Lasing and Amplified Spontaneous Emission in a Polymeric Inverse

Apr 15, 2013 - We demonstrate the lasing and amplified spontaneous emission in the polymeric inverse opal photonic crystal resonating cavity. The reso...
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Lasing and Amplified Spontaneous Emission in a Polymeric Inverse Opal Photonic Crystal Resonating Cavity Feng Jin,† Lan-Ting Shi,† Mei-Ling Zheng,† Xian-Zi Dong,† Shu Chen,†,‡ Zhen-Sheng Zhao,† and Xuan-Ming Duan*,† †

Laboratory of Organic NanoPhotonics and Key Laboratory of Functional Crystals and Laser Technology, Technical Institute of Physics and Chemistry, Chinese Academy of Sciences, No. 29, Zhongguancun East Road, Beijing, P. R. China, 100190 ‡ University of Chinese Academy of Sciences, No. 29, Zhongguancun East Road, Beijing, P. R. China, 100190 S Supporting Information *

ABSTRACT: We demonstrate the lasing and amplified spontaneous emission in the polymeric inverse opal photonic crystal resonating cavity. The resonating cavity is constructed by sandwiching tert-butyl rhodamine B doped PMMA film with polymeric inverse opal photonic crystals, which work as feedback mirrors. Laser-induced emission experiments reveal lasing or amplified spontaneous emission of the dye molecules in the resonating cavity. Amplified spontaneous emission occurs at the edges of the photonic stop band of the polymeric inverse opal photonic crystal when it partially overlaps with the photoluminescence emission band of the dye molecules. In contrast, lasing action emerges in the resonating cavity when the photonic stop band matches well with the photoluminescence emission band of the dye molecules. Single-mode lasing emission is located at the photonic stop band, indicating the photonic lasing property. The lasing threshold is determined as 4.57 μJ/pulse, and the lasing line width is about 1.0 nm. The present work provides the prospect for constructing low-threshold organic solidstate dye lasers.

1. INTRODUCTION Photonic crystals (PhCs) are materials with periodic dielectric structure, which leads to the formation of a photonic bandgap (PBG).1 PhCs have attracted much interest for their promising applications in many fields, such as solar cell, laser, light beam bending, chemical sensor, and light-emitted diode.2−6 The manipulation of spontaneous emission of light emitters by using the PBG effect of PhCs is of particular interest.7 Since the depletion of the excited state by spontaneous emission is minimized, low-threshold or even thresholdless lasing action is expected to take place in PhCs. To date, lasing action has been obtained by using one-, two-, and three-dimensional PhCs.3,8,9 Inverse opal (IO), which exhibits a PBG in the UV−visible− IR regime, is a three-dimensional PhC using colloidal crystal (CC) as the template. Compared with CC, IO is expected to possess higher refractive index contrast or stimuli response properties by incorporating functional components into IO,10−12 which boosts its applications in low-threshold laser sources. The L-point gap in IO forbids light propagation in the (111) direction, which can be utilized to manipulate the spontaneous emission of the light emitter.13 Inhibition and enhancement of the spontaneous emission of the light emitters have been observed in various IOs.14−16 Furthermore, lasing action has been reported in inorganic IOs immersed in dye solution or in ZnO IOs.17−20 Nevertheless, this kind of system often suffers from volume shrinkage of the inorganic matrix during the formation of inorganic IOs, resulting in the © XXXX American Chemical Society

spontaneous formation of cracks and deteriorating optical quality of the IOs.11 Polymeric IOs possess the advantages of low cost, inherent flexibility, easy processing, and stimuli response, which make them good candidates for tailoring the spontaneous emission of light emitters.12,21,22 Organic lasers based on polymeric IOs are especially interesting due to their inexpensive, safe, and nontoxic properties. However, it remains a challenging issue to achieve lasing action in polymeric IOs, although gain enhancement of quantum dots has been observed in polymeric IOs.23 Generally, it needs two basic elements to perform lasing oscillation, a light emitter to provide optical gain, and a resonating structure to provide optical feedback. A tunable distributed-feedback laser has been achieved by using active medium, a partial mirror of PhC, and a perfect mirror of dielectric stack.24 Recently, lasing emission has been observed in the resonating cavity constructed by sandwiching gain media by a pair of opal PhCs.25,26 These results promote us to realize lasing action in a similar resonating cavity constructed by polymeric IOs. In such a resonating cavity, demonstrating the dependence of the lasing wavelength selection and gain enhancement on the photonic stop band is of significant Received: December 21, 2012 Revised: April 7, 2013

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Scheme 1. Schematic Illustration of the Construction Process of the Polymeric IOs

water and then dried in a vacuum oven. The cleaned glass slides were dipped in KH-570 toluene solution (KH-570/toluene solution = 5 wt %) overnight, rinsed with ethanol, and then dried in a vacuum oven at 100 °C. 2.3. Preparation of Polymeric Inverse Opal Photonic Crystals. Polymeric IO PhCs were prepared by two steps. In the first step, polystyrene (PS) CCs were self-assembled on piranha solution treated glass slides by the vertical deposition method with PS nanosphere colloidal solution (Supporting Information) according to the previous procedure.27 In the second step, polymeric IO PhCs were made by using the PS CCs as template, as shown in Scheme 1. First, a glass slide, which was treated with silane coupling agent KH-570, was covered with a PS CC to form a “glass-PS CC-glass” structure. Second, the PS CC was infiltrated with photopolymerizable resin (the components were listed in Table S1, Supporting Information). An amount of 0.1 mL of photopolymerizable resin was added to the sandwiched structure. Capillary forces draw the liquid photopolymerizable resin into the void spaces between the PS nanospheres. Third, polymeric IO PhCs were obtained by polymerization of the photopolymerizable resin and removing the PS CC template. The photopolymerizable resin filling the void spaces of the PS CC was polymerized by exposing to the UV light (320 W high-pressure Hg Arc lamp) for 5 min. Then, the sandwiched structure was split, and the polymer film containing the PS CC template was transferred to the KH-570-treated glass slide owing to the polymerization between the KH-570 and the photopolymerizable resin (Figure S2, Supporting Information).28 At last, the polymeric IO PhCs were acquired by soaking the polymer film in toluene overnight and removing the PS CC template. The polymeric IO PhCs exhibited color due to the Bragg diffraction of visible light by the air voids. By using KH-570, it is unnecessary to peel off the overlayer formed by the excessive infiltration of the PS CC template, which simplifies the removal of the PS CC template. 2.4. Construction of Polymeric Inverse Opal Photonic Crystal Resonating Cavity. The resonating cavity was fabricated by sandwiching gain medium with a pair of polymeric IO PhCs (Scheme S1, Supporting Information).29 The gain medium was constructed by doping 3 wt % tert-butyl

importance for the further development of nanostructured laser devices. In this study, we present lasing and amplified spontaneous emission in polymeric IO photonic crystal resonating cavities. We have tuned the photonic stop band of the polymeric IOs and investigated the evolution of the laser-induced emission spectra in the resonating cavity. Single-mode lasing emission emerges at the photonic stop band when the photonic stop band of polymeric IO overlaps the photoluminescence (PL) band of the dye molecules. The lasing action is attributed to the feedback of the emitted light between two polymeric IOs. In contrast, amplified spontaneous emission takes place at the edges of the photonic stop band if the photonic stop band of polymeric IO only partially matches with the PL band of the dye molecules. This study would open avenues for developing solid-state dye lasers.

2. MATERIALS AND METHODS 2.1. Materials. Benzil (Aldrich), 2-benzyl-2-(dimethylamino)-4′-morpholinobutyrophenone (Aldrich), dipentaerythritol hexaacrylate (DPE-6A, Kyoeisha Chemical Co. Ltd., Japan), pemaerythritol-triacrylate (PE-3A, Kyoeisha Chemical Co. Ltd., Japan), and N-isopropyl acrylamide (NIPAm, TCI) were used. 3-Methacryloxypropyltrimethoxysilane (KH-570) was purchased from Nanjing Chuangshi Chemical Co., Ltd. Styrene (St, AR), toluene (C6H5CH3, AR), potassium persulfate (KPS, AR), sodium dodecyl benzene sulfonate (SDBS, AR), ammonium bicarbonate (NH4HCO3, AR), ethanol (C2H6O, AR), hydrogen peroxide (H2O2, AR), sulfuric acid (H2SO4, AR), hydrochloric acid (HCl, AR), and acrylic acid (AA, AR) were all purchased from Sinopharm chemical reagent Beijing Co., Ltd. Styrene was purified by distillation under reduced pressure and stored in the refrigerator. Potassium persulfate was recrystallized twice and dried overnight in a vacuum oven, then kept in the desiccator for use. All the other chemical reagents were used without further purification. 2.2. Treatment of Glass Slides. Glass slides were dealt with piranha solution (H2SO4/H2O2 = 7:3) at 80 °C for 1 h. Caution: Piranha solution is a strong oxidant and should be handled with care. The glass slides were rinsed with deionized B

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rhodamine B (t-Bu RhB) in polymethylmethacrylate (PMMA) film with a thickness of 9 μm. A piece of PMMA film with t-Bu RhB was wetted by a minute amount of ethanol, which facilitated the bonding of the PMMA film and the polymeric IO PhCs. Then, the PMMA film was carefully sandwiched by a pair of polymeric IO PhCs, and the whole structure was fixed by the binder clips. Finally, the ethanol was removed under reduced pressure in a vacuum drying oven. Polymeric IO PhCs with different photonic stop bands were chosen to investigate the effect of the photonic stop band on the gain enhancement of the dye molecules. 2.5. Characterization. Scanning electron microscopy (SEM) images were obtained with a field emission (FE)-SEM (Hitachi S-4300, Japan). The absorption and transmission spectra were collected using a Shimadzu UV-2550 spectrometer. The PL spectrum was obtained using a Hitachi F-4500 fluorescence spectrometer. For the laser-induced emission measurement, we used an excitation beam produced by a Qswitched Nd:YAG laser (Spectra Physics, USA) operating at 532 nm with pulse duration of 8 ns and repetition rate of 10 Hz. The excitation beam was focused into a laser spot with a diameter of about 14 μm and irradiated on the center of the resonating cavity with an incident angle of about 45° with the (111) plane of polymeric IOs (Figure S4, Supporting Information). The optical emission was collected from the opposite side of the excitation beam by using a fiber-coupled grating spectrometer (USB 2000, Ocean Optics), and the detection angle is perpendicular to the (111) plane of the polymeric IOs. The intensity of the pumping laser beam was controlled using a neutral-density filter. All of the measurements were carried out at room temperature.

Figure 1. SEM images of polymeric IOs using PS colloidal crystal templates constructed by PS nanospheres with the size of (a) 265 nm, (b) 344 nm, (c) 366 nm, and (d) 380 nm, respectively. The insets are the SEM images of the PS colloidal crystal templates. (e) Transmission spectra of the polymeric IOs with different photonic stop bands. The inset is the photograph of the polymeric IOs.

3. RESULTS AND DISCUSSION SEM images and transmission spectra of the polymeric IOs are presented in Figure 1. Face-centered cubic (fcc) PS CCs were fabricated on glass substrates by using PS nanospheres with the size of 265, 344, 366, and 380 nm, respectively. These PS CCs were chosen as the templates to construct polymeric IOs. Figure 1a−d presented the SEM images of the resultant polymeric IOs. Top-view SEM images verified that polymeric IOs maintained the fcc structure of the PS CCs, with the closepacked (111) plane oriented parallel to the substrate. In the polymeric IOs, each air sphere was connected to the adjacent air spheres through small “windows”, which were distinguished by the black holes in the next layer of the air spheres below. High-quality polymeric IOs were confirmed by well-ordered hexagonal structures in the 3D macroporous membrane, indicating the successful replication of the PS CCs structure. Transmission spectra of the polymeric IOs were derived using UV−vis spectroscopy measured in normal incidence, as shown in Figure 1e. The attenuation in the transmission spectra indicated the photonic stop band of the polymeric IOs, which located at the wavelength of 430, 550, 610, and 652 nm, respectively. The minimum transmissivity of the polymeric IOs decreased to 1.9%, 2.2%, 2.1%, and 5.8%, respectively. Bright iridescence arose from the Bragg diffraction of the visible light indicating the promising optical properties of the polymeric IOs (inset in Figure 1e). Compared with the PS colloidal crystal templates (Figure S3, Supporting Information), the expanded stop bandwidth combined with the increased stop band depth of the polymeric IOs made them good candidates for realizing optical gain enhancement of light emitters.

Gain medium was constructed by doping 3.0 wt % t-Bu RhB in PMMA film according to our previous report.26,29 The absorption and PL spectra of the t-Bu RhB-doped PMMA film were shown in Figure 2. The t-Bu RhB-doped PMMA film showed maximum absorption at the wavelength of 565 nm. The PL emission band of the t-Bu RhB-doped PMMA film exhibited a peak at the wavelength of 595 nm. Obviously, the relationship of the photonic stop band of the polymeric IOs

Figure 2. Absorption (black, dash) and photoluminescence (red, solid) spectra of 3.0 wt % t-Bu RhB-doped PMMA film. Inset is the molecular structure of t-Bu RhB. C

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and PL band of the gain medium could be divided into three types: mismatching, partial overlapping, and overlapping. The overlapping of the PL emission band and the photonic stop band is significant to promote stimulated emission and even lasing emission.24 Thus, it is convenient to investigate the dependence of the optical gain enhancement on the photonic stop band of the polymeric IOs. The effect of the photonic stop band on the gain enhancement was investigated by extracting the laser-induced emission spectra of the polymeric IO resonating cavity. Figure 3 presented the evolution of the emission spectra as a function of the excitation energy. For polymeric IOs with a photonic stop band at a wavelength of 430 nm, the emission spectra peaked at the wavelength of 595 nm with constant full width at halfmaximum (fwhm) irrespective of the incident pump energy, as shown in Figure 3a. An increase of excitation energy resulted in the linear increase of the emission intensity in the resonating cavity. The constant line width and linear relationship of emission intensities on the pump energy were consistent with that of the control sample (3.0 wt % t-Bu RhB-doped PMMA film, Figure S5, Supporting Information). Gain enhancement was not obtained due to the mismatching of the photonic stop band and PL emission band. In contrast, gain enhancement was observed in the resonating cavity constructed by the polymeric IOs with photonic stop band at the wavelength of 550 and 652 nm, respectively. For the resonating cavity with photonic stop band at a wavelength of 550 nm, the increase of the excitation energy led to the appearance of a new peak at around 609 nm on the emission spectra, that is, at the long-wavelength edge of the photonic stop band. The fwhm dropped dramatically from 49 to 12 nm (inset in Figure 3b). The peak was unobservable from the control sample at the same pump energy as shown in Figure S5 (Supporting Information). The dependence of emission intensity on the incident pump energy verified the threshold characteristics of amplified spontaneous emission, from which the threshold was estimated to be 39.2 μJ/pulse. Similarly, amplified spontaneous emission could be identified by the emergence of a sharp peak at the wavelength of 627 nm in the resonating cavity with photonic stop band of 652 nm. Amplified spontaneous emission occurred at the short-wavelength edge of the photonic stop band, with the threshold of 24.8 μJ/pulse (Figure 3c). Amplified spontaneous emission emerged at either short-wavelength or long-wavelength photonic stop band edges due to the enhanced density of the optical state near the stop band edges.30 A strong increase of the fractional local density of the optical state occurred at both the short- and long-wavelength band edge, especially at the short-wavelength stop band edge.31 Consequently, the threshold of amplified spontaneous emission is much lower at the short-wavelength stop band edge than that at the longwavelength stop band edge, which is consistent with the gain enhancement of the light emitters in the previously reported results.20,32,33 Furthermore, lasing emission was observed in the resonating cavity with a photonic stop band at a wavelength of 610 nm. Emission spectra of the resonating cavity with different excitation intensities were shown in Figure 4a. The emission spectra of the resonating cavity at low excitation intensity showed a broad emission band peaked at about 600 nm. However, a narrow peak at the wavelength of 606 nm emerged when the excitation energy increased above the threshold, indicating the emergence of lasing action in the resonating cavity. The dependence of the emission intensity and fwhm on

Figure 3. Emission spectra as a function of the excitation energy in the resonating cavity with photonic stop band at the wavelength of (a) 430 nm, (b) 550 nm, and (c) 652 nm, respectively. The inset is the dependence of the fwhm (red, triangle) and emission intensity (black, square) on the excitation energy in the resonating cavity with photonic stop band at the wavelength of 430, 550, and 652 nm, respectively.

the pump energy was plotted in Figure 4b. With the increase of the excitation energy, the fwhm of the emission band decreased abruptly from 38 to 1.0 nm, and a simultaneous change in the slope of the emission intensity−pump energy was observed. This spectral line width narrowing and superlinear growth of the emission intensity verified the development of lasing action in the resonating cavity. The lasing threshold was determined to be 4.57 μJ/pulse, and the fwhm of the lasing peak was 1.0 nm. The calculated lasing threshold is 0.74 MW/cm2, which is much lower than the previously reported results in the D

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struction of the polymeric IO resonating cavity and the optical measurement setup (Figure S4); Emission spectra of the t-BuRhB doped PMMA film as a function of the excitation energy. Inset is the dependence of the emission intensity and fwhm of the t-Bu RhB-doped PMMA film on the excitation energy (Figure S5). This material is available free of charge via the Internet at http://pubs.acs.org.

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AUTHOR INFORMATION

Corresponding Author

*E-mail: [email protected]. Notes

The authors declare no competing financial interest.

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ACKNOWLEDGMENTS The authors are grateful to the National Natural Science Foundation of China (Grant No. 51003113, 91123032, 61205194, 61275048, 61275171), the National Basic Research Program of China (2010CB934103), and the International Cooperation Program of MOST (2010DFA01180) for financial support.

Figure 4. (a) Emission spectra of the resonating cavity with photonic stop band at the wavelength of 610 nm under different excitation energy. Offset of the spectra is made for clarity. (b) Dependence of the fwhm and integrated emission intensity on the excitation energy in the resonating cavity with 610 nm photonic stop band.

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colloidal-crystal lasers.9,30 Such a low threshold satisfies the fundamental requirements for practical application of solid-state dye lasers. Single-mode lasing action occurred at the photonic stop band of the polymeric IOs instead of the PL peak of the dye molecules, indicating that the lasing action can be classified as photonic lasing.18,34 Single-mode and low-threshold lasing action in our polymeric IO resonating cavity is significant in fabricating organic solid-state dye lasers.

4. CONCLUSIONS We have successfully demonstrated the lasing and amplified spontaneous emission in the polymeric IO photonic crystal resonating cavity. The resonating cavity was fabricated by sandwiching 3.0 wt % t-Bu RhB-doped PMMA film with a pair of polymeric IOs. Amplified spontaneous emission emerged at the photonic stop band edges of the polymeric IOs, and the threshold was much lower at the short-wavelength stop band edge than that at the long-wavelength stop band edge, which was attributed to the increase of the local density of state at the stop band edges. Furthermore, single-mode lasing action occurred at the photonic stop band of the polymeric IO, indicating the photonic lasing in the resonating cavity. The lasing threshold was 4.57 μJ/pulse, and the fwhm was 1.0 nm. Our experimental results would open up a broad prospect for developing organic solid-state dye lasers.

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ASSOCIATED CONTENT

S Supporting Information *

Experimental details and general characterizations; Components of the photopolymerizable resin used for the construction of the polymeric IO PhCs (Table S1); Molecular structures of the chemicals used (Figure S1); Schematic illustration of the chemical process in the preparation of the polymeric IOs (Figure S2); Transmission spectra of the PS colloidal crystal templates (Figure S3); Schematic illustration of the conE

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