAφRD. The maximum is 0.25 (a fourphoton process).

Akinori Saeki: 0000-0001-7429-2200 Notes

The authors declare no competing financial interest.

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ACKNOWLEDGMENTS The authors thank Prof. Takahiro Kozawa at The Institute of Scientific and Industrial Research (ISIR), Osaka University for his permission to use a femtosecond laser. This work was supported by the PRESTO program (Grant No. JPMJPR15N6) from the Japan Science and Technology Agency (JST) of Japan; the Japan Society for the Promotion of Science (JSPS) with the KAKENHI Grant-in-Aid for

process, the requisite high density excitation is a drawback of the upstream TPA process, whereas the downstream process, except for TTA, was found to be relatively efficient, which can be further improved by molecular engineering. The reabsorption of 430 nm emission by PQDs due to their high absorption coefficient at the short-wavelength region is another issue for the extraction of the upconverted photons, as evident from the F

DOI: 10.1021/acs.jpcc.8b05508 J. Phys. Chem. C XXXX, XXX, XXX−XXX

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(18) Singh-Rachford, T. N.; Castellano, F. N. Pd(II) Phthalocyanine-Sensitized Triplet−Triplet Annihilation from Rubrene. J. Phys. Chem. A 2008, 112, 3550−3556. (19) Cheng, Y. Y.; Fückel, B.; MacQueen, R. W.; Khoury, T.; Clady, R. G. C. R.; Schulze, T. F.; Daukes, N. J. E.; Crossley, M. J.; Stannowski, B.; Lips, K.; Schmidt, T. W. Improving the LightHarvesting of Amorphous Silicon Solar Cells with Photochemical Upconversion. Energy Environ. Sci. 2012, 5, 6953−6959. (20) Duan, P.; Yanai, N.; Nagatomi, H.; Kimizuka, N. Photon Upconversion in Supramolecular Gel Matrixes: Spontaneous Accumulation of Light-Harvesting Donor−Acceptor Arrays in Nanofibers and Acquired Air Stability. J. Am. Chem. Soc. 2015, 137, 1887−1894. (21) Lee, D.-I.; Goodson, T., III Entangled Photon Absorption in an Organic Porphyrin Dendrimer. J. Phys. Chem. B 2006, 110, 25582− 25585. (22) Nanda, K. D.; Krylov, A. I. Visualizing the Contributions of Virtual States to Two-Photon Absorption Cross Sections by Natural Transition Orbitals of Response Transition Density Matrices. J. Phys. Chem. Lett. 2017, 8, 3256−3265. (23) Kojima, A.; Teshima, K.; Shirai, Y.; Miyasaka, T. Organometal Halide Perovskites as Visible-Light Sensitizers for Photovoltaic Cells. J. Am. Chem. Soc. 2009, 131, 6050−6051. (24) Kim, H.-S.; Lee, C.-R.; Im, J.-H.; Lee, K.-B.; Moehl, T.; Marchioro, A.; Moon, J. S.; Humphry-Baker, R.; Yum, J.-H.; Moser, J. E.; et al. Lead Iodide Perovskite Sensitized All-Solid-State Submicron Thin Film Mesoscopic Solar Cell with Efficiency Exceeding 9%. Sci. Rep. 2012, 2, No. 591. (25) Lee, M. M.; Teuscher, J.; Miyasaka, T.; Murakami, T. N.; Snaith, H. J. Efficient Hybrid Solar Cells Based on Meso-Superstructured Organometal Halide Perovskites. Science 2012, 338, 643− 647. (26) Yang, W. S.; Park, B.-W.; Jung, E. H.; Jeon, N. J.; Kim, Y. C.; Lee, D. U.; Shin, S. S.; Seo, J.; Kim, E. K.; Noh, J. H.; et al. Iodide Management in Formamidinium-Lead-Halide−Based Perovskite Layers for Efficient Solar Cells. Science 2017, 356, 1376−1379. (27) Cho, H.; Jeong, S.-H.; Park, M.-H.; Kim, Y.-H.; Wolf, C.; Lee, C.-L.; Heo, J. H.; Sadhanala, A.; Myoung, N.; Yoo, S.; et al. Overcoming the Electroluminescence Efficiency Limitations of Perovskite Light-Emitting Diodes. Science 2015, 350, 1222−1225. (28) Yuan, M.; Quan, L. N.; Comin, R.; Walters, C.; Sabatini, R.; Voznyy, O.; Hoogland, S.; Zhao, Y.; Beauregard, E. M.; Kanjanaboos, P.; et al. Perovskite Energy Funnels for Efficient Light-Emitting Diodes. Nat. Nanotechnol. 2016, 11, 872−877. (29) Wang, N.; Cheng, L.; Ge, R.; Zhang, S.; Miao, Y.; Zou, W.; Yi, C.; Sun, Y.; Cao, Y.; Yang, R.; et al. Perovskite Light-Emitting Diodes Based on Solution Processed Self-Organized Multiple Quantum Wells. Nat. Photonics 2016, 10, 699−704. (30) Li, G.; Rivarola, F. W. R.; Davis, N. J. L. K.; Bai, S.; Jellicoe, T. C.; de la Peña, F.; Hou, S.; Ducati, C.; Gao, F.; Friend, R. H.; et al. Highly Efficient Perovskite Nanocrystal Light-Emitting Diodes Enabled by a Universal Crosslinking Method. Adv. Mater. 2016, 28, 3528−3534. (31) Luo, J.; Im, J.-H.; Mayer, M. T.; Schreier, M.; Nazeeruddin, M. K.; Park, N.-G.; Tilley, S. D.; Fan, H. J.; Grätzel, M. Water Photolysis at 12.3% Efficiency via Perovskite Photovoltaics and Earth-Abundant Catalysts. Science 2014, 345, 1593−1596. (32) Deschler, F.; Price, M.; Pathak, S.; Klintberg, L. E.; Jarausch, D.-D.; Higler, R.; Hüttner, S.; Leijtens, T.; Stranks, S. D.; Snaith, H. J.; et al. High Photoluminescence Efficiency and Optically Pumped Lasing in Solution-Processed Mixed Halide Perovskite Semiconductors. J. Phys. Chem. Lett. 2014, 5, 1421−1426. (33) Yakunin, S.; Protesescu, L.; Krieg, F.; Bodnarchuk, M. I.; Nedelcu, G.; Humer, M.; De Luca, G.; Fiebig, M.; Heiss, W.; Kovalenko, M. V. Low-Threshold Amplified Spontaneous Emission and Lasing from Colloidal Nanocrystals of Caesium Lead Halide Perovskites. Nat. Commun. 2015, 6, No. 8056. (34) Cannavale, A.; Eperon, G. E.; Cossari, P.; Abate, A.; Snaith, H. J.; Gigli, G. Perovskite Photovoltachromic Cells for Building Integration. Energy Environ. Sci. 2015, 8, 1578−1584.

Scientific Research (A) (Grant No. JP16H02285); a grant from The Murata Science Foundation. R.N. acknowledges the financial support of a JSPS scholarship (No. 201820108).

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REFERENCES

(1) He, G. S.; Tan, L.-S.; Zheng, Q.; Prasad, P. N. Multiphoton Absorbing Materials: Molecular Designs, Characterizations, and Applications. Chem. Rev. 2008, 108, 1245−1330. (2) Ye, C.; Zhou, L.; Wang, X.; Liang, Z. Photon Upconversion: from Two-Photon Absorption (TPA) to Triplet−Triplet Annihilation (TTA). Phys. Chem. Chem. Phys. 2016, 18, 10818−10835. (3) Yanai, N.; Kimizuka, N. New Triplet Sensitization Routes for Photon Upconversion: Thermally Activated Delayed Fluorescence Molecules, Inorganic Nanocrystals, and Singlet-to-Triplet Absorption. Acc. Chem. Res. 2017, 50, 2487−2495. (4) Guzelturk, B.; Demir, H. V. Near-Field Energy Transfer Using Nanoemitters for Optoelectronics. Adv. Funct. Mater. 2016, 26, 8158−8177. (5) Pichaandi, J.; Boyer, J.-C.; Delaney, K. R.; van Veggel, F. C. J. M. Two-Photon Upconversion Laser (Scanning and Wide-Field) Microscopy Using Ln3+-Doped NaYF4 Upconverting Nanocrystals: A Critical Evaluation of their Performance and Potential in Bioimaging. J. Phys. Chem. C 2011, 115, 19054−19064. (6) Zhao, F.; Li, Z.; Wang, L.; Hu, C.; Zhang, Z.; Li, C.; Qu, L. Supramolecular Quantum Dots as Biodegradable Nano-Probes for Upconversion-Enabled Bioimaging. Chem. Commun. 2015, 51, 13201−13204. (7) Karimi, M.; Zangabad, P. S.; Baghaee-Ravari, S.; Ghazadeh, M.; Mirshekari, H.; Hamblin, M. R. Smart Nanostructures for Cargo Delivery: Uncaging and Activating by Light. J. Am. Chem. Soc. 2017, 139, 4584−4610. (8) Zhou, W.; Kuebler, S. M.; Braun, K. L.; Yu, T.; Cammack, J. K.; Ober, C. K.; Perry, J. W.; Marder, S. R. An Efficient Two-PhotonGenerated Photoacid Applied to Positive-Tone 3D Microfabrication. Science 2002, 296, 1106−1109. (9) Gan, Z.; Cao, Y.; Evans, R. A.; Gu, M. Three-Dimensional Deep Sub-Diffraction Optical Beam Lithography with 9 nm Feature Size. Nat. Commun. 2013, 4, No. 2061. (10) Ushiba, S.; Shoji, S.; Masui, K.; Kono, J.; Kawata, S. Direct Laser Writing of 3D Architectures of Aligned Carbon Nanotubes. Adv. Mater. 2014, 26, 5653−5657. (11) Xing, J.-F.; Zheng, M.-L.; Duan, X.-M. Two-Photon Polymerization Microfabrication of Hydrogels: An Advanced 3D Printing Technology for Tissue Engineering and Drug Delivery. Chem. Soc. Rev. 2015, 44, 5031−5039. (12) Monguzzi, A.; Braga, D.; Gandini, M.; Holmberg, V. C.; Kim, D. K.; Sahu, A.; Norris, D. J.; Meinardi, F. Broadband Up-Conversion at Subsolar Irradiance: Triplet−Triplet Annihilation Boosted by Fluorescent Semiconductor Nanocrystals. Nano Lett. 2014, 14, 6644− 6650. (13) Frazer, L.; Gallaher, J. K.; Schmidt, T. W. Optimizing the Efficiency of Solar Photon Upconversion. ACS Energy Lett. 2017, 2, 1346−1354. (14) Li, D.; Ågren, H.; Chen, G. Near Infrared Harvesting DyeSensitized Solar Cells Enabled by Rare-Earth Upconversion Materials. Dalton Trans. 2018, DOI: 10.1039/C7DT04461E. (15) Baluschev, S.; Yakutkin, V.; Miteva, T.; Avlasevich, Y.; Chernov, S.; Aleshchenkov, S.; Nelles, G.; Cheprakov, A.; Yasuda, A.; Müllen, K.; et al. Blue-Green Up-Conversion: Noncoherent Excitation by NIR Light. Angew. Chem., Int. Ed. 2007, 46, 7693−7696. (16) Ye, C. Q.; Wang, J. J.; Wang, X. M.; Ding, P.; Liang, Z. Q.; Tao, X. T. A New Medium for Triplet−Triplet Annihilated Upconversion and Photocatalytic Application. Phys. Chem. Chem. Phys. 2016, 18, 3430−3437. (17) Xun, Z.; Zeng, Y.; Chen, J.; Yu, T.; Zhang, X.; Yang, G.; Li, Y. Pd−Porphyrin Oligomers Sensitized for Green-to-Blue Photon Upconversion: The More the Better? Chem. - Eur. J. 2016, 22, 8654−8662. G

DOI: 10.1021/acs.jpcc.8b05508 J. Phys. Chem. C XXXX, XXX, XXX−XXX

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The Journal of Physical Chemistry C (35) Halder, A.; Choudhury, D.; Ghosh, S.; Subbiah, A. S.; Sarkar, S. K. Exploring Thermochromic Behavior of Hydrated Hybrid Perovskites in Solar Cells. J. Phys. Chem. Lett. 2015, 6, 3180−3184. (36) Nishikubo, R.; Tohnai, N.; Hisaki, I.; Saeki, A. Thermoresponsive Emission Switching via Lower Critical Solution Temperature Behavior of Organic−Inorganic Perovskite Nanoparticles. Adv. Mater. 2017, 29, No. 1700047. (37) Wheeler, L. M.; Moore, D. T.; Ihly, R.; Stanton, N. J.; Miller, E. M.; Tenent, R. C.; Blackburn, J. L.; Neale, N. R. Switchable Photovoltaic Windows Enabled by Reversible Photothermal Complex Dissociation from Methylammonium Lead Iodide. Nat. Commun. 2017, 8, No. 1722. (38) Wei, W.; Zhang, Y.; Xu, Q.; Wei, H.; Fang, Y.; Wang, Q.; Deng, Y.; Li, T.; Gruverman, A.; Cao, L.; et al. Monolithic Integration of Hybrid Perovskite Single Crystals with Heterogenous Substrate for Highly Sensitive X-ray Imaging. Nat. Photonics 2017, 11, 315−321. (39) Xu, Y.; Chen, Q.; Zhang, C.; Wang, R.; Wu, H.; Zhang, X.; Xing, G.; Yu, W. W.; Wang, X.; Zhang, Y.; et al. Two-Photon-Pumped Perovskite Semiconductor Nanocrystal Lasers. J. Am. Chem. Soc. 2016, 138, 3761−3768. (40) Wang, Y.; Li, X.; Zhao, X.; Xiao, L.; Zeng, H.; Sun, H. Nonlinear Absorption and Low-Threshold Multiphoton Pumped Stimulated Emission from All-Inorganic Perovskite Nanocrystals. Nano Lett. 2016, 16, 448−453. (41) Chen, J.; Ž ídek, K.; Chábera, P.; Liu, D.; Cheng, P.; Nuuttila, L.; Al-Marri, M. J.; Lehtivuori, H.; Messing, M. E.; Han, K.; Zheng, K.; Pullerits, T. Size- and Wavelength-Dependent Two-Photon Absorption Cross-Section of CsPbBr3 Perovskite Quantum Dots. J. Phys. Chem. Lett. 2017, 8, 2316−2321. (42) Chen, W.; Bhaumik, S.; Veldhuis, S. A.; Xing, G.; Xu, Q.; Grätzel, M.; Mhaisalkar, S.; Mathews, N.; Sum, T. C. Giant FivePhoton Absorption from Multidimensional Core-Shell Halide Perovskite Colloidal Nanocrystals. Nat. Commun. 2017, 8, No. 15198. (43) Protesescu, L.; Yakunin, S.; Bodnarchuk, M. I.; Krieg, F.; Caputo, R.; Hendon, C. H.; Yang, R. X.; Walsh, A.; Kovalenko, M. V. Nanocrystals of Cesium Lead Halide Perovskites (CsPbX3, X = Cl, Br, and I): Novel Optoelectronic Materials Showing Bright Emission with Wide Color Gamut. Nano Lett. 2015, 15, 3692−3696. (44) Koscher, B. A.; Swabeck, J. K.; Bronstein, N. D.; Alivisatos, A. P. Essentially Trap-Free CsPbBr3 Colloidal Nanocrystals by Postsynthetic Thiocyanate Surface Treatment. J. Am. Chem. Soc. 2017, 139, 6566−6569. (45) Liu, H.; Wu, Z.; Gao, H.; Shao, J.; Zou, H.; Yao, D.; Liu, Y.; Zhang, H.; Yang, B. One-Step Preparation of Cesium Lead Halide CsPbX3 (X = Cl, Br, and I) Perovskite Nanocrystals by Microwave Irradiation. ACS Appl. Mater. Interfaces 2017, 9, 42919−42927. (46) Walters, G.; Sutherland, B. R.; Hoogland, S.; Shi, D.; Comin, R.; Sellan, D. P.; Bakr, O. M.; Sargent, E. H. Two-Photon Absorption in Organometallic Bromide Perovskites. ACS Nano 2015, 9, 9340− 9346. (47) Schmidt, L. C.; Pertegás , A.; Gonzál ez-Carrero, S.; Malinkiewicz, O.; Agouram, S.; Espallargas, G. M.; Bolink, H. J.; Galian, R. E.; Pér ez-Prieto, J. Nontemplate Synthesis of CH3NH3PbBr3 Perovskite Nanoparticles. J. Am. Chem. Soc. 2014, 136, 850−853. (48) Huang, H.; Susha, A. S.; Kershaw, S. V.; Hung, T. F.; Rogach, A. L. Control of Emission Color of High Quantum Yield CH3NH3PbBr3 Perovskite Quantum Dots by Precipitation Temperature. Adv. Sci. 2015, 2, No. 1500194. (49) Huang, S.; Li, Z.; Kong, L.; Zhu, N.; Shan, A.; Li, L. Enhancing the Stability of CH3NH3PbBr3 Quantum Dots by Embedding in Silica Spheres Derived from Tetramethyl Orthosilicate in “Waterless” Toluene. J. Am. Chem. Soc. 2016, 138, 5749−5752. (50) Zhang, F.; Zhong, H.; Chen, C.; Wu, X.-g.; Hu, X.; Huang, H.; Han, J.; Zou, B.; Dong, Y. Brightly Luminescent and Color-Tunable Colloidal CH3NH3PbX3 (X = Br, I, Cl) Quantum Dots: Potential Alternatives for Display Technology. ACS Nano 2015, 9, 4533−4542. (51) Laquai, F.; Wegner, G.; Im, C.; Büsing, A.; Heun, S. Efficient Upconversion Fluorescence in a Blue-Emitting Spirobifluorene-

Anthracene Copolymer Doped with Low concentrations of Pt(II)octaethylporphyrin. J. Chem. Phys. 2005, 123, No. 074902. (52) Lissau, J. S.; Nauroozi, D.; Santoni, M.-P.; Edvinsson, T.; Ott, S.; Gardner, J. M.; Morandeira, A. What Limits Photon Upconversion on Mesoporous Thin Films Sensitized by Solution-Phase Absorbers? J. Phys. Chem. C 2015, 119, 4550−4564. (53) Wu, C.-L.; Chang, C.-H.; Chang, Y.-T.; Chen, C.-T.; Chen, C.T.; Su, C.-J. High Efficiency Non-Dopant Blue Organic Light Emitting Diodes Based on Anthracene-Based Fluorophores with Molecular Design of Charge Transport and Red-Shifted Emission Proof. J. Mater. Chem. C 2014, 2, 7188−7200. (54) Cao, X.; Hu, B.; Zhang, P. High Upconversion Efficiency from Hetero Triplet−Triplet Annihilation in Multiacceptor Systems. J. Phys. Chem. Lett. 2013, 4, 2334−2338. (55) Ravi, V. K.; Markad, G. B.; Nag, A. Band Edge Energies and Excitonic Transition Probabilities of Colloidal CsPbX3 (X = Cl, Br, I) Perovskite Nanocrystals. ACS Energy Lett. 2016, 1, 665−671. (56) Mase, K.; Okumura, K.; Yanai, N.; Kimizuka, N. Triplet Sensitization by Perovskite Nanocrystals for Photon Upconversion. Chem. Commun. 2017, 53, 8261−8264. (57) Yamada, Y.; Yamada, T.; Phuong, L. Q.; Maruyama, N.; Nishimura, H.; Wakamiya, A.; Murata, Y.; Kanemitsu, Y. Dynamic Optical Properties of CH3NH3PbI3 Single Crystals As Revealed by One- and Two-Photon Excited Photoluminescence Measurements. J. Am. Chem. Soc. 2015, 137, 10456−10459. (58) Yamada, T.; Yamada, Y.; Nishimura, H.; Nakaike, Y.; Wakamiya, A.; Murata, Y.; Kanemitsu, Y. Fast Free-Carrier Diffusion in CH3NH3PbBr3 Single Crystals Revealed by Time-Resolved One and Two-Photon Excitation Photoluminescence Spectroscopy. Adv. Electron. Mater. 2016, 2, No. 1500290. (59) Pazos-Outón, L. M.; Szumilo, M.; Lamboll, R.; Richter, J. M.; Crespo-Quesada, M.; Abdi-Jalebi, M.; Beeson, H. J.; Vrućinić, M.; Alsari, M.; Snaith, H. J.; et al. Photon Recycling in Lead Iodide Perovskite Solar Cells. Science 2016, 351, 1430−1433. (60) Fang, Y.; Wei, H.; Dong, Q.; Huang, J. Quantification of ReAbsorption and Re-Emission Processes to Determine Photon Recycling Efficiency in Perovskite Single Crystals. Nat. Commun. 2017, 8, No. 14417. (61) Miyata, A.; Mitioglu, A.; Plochocka, P.; Portugall, O.; Wang, J. T.-W.; Stranks, S. D.; Snaith, H. J.; Nicholas, R. J. Direct Measurement of the Exciton Binding Energy and Effective Masses for Charge Carriers in Organic−Inorganic Tri-Halide Perovskites. Nat. Phys. 2015, 11, 582−587. (62) Ziffer, M. E.; Mohammed, J. C.; Ginger, D. S. Electroabsorption Spectroscopy Measurements of the Exciton Binding Energy, Electron−Hole Reduced Effective Mass, and Band Gap in the Perovskite CH3NH3PbI3. ACS Photonics 2016, 3, 1060−1068. (63) Phuong, L. Q.; Nakaike, Y.; Wakamiya, A.; Kanemitsu, Y. Free Excitons and Exciton−Phonon Coupling in CH3NH3PbI3 Single Crystals Revealed by Photocurrent and Photoluminescence Measurements at Low Temperatures. J. Phys. Chem. Lett. 2016, 7, 4905−4910. (64) Aulin, Y. V.; van Sebille, M.; Moes, M.; Grozema, F. C. Photochemical Upconversion in Metal-Based Octaethyl Porphyrin− Diphenylanthracene Systems. RSC Adv. 2015, 5, No. 107896. (65) Staroske, W.; Pfeiffer, M.; Leo, K.; Hoffmann, M. Single-Step Triplet-Triplet Annihilation: An Intrinsic Limit for the High Brightness Efficiency of Phosphorescent Organic Light Emitting Diodes. Phys. Rev. Lett. 2007, 98, No. 197402. (66) Evans, R. C.; Douglas, P. Design and Color Response of Colorimetric Multilumophore Oxygen Sensors. ACS Appl. Mater. Interfaces 2009, 1, 1023−1030. (67) Kenner, R. D.; Khan, A. U. Molecular Oxygen Enhanced Fluorescence of Organic Molecules in Polymer Matrices: A Singlet Oxygen Feedback Mechanism. J. Chem. Phys. 1976, 64, 1877−1882. (68) Sewell, G.; Forster, R. J.; Keyes, T. E. Influence of Steric Confinement within Zeolite Y on Photoinduced Energy Transfer between [Ru(bpy)3]2+ and Iron Polypyridyl Complexes. J. Phys. Chem. A 2008, 112, 880−888. H

DOI: 10.1021/acs.jpcc.8b05508 J. Phys. Chem. C XXXX, XXX, XXX−XXX

Article

The Journal of Physical Chemistry C (69) Brownrigg, J. T.; Kenny, J. E. Fluorescence Intensities and Lifetimes of Aromatic Hydrocarbons in Cyclohexane Solution: Evidence of Contact Charge-Transfer Interactions with Oxygen. J. Phys. Chem. A 2009, 113, 1049−1059. (70) Pal, A.; Srivastava, S.; Saini, P.; Raina, S.; Ingole, P. P.; Gupta, R.; Sapra, S. Probing the Mechanism of Fluorescence Quenching of QDs by Co(III)-Complexes: Size of QD and Nature of the Complex Both Dictate Energy and Electron Transfer Processes. J. Phys. Chem. C 2015, 119, 22690−22699. (71) De, A.; Mondal, N.; Samanta, A. Hole Transfer Dynamics from Photoexcited Cesium Lead Halide Perovskite Nanocrystals: 1Aminopyrene as Hole Acceptor. J. Phys. Chem. C 2018, DOI: 10.1021/acs.jpcc.7b12813. (72) Nair, V. C.; Muthu, C.; Rogach, A. L.; Kohara, R.; Biju, V. Channeling Exciton Migration into Electron Transfer in Formamidinium Lead Bromide Perovskite Nanocrystal/Fullerene Composites. Angew. Chem., Int. Ed. 2017, 56, 1214−1218. (73) Uematsu, T.; Doko, A.; Torimoto, T.; Oohora, K.; Hayashi, T.; Kuwabata, S. Photoinduced Electron Transfer of ZnS−AgInS2 SolidSolution Semiconductor Nanoparticles: Emission Quenching and Photocatalytic Reactions Controlled by Electrostatic Forces. J. Phys. Chem. C 2013, 117, 15667−15676. (74) Zhang, D.; Zhu, M.; Zhao, L.; Zhang, J.; Wang, K.; Qi, D.; Zhou, Y.; Bian, Y.; Jiang, J. Ratiometric Fluorescent Detection of Pb2+ by FRET-Based Phthalocyanine-Porphyrin Dyads. Inorg. Chem. 2017, 56, 14533−14539. (75) Leonardi, M. J.; Topka, M. R.; Dinolfo, P. H. Efficient Förster Resonance Energy Transfer in 1,2,3-Triazole Linked BODIPY-Zn(II) Meso-tetraphenylporphyrin Donor−Acceptor Arrays. Inorg. Chem. 2012, 51, 13114−13122. (76) Sapunov, V. V. Mechanism of Formation and Spectral Characteristics of Triplet Excimers of Pd-Porphyrins in Liquid Solutions. J. Appl. Spectrosc. 1998, 65, 898−904. (77) Yokoyama, K.; Wakikawa, Y.; Miura, T.; Fujimori, J.-i.; Ito, F.; Ikoma, T. Solvent Viscosity Effect on Triplet−Triplet Pair in Triplet Fusion. J. Phys. Chem. B 2015, 119, 15901−15908.

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DOI: 10.1021/acs.jpcc.8b05508 J. Phys. Chem. C XXXX, XXX, XXX−XXX