Two-Photon Absorption-Based Upconverted Circularly Polarized

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Surfaces, Interfaces, and Catalysis; Physical Properties of Nanomaterials and Materials

Two-Photon Absorption-Based Upconverted Circularly Polarized Luminescence Generated in Chiral Perovskite Nanocrystals Wenjie Chen, Shuai Zhang, Minghao Zhou, Tonghan Zhao, Xujin Qin, Xinfeng Liu, Minghua Liu, and Pengfei Duan J. Phys. Chem. Lett., Just Accepted Manuscript • DOI: 10.1021/acs.jpclett.9b01224 • Publication Date (Web): 30 May 2019 Downloaded from http://pubs.acs.org on May 31, 2019

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The Journal of Physical Chemistry Letters

Two-Photon Absorption-based Upconverted Circularly Polarized Luminescence Generated in Chiral Perovskite Nanocrystals Wenjie Chen,†,‡, ǂ # Shuai Zhang,§, ǂ # Minghao Zhou,‡ Tonghan Zhao,‡, ǂ Xujin Qin,‡ Xinfeng Liu,§, ǂ,* Minghua Liu, †,‡,ǂ,* Pengfei Duan,‡, ǂ,* †Beijing

National Laboratory for Molecular Science, CAS Key Laboratory of Colloid,

Interface and Chemical Thermodynamics, Institute of Chemistry, Chinese Academy of Sciences, No. 2 ZhongGuanCun BeiYiJie, 100190, Beijing, P. R. China. Beijing, P.R. China. ‡CAS

Center for Excellence in Nanoscience, CAS Key Laboratory of Nanosystem and

Hierarchical Fabrication, National Center for Nanoscience and Technology (NCNST), No. 11 ZhongGuanCun BeiYiTiao, 100190 Beijing, P.R. China. §CAS

Center for Excellence in Nanoscience, CAS Key Laboratory of Standardization and

Measurement for Nanotechnology, National Center for Nanoscience and Technology (NCNST), No. 11 ZhongGuanCun BeiYiTiao, 100190 Beijing, P.R. China. ǂUniversity

of Chinese Academy of Sciences, Beijing 100049, P. R. China.

AUTHOR INFORMATION Corresponding Author *E-mail: [email protected] (X.L.). 1 ACS Paragon Plus Environment

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*E-mail: [email protected] (M.L.). *E-mail: [email protected] (P.D.).

ABSTRACT: Upconverted circularly polarized luminescence (UCPL) processes have attracted great interest, because the chiroptical properties could be expressed in different photophysical processes. In this letter, the first example of two-photon absorption based upconverted circularly polarized luminescence (TP-UCPL) was demonstrated. The chiral α-octylamine modified cesium lead bromides perovskite nanocrystals exhibited TP-UCPL with two-photon absorption cross-section at 800 nm (σ2,

800 nm)

up to 3.68×104 GM and

luminescence

dissymmetric factor (glum) up to 7.0 ×10-3. Depending on the molecular chirality of capping ligands, the TP-UCPL sense can be selected and the mirror-imaged CPL is obtained. It is envisaged that this approach will afford a new viewpoint into designing of UCPL processes.

TOC GRAPHICS

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KEYWORDS circularly polarized luminescence, chirality, perovskite, upconversion, twophoton absorption



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Circularly polarized luminescence (CPL) has been attracting enormous attention for their wide potential applications in asymmetric catalysis,1-2 bioencoding,3 3D displays,4-5 and photoelectric devices.6-7 While there have been many reports of organic CPL-active materials due to their facile accessibility,8-11 CPL emission of inorganic systems was not that common. One way to endow the inorganic nanomaterials with CPL ability is to co-assemble with the organic molecules through supramolecular assembly strategy, while the co-assembled systems have good chiroptical and luminescent abilities.12-13 However, the co-assembled supramolecules usually possess strong light scattering, which limits their deeper investigation and applications. Another general method to activate the chiroptical ability of inorganic nanomaterials is capping with chiral reagents such as amino acid, protein or DNA.14-21 The nanomaterials with chiral capping reagents show low scattering, decent chiroptical properties and high luminescence ability,15, 20, 22 which provide a solution for realizing high performance CPL emitter. Photon upconversion (UC) process could generate high-energy photons by converting low-energy photons, which provides a novel view for achieving higher-energy emission. The CPL characteristics within upconversion processes were also interesting. To date, pathways towards upconverted circularly polarized luminescence (UCPL) have been reported in mainly two methods. Firstly, triplet-triplet annihilation based upconversion processes (TTA-UC) with CPL characteristic has been reported.23-25 In this process, at least two species, sensitizers and acceptors, are involved. Secondly, upconversion nanocrystals (UCNPs) composed with rare-earth elements showed excellent upconversion ability when UCNPs excited by nearinfrared light.26-28 However, since the syntheses of UCNPs usually involve high temperature 4 ACS Paragon Plus Environment

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reactions (>200 oC),26-27 where most chiral molecules could not survive without racemization, the UCPL ability of UCNPs were only reported in co-assembly systems.28 Realizing UCPL from solely chiral UCNPs were extremely difficult. Beyond those upconversion process mentioned above, a three-order nonlinear optical (NLO) process: two-photon absorption (TPA) luminescence process, in which fluorophores absorb two low-energy photons simultaneously and emit one high-energy photon through radiation transition,29-30 provides another interesting approach for achieving novel UCPL. Recently, Campaña et al. have reported CPL-active organic π-conjugated systems with TPA luminescence ability.31-32 But the real two-photon absorption upconverted circularly polarized luminescence (TP-UCPL) hasn’t achieved yet. This might due to the relatively low intrinsic TPA cross-sections (in 102 GM magnitude, 1 GM = 10-50 cm4 s photon-1) of organic molecules, which limited the investigation of TP-UCPL process directly. In the meantime, as the counterpart of organic system, all-inorganic semiconductor nanostructures showed excellent TPA property, which provides an excellent platform for investigating chiroptical properties accompanied with TPA.33-35 Herein, we report an approach for achieving TP-UCPL by adapting chiral ligands modification on the nanostructures with high two-photon absorption and luminescence ability. The chiroptical properties were endowed by the surface induction by the chiral ligands. We provide definitive experimental evidences that CPL property could be expressed by two-photon absorption process. This feasible approach will open up a new research field about UCPL processes designing. In this work, all-inorganic colloidal nanocrystals of cesium lead bromides (CsPbBr3) were chosen for TPA-active cores for their high NLO coefficients and high luminescence quantum 5 ACS Paragon Plus Environment


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yields.30, 35-36 The chiral α-octylamine were selected as the chiral capping ligands. Detailed preparation process is available in Supporting Information.

Figure 1. (a) HRTEM image of prepared R-Pero-NC, scale bar: 10 nm. The insert image shows the corresponding TEM image, scale bar: 100 nm. (b) XRD spectra of prepared R- and S-Pero-NC cast film. (c) UV-Vis absorption spectra and (d) Normalized photoluminescence spectra of R- and S-Pero-NC dispersed in n-hexane. Inset images: in (c), bright field image of prepared chiral perovskite nanocrystals’ dispersant; in (d), luminescence image of prepared chiral perovskite nanocrystals’ dispersant under excitation by a 365 nm hand-hold UV lamp.


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The high-resolution transmission electron microscope (HRTEM) image (Figure 1a and S1) illustrates the cubic shapes of prepared chiral nanocrystals with high crystallinity of the perovskite structure. The X-ray diffraction (XRD) patterns of cast films of R-octylamine modified perovskite nanocrystals (R-Pero-NCs) and S-octylamine modified perovskite nanocrystals (S-Pero-NCs) show the similar diffraction peaks compared with the CsPbBr3 crystallographic data (COD #1533063). The energy-dispersive X-ray spectroscopy (EDS) analysis also confirmed the composition of fabricated chiral nanocrystals (Figure S2). The characterizations confirmed the CsPbBr3 perovskite structures of prepared chiral nanocrystals with the average sizes in range of ~20 nm (Table S1). Figure 1c and 1d show the linear absorption and fluorescence spectra of R- and S-Pero-NCs in n-hexane solution. It can be seen that the chiral perovskite nanocrystals have an absorption peak at ~508 nm and exhibit narrow green emission peaks at ~520 nm (insets of Figure 1c and 1d). The photoluminescence quantum yields (ΦPL) of fabricated chiral nanocrystals in n-hexane reach to 60-70%, which confirmed a good luminescence ability.

Figure 2. Chiroptical characteristics of chiral perovskite nanocrystals within one-photon absorption (OPA). (a) Electronic circular dichroism of prepared chiral perovskite nanocrystals dispersed in n-Hexane.

(b,c) One-photon circularly polarized luminescence spectra of chiral 7 ACS Paragon Plus Environment


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perovskite nanocrystals in (b) n-hexane and (c) PMMA film. Excitation for subfigure (b) and (c): 375 nm CW-laser.

Firstly, one-photon luminescence (OPL) properties were investigated using 375 CW laser (experiment setup performed in Scheme S1 and S2). As shown in Figure S3, the green emission intensity of chiral perovskite in n-hexane increased with the increasing power density of 375 nm excitation. And the power dependent luminescence curves fit a relationship, in which PL intensity near linearly depends on the incident energy, indicating that an OPL process occurs in R-Pero-NCs. The enantiomer ligands modified perovskite nanocrystals shows the same linear power dependency in OPL process, as demonstrated in Figure S4. The electronic circular dichroism (CD) and circularly polarized luminescence (CPL) spectra were used to study the chiroptical activity of chiral nanocrystals. The CD spectra of prepared chiral perovskite nanocrystals were shown in Figure 2a. Mirror-image signals at 504 nm were assigned to the exciton absorption, which might have been due to the interaction between chiral α-octylamines and the nanocrystals’ surface.15 The corresponding dissymmetry factors (gCD) at 504 nm for R- and S-Pero-NCs are -2.3×10-4 and 2.4×10-4, respectively. The CPL signals of chiral perovskite nanocrystals were detected in n-hexane as shown in Figure 2b. The luminescence dissymmetry factors (glum) of R- and S-Pero-NCs were calculated as 6.5× 10-4 and -1.0×10-3 at maximum emission wavelength (Figure S5), respectively. The CPL signal with different handedness could be regulated. This indicates that the circular direction of emitted light could be regulated by the chirality of the capping ligands. Moreover, we examined 8 ACS Paragon Plus Environment

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the chiroptical signals of chiral nanocrystals dispersed in PMMA films, where were a relatively confined environment. As shown in Figure 2c, compared with Figure 2b, the CPL peaks were more distinct. The obtained glum value of R- and S-Pero-NCs in PMMA films were 4.5 ×10-3 and -2.8×10-3 at maximum emission wavelength (Figure S6), respectively. To avoid the linear polarized luminescence caused false signal, we checked the linear polarized luminescence as shown in Figure S7, the results showed that the PL intensity was almost constant at different angles of linear polarizer for detection, which implied that the emission of chiral CsPbBr3 perovskite have little linear PL component, and the CPL test was not affected with linear polarized light. These results indicated an obvious amplification of CPL emission property in solid films than in dispersant state. For deeper investigate the influence in sample fabrication process, chiral perovskite nanocrystals fabricated with different molar ratio of oleyl amine (OA) and chiral R-αoctylamine was fabricated, and their CPL signals were tested. The CsPbBr3 nanocrystals could not be fabricated using our method when oleyl amine was absent. As illustrated in Figure S8, the CPL signals showed that, when the molar ratio of α-octylamine and oleyl amine increased, the glum also increased. However, with further increasing of this ratio, the glum hardly changed. Furthermore, influence of the molar weight of PMMA was also investigated for checking whether the rigidity of polymer matrix could affect the chirality expression. As shown in Figure S9, the R-Pero-NCs in lower molar weight PMMA possessed almost the same CPL signal compared with the one in higher molar weight, which indicated that the PMMA is set only as a rigid matrix, while the M.W. could hardly affect the CPL signals.



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Figure 3. Characteristics of chiral perovskite nanocrystals by two-photon absorption (TPA). (a,b) Emission intensity of R-Pero-NC in (a) n-hexane and (b) PMMA film under increasing excitation power density. The insets in (a) and (b) show the two-photon luminescence (TPL) photographs of R-Pero-NC in n-hexane and PMMA film taken before a 730 nm short pass filter, respectively. (c,d) Power dependent TPL profiles of R-Pero-NC in (c) n-hexane and (d) PMMA film under increasing excitation power density. (e,f) Two-photon upconverted circularly polarized luminescence (TP-UCPL) spectra of chiral perovskite nanocrystals in (e) n-hexane and (f) PMMA film. Excitation for all subfigures: 800 nm fs-laser, 1 kHz, pulse width: 100 fs.

Cesium lead halide perovskites possess remarkable two-photon absorption (TPA) and luminescence (TPL) properties, which provides us an opportunity to investigate the chiroptical behavior when the nonlinear optical phenomenon happens. As shown in Figure 3a and 3b, intense green light emitted from the prepared R-Pero-NCs under excitation of 800 nm 10 ACS Paragon Plus Environment

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femtosecond laser (1 kHz, pulse width: 100 fs, experiment setup performed in Scheme S3 and S4). With increasing incident energy, the green emission intensity of chiral perovskite nanocrystals increased quadratically, which clearly confirms the two-photon absorption and luminescence process under excitation of 800 nm (Figure 3c, 3d, S10-S12). It was found that the photoluminescence spectra by one- and two-photon absorption are nearly identical. The TPA cross-section of prepared chiral perovskite nanocrystals is as large as 3.68×104 GM at 800 nm (Table S1), which is orders of magnitude larger than those commonly reported semiconductor quantum dots and organic dyes, suggesting that the prepared chiral perovskite nanocrystals can function as excellent upconverted luminescence media. With this in mind, we further investigated the two-photon upconverted circularly polarized luminescence (TP-UCPL) of those chiral perovskite nanocrystals. As shown in Figure 3e, under 800 nm femtosecond laser (fs-laser) excitation, both R- and S-Pero-NCs showed CPL emission ability. The glum of R- and S-Pero-NCs in TP-UCPL process are calculated as 3.5×10-3 and -2.3×10-3 at maximum emission wavelength. Comparably, when the chiral nanocrystals were confined within the PMMA film, the TP-UCPL ability were also enhanced, as shown in Figure 3f. The glum value of R- and S-Pero-NCs in TP-UCPL process are amplified to 7.0×10-3 and -6.5×10-3 at maximum emission wavelength (Figure S13 and S14). Meanwhile, the racemic α-octylamine modified perovskite nanocrystals showed no TPUCPL behavior, as shown in Figure S15. These results indicated that the CPL emission from chiral CsPbBr3 nanocrystals were almost the same within one- or two-photon excitation process, which indicated that this approach could hardly amplify the glum. Actually, the



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excited states through one- or two-photon excitation should be identical. Thus, the final CPL emission should be nearly the same.

Scheme 1. Schematic illustration of the origin of chirality in chiral CsPbBr3 perovskite. R- and S-octylamine could induce an asymmetric distortion of the surface perovskite lattice, which endow the chirality to perovskite nanocrystals.

The origin of chirality of this system were also analyzed. It has been reported that the origin of chirality of inorganic nanomaterials were attributed in two main hypotheses. First, the nanomaterials don’t have high symmetry operation, hence, the nanostructures themselves are chiral, and the chiroptical characteristics were high and not related to the environment;37-40 Second, the inside nanostructures are highly symmetrical, and the chirality was transferred from the attached chiral molecules shell to the achiral core through surface distorting or so called chiral footprint.15, 41-42 Firstly, we checked the HRTEM images, in which all CsPbBr3 cores crystallized in centrosymmetric form, they are not expected to be chiroptical active by themselves. Secondly, we examined the chiroptical signals of chiral nanocrystals dispersed in n-hexane, where is a 12 ACS Paragon Plus Environment

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relatively free environment, and they in PMMA films, where is a relatively constricted environment. As shown in Figure 2 and 3, CPL signals of chiral CsPbBr3 nanocrystals were stronger in PMMA films compared with the one in solution state. In addition, as reported in previous results, excess bromide atoms existed on the surface of perovskite nanocrystals.43 The chiral amine could specifically bind with the Br-rich defects, as illustrated in Scheme 1. The chiral ligand could distort the surface pattern of nanocrystals effectively and endow them with chiroptical properties. Furthermore, compared with the works on the chiral inorganic nanomaterials shown in Table S3, the absorption and luminescence anisotropy of synthesized chiral CsPbBr3 nanocrystals have dissymmetric factors with similar magnitudes using surface modification theory. In conclusion, we demonstrated the first example of TP-UCPL by adapting chiral ligands modification on TPA-active perovskite nanocrystal core, which enables CPL emission happen in two-photon absorption luminescence process. Chiral ligands, α-octylamines, modified cesium lead bromide perovskite nanocrystals showed good luminescence ability accompanied with both downshift and upconverted CPL emission ability. The origin of chirality in this system could be attributed to the surface induction from chiral capping ligands. In addition, this TP-UCPL emitter reveals a new mechanism to achieve UCPL, which would guide the realization of the TP-UCPL in more chiroptical systems.



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ASSOCIATED CONTENT Supporting Information. Detailed fabrication processes of chiral perovskite nanocrystals and PMMA films, experiment setup for luminescence detection and CPL detection and detailed characterization data. This material is available free of charge via Internet at http://pubs.acs.org (PDF)

AUTHOR INFORMATION Notes #

These authors contribute equally.

The authors declare no competing financial interests. ACKNOWLEDGMENT This work was supported by National Natural Science Foundation of China (91856115, 51673050); the Ministry of Science and Technology of the People's Republic of China (2017YFA0206600, 2016YFA0203400); Key Research Program of Frontier Sciences, CAS, (QYZDJ-SSW-SLH044); P.D. thanks for the support of “New Hundred-Talent Program” research fund of the Chinese Academy of Sciences. REFERENCES (1) Sato, I.; Sugie, R.; Matsueda, Y.; Furumura, Y.; Soai, K. Asymmetric synthesis utilizing circularly polarized light mediated by the photoequilibrium of chiral olefins in conjunction with asymmetric autocatalysis. Angew. Chem. Int. Ed. 2004, 43, 4490-4492. (2) Kawasaki, T.; Sato, M.; Ishiguro, S.; Saito, T.; Morishita, Y.; Sato, I.; Nishino, H.; Inoue, Y.; Soai, K. Enantioselective synthesis of near enantiopure compound by asymmetric 14 ACS Paragon Plus Environment

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