Photon Upconversion through a Cascade Process of Two-Photon

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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

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

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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

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

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