Nanoparticles Incorporated inside Single-Crystals: Enhanced

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Nanoparticles Incorporated inside SingleCrystals: Enhanced Fluorescent Properties Yujing Liu, Huidong Zang, Ling Wang, Weifei Fu, Wentao Yuan, Jiake Wu, Xinyi Jin, Jishu Han, Changfeng Wu, Yong Wang, Huolin L. Xin, Hongzheng Chen, and Hanying Li Chem. Mater., Just Accepted Manuscript • DOI: 10.1021/acs.chemmater.6b03589 • Publication Date (Web): 25 Sep 2016 Downloaded from http://pubs.acs.org on September 29, 2016

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Chemistry of Materials

Nanoparticles Incorporated inside Single-Crystals: Enhanced Fluorescent Properties Yujing Liu,†,‡,⊥ Huidong Zang,‡,a Ling Wang,†,⊥ Weifei Fu,†,⊥ Wentao Yuan,⊥,§ Jiake Wu,†,⊥ Xinyi Jin,†,⊥ Jishu Han,∥ Changfeng Wu, Yong Wang,⊥,§ Huolin L. Xin,‡ Hongzheng Chen,†,⊥ Hanying Li,*,†,⊥ †

MOE Key Laboratory of Macromolecular Synthesis and Functionalization, Department of Polymer Science and Engineering, Zhejiang University, Hangzhou 310027, P. R. China. ‡Center for Functional Nanomaterials, Brookhaven National Laboratory, Upton, NY 11973, USA. ⊥State Key Laboratory of Silicon Materials, Zhejiang University, Hang‐ zhou 310027, P. R. China. ⊥Center of Electron Microscopy, Department of Materials Science and Engineering, Zhejiang University, Hangzhou 310027, P. R. China. ∥State Key Laboratory of Supramolecular Structure and Materi‐ als, College of Chemistry, Jilin University, Changchun, 130012, P. R. China. State Key Laboratory on Integrated Op‐ toelectronics, College of Electronic Science and Engineering, Jilin University, Changchun, 130012, P. R. China. a Present address: Center for Advanced Solar Photophysics, Chemistry Division, Los Alamos National Laboratory, Los Alamos, New Mexico 87545, USA. ABSTRACT: Incorporation of guest materials inside single‐crystalline hosts leads to single‐crystal composites that have become more and more frequently seen in both biogenic and synthetic crystals. The unique composite structure together with long‐range ordering promises special properties that are, however, less often demonstrated. Here, we examine the fluorescent properties of quantum dots (QDs) and polymer dots (Pdots) encapsulated inside the hosts of calcite single‐ crystals. Two CdTe QDs and two Pdots are incorporated into growing calcite crystals, as the QDs and Pdots are dispersed in the crystallization media of agarose gels. As a result, enhanced fluorescent properties are obtained from the QDs and Pdots inside calcite single‐crystals with greatly improved photostability and significantly prolonged fluorescence lifetime, compared to those in solutions and gels. Specially, the fluorescence lifetime increases by 0.5‐1.6 times after the QDs or Pdots are incorporated. The enhanced fluorescent properties indicate the advantages of encapsulation by single‐crystal hosts that provide dense shells to isolate the fluorescent nanoparticles from atmosphere. As such, this work has implica‐ tions for advancing the research of single‐crystal composites toward their functional design.

INTRODUCTION Single‐crystals are conventionally recognized as homogeneous solids. However, guest materials may be kinetically introduced into a single‐crystalline host that become, consequently, heterogeneous. Examples of this “impure single‐crystal” are seen in nature, including the biogenic single‐crystals1‐8 in echinoderms and mollusks where biomacromolecules are found incorporated inside single‐crystals of calcium carbonate. In addition to biominerals, similar examples were occasionally found in synthetic single‐crystals and have, recently, become more frequently reported. The chemical compositions of the host‐guest pairs have been continuously expanding9‐17 and, particularly, functional materials such as semiconducting crystal hosts18‐24 as well as optically and magnetically active guest materials25‐31 have been kinetically or thermodynamically introduced. Also, a variety of aggregate states of the guest materials in the crystal host have been reported, including separated particle19,32,33 and

micelles,34 continuous networks,9,10,35‐41 and possibly individual molecules.18,42‐44 Based upon these accumulating examples and gradually revealed incorporation mechanisms,25,45‐47 it becomes clear that crystallization allows, generally, incorporation of foreign guest materials to provide an unconventional class of materials called single‐crystal composites. For the single‐crystal composites, their unique composite structure together with dense and ordered molecular packing in the crystal host promises special properties that are, however, less often studied. Limited efforts have been made to examine the mutual interactions between the crystal host and the incorporated foreign materials. One the one hand, the effects of the guest materials on the properties of the crystal host were demonstrated in the sense of mechanical enhancement34,48‐51 and band gap modification.18,52 On the other hand, the effects of the crystal host on the incorporated foreign materials has

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been studied, focusing on the luminescence properties. It has been shown that dye molecules can be incorporated in particular growth zones, instead of a uniform distribution fashion, inside single‐crystals.43 Interestingly, the dye incorporation occasionally leads to prolonged decay time of the steady‐state fluorescence53,54 and room temperature phosphorescence.55 In addition to the dyes, quantum dots (QDs) have been incorporated inside crystals to improve the photostability for lighting applications.27,56,57 Considering the dense and ordered nature of a single‐crystal matrix, incorporation of optically active materials should provide an isolated chemical and physical environments and, very possibly, result in modified optical properties. In this study, we have examined the fluorescence properties of both QDs and polymer dots (Pdots) incorporated inside calcite single‐crystals. Using both steady‐state and transient photoluminescence (PL) spectroscopy, we have demonstrated greatly enhanced photostability and prolonged fluorescence lifetime of the QDs and Pdots inside calcite single‐crystals, compared to those in solutions and gels, exemplifying the “positive” optical effect of incorporating guest materials into single‐crystal hosts. The obtained luminescent crystals might be used as emitters for lighting and lasing.54,56,58‐59

RESULTS AND DISCUSSION Two types of CdTe QDs60 with different emission wavelength of 525 nm and 595 nm (termed as CdTe‐525 and CdTe‐595) were selected as fluorescent guest materials, while calcite crystals were used as the single‐ crystal hosts. The QD guests (4 mg mL‐1)61 were incorporated into the calcite hosts through our previously‐reported gel method.25 QDs were first dispersed in the 0.5 w/v % agarose hydrogels (Figure S1) and subsequent crystallization of calcite in the hydrogel media induced the incorporation of hydrogel networks as well as the QDs (Figure 1a). The obtained crystals exhibit the typical rhombohedral morphology of calcite single‐ crystals, but they are slightly colored in contrast to the colorless calcite solids (Figure 1b and 1e). Under the laser beam (488 nm) (Figure 1c and 1f) and UV light (400 nm) (Figure S2) illumination, intensive fluorescence emits from the crystals and steady‐state PL spectra show emission peaks at 525 nm or 595 nm respectively, in consistent with those of CdTe QDs in solutions and gels (Figure 1d and 1g). Accordingly, the UV‐vis diffuse reflectance spectroscopy (UV‐DRS) of the crystals shows absorption peaks very close to those of the QDs dispersed in both aqueous solution and gel media (Figure S3). The absorption and PL spectra indicate that the CdTe QDs are incorporated inside the calcite crystals as well‐dispersed individual particles but not aggregates. The concentrations of the QDs in the crystals are 0.144 wt % for CdTe‐525 and 0.136 wt % for CdTe‐595 measured using an inductively coupled plasma atomic emission spectrometer (ICP‐AES). These values are slightly lower than 0.148 wt % that is calculated by assuming that a growing crystal incorporates every QD it encounters,

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indicating the efficient QD incorporation through the gel method.

Figure 1. (a) Schematic representation calcite crystallization in gel media containing QDs. (b, c) Optical microscopy (OM) images in dark field (b) and confocal fluorescence image (c) of calcite crystals grown in agarose gel containing CdTe‐525 QDs. (d) PL emission spectrum of the crystals containing CdTe‐525 QDs, with the spectra of the QDs in solutions and gels shown for comparison. (e, f) OM images in dark field (e) and confocal fluorescence image (f) of calcite crystals grown in agarose gel containing CdTe‐595 QDs. (g) PL emission spectrum of the crystals containing CdTe‐595 QDs, with the spectra of the QDs in solutions and gels shown for comparison.

Electron microscopy was employed to further reveal the distribution of CdTe QDs in the crystals. Focused ion beam (FIB) was used to prepare thin sections cut from the calcite crystals grown in presence of the CdTe‐595 QDs and the thin sections were further imaged by high‐angle annular dark‐field scanning transmission electron microscopy (HAADF‐STEM). The HAADF‐STEM image shows random interconnected networks that are assigned as the incorporated agarose gel fibers, consistently with the previous STEM study40 on gel‐grown calcite crystals (Figure 2a). An HAADF‐STEM image with higher magnification reveals brighter particles in between the gel fibers (Figure 2b). These particles are assigned to CdTe‐ 595 QDs incorporated in the crystal because their sizes are very close to those of the QDs (Figure 2e and 2f). As a supporting evidence for QD incorporation, the fluorescent intensity mapping shows the fluorescence of the QDs throughout the thin section imaged in STEM (Figure S4a and S4b). Despite the presence of the incorporated guest materials including both gel fibers and QDs, the crystal hosts still maintain the single‐ crystallinity. Selected‐area electron diffraction (SAED) of a large area (diameter: 3 m) shows a single set of diffraction spots consistent with the calcite single‐crystal

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(Figure 2d). Furthermore, the regular two dimensional lattice fringes are clearly seen in the high‐resolution TEM (HR‐TEM) image (Figure 2c). Therefore, the OM, absorption, PL, STEM, SAED evidences demonstrated that the CdTe QDs are incorporated inside the calcite single‐crystals, together with the agarose gel fibers. In other words, the CdTe QDs are encapsulated with a dense calcite single‐crystalline “shell” (Figure 2b, inset).

concentration were also studied. First, we carried out the photobleaching investigation in the air using steady‐state PL decay (Figure 3b). The fluorescent intensity of bare CdTe‐525 QDs in solution rapidly decreases to about 50 % of the initial value after 30 min illumination of a focused laser beam (488 nm). CdTe QDs dispersed in gels show slightly improved photostability. In sharp contrast, the CdTe QDs incorporated in the crystals exhibit significantly enhanced photostability and the PL intensity remains more than 90 % of the initial value after 30 mins irradiation under the same illumination intensity. Similarly, the photostability of CdTe‐595 QDs is also greatly improved when incorporated inside calcite single‐ crystal (Figure 3c).

Figure 2. (a) An HAADF‐STEM image of a thin section cut from a calcite crystal containing CdTe‐595 QDs. (b) A high magnification HAADF‐STEM image of the thin section, showing uniform distribution of QDs inside calcite crystal. Inset: Schematic image illustrating a QD inside the calcite lattice. (c) An HR‐TEM lattice image viewed down the ( ) zone axis of calcite. (d) A SAED pattern of a region (3 m diameter) containing calcite crystal host, gel fibers, and CdTe‐595 QDs. (e) A TEM image of CdTe‐595 QDs (red circles) dispersed in an aqueous solution and dried on a carbon‐coated film. (f) Histogram of particle sizes of CdTe‐ 595 QDs incorporated inside the thin section (blue). For comparison, histogram of the QDs dispersed in an aqueous solution is shown (red). The average particle sizes are labeled by the dash lines.

Next we proceeded to examine the optical properties of CdTe QDs with the single‐crystalline shells (Figure 3a, state 3). For comparison, the CdTe QDs dispersed in aqueous solution (Figure 3a, state 1) and agarose gel media (Figure 3a, state 2) with the same QD

Figure 3. PL properties of the CdTe‐525 (b, d, f) and CdTe‐ 595 (c, e, g) QDs. (a) Schematic representation of QDs dispersed in aqueous solutions (state 1), gel media (state 2) and incorporated inside calcite single‐crystals (state 3). (b, c) Evolutions of time‐dependent steady‐state PL spectra. (d, e) Transient PL spectra. (f, g) Histogram of pixel‐by‐pixel fluorescence lifetimes extracted by high‐resolution fluorescence‐lifetime imaging microscopy (FLIM) from the QDs in the single‐crystal hosts. For comparison, the fluorescence lifetimes for the QDs in solutions (state 1) and gels (state 2) extracted from the d, e were labeled by dash lines.

In addition to the steady‐state PL spectra, the transient PL spectra were used to study the excitonic relaxation

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dynamics of the CdTe QDs incorporated in the crystals. Confocal FLIM was used to extract the distribution of fluorescence lifetimes pixel‐by‐pixel (Figure S5).62 For comparison, the time resolved fluorescence decay of the QDs dispersed in solution and gels were also measured. As shown in Figure 3d and Figure 3e, the time resolved fluorescence intensity decays much slower for the QDs incorporated in the crystals than those dispersed in solutions or gels, indicative of longer fluorescence lifetime. For CdTe‐525 QDs, the average lifetime is 19.37 ns. Compared to 7.47 and 8.15 ns for those in solutions and gels, the fluorescence lifetime has been prolonged almost 1.6 times as the QDs are encapsulated by the single‐ crystal hosts (Figure 3d and 3f). Similarly, for CdTe‐595 QDs, the average fluorescence lifetime of 23.75 ns for the QDs in the crystal hosts is much longer than those in the solution (11.73 ns) and the gel media (11 ns) (Figure 3e and 3g). The enhanced photostability and the prolonged fluorescence lifetime for the QDs incorporated in the single‐crystal hosts are attributed to two reasons. First, the single‐crystalline hosts prevent the CdTe QDs from aggregation and reduce the self‐quenching.63,64 As a result, the decay process of excited species is delayed. Second, the single‐crystalline hosts serve as dense shells to reduce the diffusivity of oxygen to the QDs. Oxidation of QDs leads to shortened fluorescence lifetime65,66 and decrease of fluorescence.67,68 For QDs in shells, the oxygen molecules are generally believed to diffuse into the fluorescent center from grain boundaries of the shell and the interfaces between QDs and shell.68,69 The single‐ crystal hosts, in the current work, shut down the pathways for oxygen diffusion, protecting the QDs from oxygen induced degradation. As a supporting evidence, 1 m and ~ 100 nm thin sections cut from the crystals containing CdTe‐595 QDs by means of FIB exhibit average fluorescence lifetimes of 16.06 ns and 12.18 ns, respectively (Figure S4c‐S4e). These values are longer than the CdTe‐595 QDs in solution (11.73 ns), and shorter than the CdTe‐595 QDs in bulk single‐crystal (23.75 ns). Also, the QDs inside bulk single‐crystal reveal remarkable photostability than those inside the thin section (1 m) (Figure S6). The reduced fluorescence lifetimes and photostability with the decrease of crystal thickness reconfirm the shielding effect of the crystal shells. Varied materials have been used to encapsulate QDs to improve the photostability.56,57,70‐76 Core‐shell structures are widely used to passivate the surface defects.73,74 As a result, photostability and lifetime as well as dispersity are improved. Further, the QDs and their core/shell particles are encapsulated inside a 3D matrix such as polymers,71,75 aerogels,76 and poly‐crystals,56,57,72 and, subsequently, become photostable to broaden the applications. However, encapsulation inside the 3D matrix typically leads to unchanged or even reduced fluorescence lifetime. Here, the QDs incorporated inside 3D single‐crystal matrix have an apparently improved fluorescence lifetime (increased by 1 and 1.6 times for the two types of QDs respectively), showing the advantage of the single‐crystal

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matrix that provides a denser encapsulation. Previously, dramatically increased emission lifetime up to 1.6 s was reported as matrix‐assisted room temperature phosphorescence in the crystals with incorporated dye molecules.55 The mechanism of the lifetime increase is different from the elongated lifetime observed in this work where the nature of the emission does not change from fluorescence to phosphorescence. Apart from inorganic CdTe QDs, we also investigated the fluorescent properties of two Pdots, poly [(9,9‐ dioctylfluorenyl‐2,7‐diyl)‐co‐(1,4‐benzo‐1‐thiadiazole)] (PF‐10BT) and poly(9,9‐dioctylfluorene)‐co‐(4,7‐di‐2‐ thienyl‐2,1,3‐benzothiadiazole) (PF‐5DTBT) Pdots (Figure S7).77,78 Similarly, the incorporation of PF‐10BT and PF‐ 5DTBT Pdots resulted in colorful calcite single‐crystals, with the absorption and PL peaks close to the Pdots dispersed in solution or gels (Figure S8 and Figure 4a‐f). As the crystals grown in presence of PF‐5DTBT Pdots were gently etched, the incorporated PF‐5DTBT Pdots were exposed in the etched pits, as showed by SEM imaging (Figure 5). Similar to the QDs, the Pdots exhibit enhanced photostability and prolonged fluorescence lifetime after being incorporated in the single‐crystal hosts (Figure 4g‐4j and S9). For the PF‐10BT Pdots, the fluorescence lifetime increases to 2.79 ns, compared to 1.21 ns and 1.4 ns for those in solutions and gels, respectively (Figure 4i). For the PF‐5DTBT Pdots, the fluorescence lifetime also increases to 3.04 ns from 2.01 ns in solutions and 2.16 ns in gels, respectively (Figure 4j). The absorption and PL peaks of Pdots inside single‐crystal are consistent with those of Pdots dispersed in solution or gels, indicating that the Pdots incorporated inside the calcite crystals are dispersed well without severe aggregation. Since the photo‐oxidation are generally accepted as the mechanism for the photobleaching of Pdots,79 the Pdots inside calcite single‐crystal with greatly improved photostability and fluorescence lifetime suggest the stabilizing nature of single‐crystalline host due to the blocking of oxygen by dense molecular packing. Based on the studies of both QDs and Pdots, we conclude that encapsulation inside single‐crystal hosts is an effective approach to prepare photostable emitters. Furthermore, we have fabricated a white light‐emitting diode (WLED) by depositing the crystals with incorporated CdTe QDs on a commercial InGaN LED chips and white light emission was obtained (Figure S10).80,81

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Figure 5. SEM images of calcite crystals grown in an agarose gel containing PF‐5DTBT Pdots: (a) as‐grown; (b, c) gently etched in low and high magnifications. Red dotted circles highlight parts of the PF‐5DTBT Pdots exposed in the etched surfaces. For comparison, a TEM image of a single PF‐5DTBT Pdots dispersed on carbon film is shown in the inset.

CONCLUSIONS

Figure 4. Fluorescent properties of calcite crystals with incorporated PF‐10BT (a, c, e, g, i) and PF‐5DTBT (b, d, f, h, j) Pdots. (a‐d) OM images in dark field (a, b) and fluorescent (c, d) modes. (e, f) PL emission spectra. (g, h) Evolutions of time‐dependent steady‐state PL spectra. (i, j) Transient PL spectra.

In summary, we have demonstrated the enhanced fluorescent properties of both QDs and Pdots that were incorporated into calcite single‐crystals, including CdTe QDs as well as PF‐10BT and PF‐5DTBT Pdots. The incorporated QDs and Pdots are distributed separately inside the single‐crystal hosts, as evidenced by spectroscopy (absorption and fluorescence) and microscopy (STEM, TEM, OM, SEM). Compared to those in solutions or gels, the QDs and Pdots inside the single‐ crystal hosts exhibit greatly enhanced photostability and prolonged fluorescence lifetime, as shown by steady‐state and transient PL spectroscopy. The enhanced fluorescent properties are mainly associated with the dense single‐ crystalline shells that block the oxygen from diffusing toward the nanoparticles. By showing the positive effect of incorporation into a single‐crystalline host in the sense of fluorescence enhancement, this work presents a significant step toward the potential applications of synthetic single‐crystal composites.

ASSOCIATED CONTENT Supporting Information. The Supporting Information is available free of charge on the ACS Publications website at DOI: Complete details of the synthesis of CdTe QDs and Pdots, gel preparation, crystallization and analytical methods. Additional photographs, OM images, confocal fluores‐

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cence images, steady‐state and transient PL spectroscopy, UV‐vis spectrum and electron microscopy, as well as WLED characterization.

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(7) Gries, K.; Kroger, R.; Kubel, C.; Fritz, M.; Rosenauer, A. Investigations of voids in the aragonite platelets of nacre. Acta

AUTHOR INFORMATION

Biomater., 2009, 5, 3038‐3044.

Corresponding Author

(8) Dauphin, Y. Soluble organic matrices of the calcitic prismatic

*E‐mail: [email protected]

shell layers of two pteriomorphid bivalves‐Pinna nobilis and

Notes The authors declare no competing financial interest.

Pinctada margaritifera. J. Biol. Chem., 2003, 278, 15168‐15177.

ACKNOWLEDGMENTS

(9) Nickl, H. J.; Henisch, H. K. Growth of Calcite Crystals in Gels.

This work was supported by 973 Program (2014CB643503), National Natural Science Foundation of China (51373150, 51461165301) and Zhejiang Province Natural Science Founda‐ tion (LZ13E030002). This research used resources of the Center for Functional Nanomaterials, which is a U.S. DOE Office of Science Facility, at Brookhaven National Laboratory under Contract No. DE‐SC0012704. Y. L. acknowledges finan‐ cial support from the China Scholar Council.

J. Electrochem. Soc., 1969, 116, 1258‐1270.

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