Steric-Hindrance-Functionalized Polydiarylfluorenes: Conformational

Oct 9, 2017 - Key Laboratory for Organic Electronics and Information Displays & Institute of Advanced Materials (IAM), Jiangsu National Synergetic Inn...
0 downloads 14 Views 1MB Size
Subscriber access provided by University of Virginia Libraries & VIVA (Virtual Library of Virginia)

Article

Steric-Hindrance-Functionalized Polydiarylfluorenes: Conformational Behavior, Stabilized Blue Electroluminescence, and Efficient Amplified Spontaneous Emission Lu-Bing Bai, Bin Liu, Ya-Min Han, Meng-Na Yu, Jiong Wang, Xin-Wen Zhang, Chang-Jin Ou, Jin-Yi Lin, WenSai Zhu, Linghai Xie, Cheng-Rong Yin, Jianfeng Zhao, Jianpu Wang, Donal D.C. Bradley, and Wei Huang ACS Appl. Mater. Interfaces, Just Accepted Manuscript • DOI: 10.1021/acsami.7b08980 • Publication Date (Web): 09 Oct 2017 Downloaded from http://pubs.acs.org on October 10, 2017

Just Accepted “Just Accepted” manuscripts have been peer-reviewed and accepted for publication. They are posted online prior to technical editing, formatting for publication and author proofing. The American Chemical Society provides “Just Accepted” as a free service to the research community to expedite the dissemination of scientific material as soon as possible after acceptance. “Just Accepted” manuscripts appear in full in PDF format accompanied by an HTML abstract. “Just Accepted” manuscripts have been fully peer reviewed, but should not be considered the official version of record. They are accessible to all readers and citable by the Digital Object Identifier (DOI®). “Just Accepted” is an optional service offered to authors. Therefore, the “Just Accepted” Web site may not include all articles that will be published in the journal. After a manuscript is technically edited and formatted, it will be removed from the “Just Accepted” Web site and published as an ASAP article. Note that technical editing may introduce minor changes to the manuscript text and/or graphics which could affect content, and all legal disclaimers and ethical guidelines that apply to the journal pertain. ACS cannot be held responsible for errors or consequences arising from the use of information contained in these “Just Accepted” manuscripts.

ACS Applied Materials & Interfaces is published by the American Chemical Society. 1155 Sixteenth Street N.W., Washington, DC 20036 Published by American Chemical Society. Copyright © American Chemical Society. However, no copyright claim is made to original U.S. Government works, or works produced by employees of any Commonwealth realm Crown government in the course of their duties.

Page 1 of 24

1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21 22 23 24 25 26 27 28 29 30 31 32 33 34 35 36 37 38 39 40 41 42 43 44 45 46 47 48 49 50 51 52 53 54 55 56 57 58 59 60

ACS Applied Materials & Interfaces

Steric-Hindrance-Functionalized Polydiarylfluorenes: Conformational Behavior, Stabilized Blue Electroluminescence, and Efficient Amplified Spontaneous Emission Lubing Bai,†,⊥ Bin Liu,‡,⊥ Yamin Han,† Mengna Yu,‡ Jiong Wang,‡ Xinwen Zhang,‡ Changjin Ou,† Jinyi Lin,†* Wensai Zhu,† Linghai Xie,‡* Chengrong Yin,† Jianfeng Zhao,† Jianpu Wang,† Donal D. C. Bradley,& Wei Huang†,‡,§* †

Key Laboratory of Flexible Electronics (KLOFE) & Institute of Advanced Materials (IAM),

Jiangsu National Synergetic Innovation Center for Advanced Materials (SICAM), Nanjing Tech University (NanjingTech), 30 South Puzhu Road, Nanjing 211816, China ‡

Key Laboratory for Organic Electronics and Information Displays & Institute of Advanced

Materials (IAM), Jiangsu National Synergetic Innovation Center for Advanced Materials (SICAM), Nanjing University of Posts & Telecommunications, 9 Wenyuan Road, Nanjing 210023, China §

Shaanxi Institute of Flexible Electronics (SIFE), Northwestern Polytechnical University (NPU),

127 West Youyi Road, Xi’an 710072, Shaanxi, China &

Departments of Engineering Science and Physics and Division of Mathematical, Physical and

Life Sciences, Oxford University, 9 Parks Road, Oxford OX1 3PD, UK KEYWORDS: Polydiarylfluorene, Spirofluorene, β-Phase Conformation, Electroluminescence, Amplified Spontaneous Emission.

ACS Paragon Plus Environment

1

ACS Applied Materials & Interfaces

1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21 22 23 24 25 26 27 28 29 30 31 32 33 34 35 36 37 38 39 40 41 42 43 44 45 46 47 48 49 50 51 52 53 54 55 56 57 58 59 60

Page 2 of 24

ABSTRACT. Control of the hierarchical molecular organization of polydiarylfluorenes by synthetic strategies is significant for optimizing photophysical properties as well as the performance of light-emitting devices. Herein, in order to suppress molecular aggregation and enhance luminescence efficiency, a series of steric units were introduced into polydiarylfluorenes by copolymerization, with the aim of integrating the advantages of the steric hindrance effect and of the β-phase. Optical and Raman spectroscopies revealed a β-phase conformation for a polymer copolymerized with spiro[fluorene-9,9’-xanthene] (SFX), with photoluminescence (PL) peaks at 454, 482, and 517 nm. Moreover, the morphology stability and electroluminescence (EL) stability were also improved without compromising the performance of the polymer lightemitting diodes (PLEDs). Furthermore, three steric-hindrance-functionalized copolymers showed significantly decreased thresholds for amplified spontaneous emission (EthASE) and enhanced stability following thermal annealing treatment. These results indicate that steric hindrance functionalization is a superior approach to improve the overall stability and optoelectronic properties for blue light-emitting π-conjugated polymers.

INTRODUCTION π-Conjugated polymers have attracted wide attention for application in flexible and large-area optoelectronic devices built using low-cost solution processing techniques.1-3 For light-emitting π-conjugated polymers (LCPs), particular interest has been devoted to explore the behavior of the main chain in the solid state,4 where chain aggregates with diverse π-π interactions can influence both the charge transport properties and neutral excited state species.5-7 Consequently, a wide range of photoelectrical processes, such as self-absorption, excimer formation, charge separation and transport, and energy transfer, are sensitive to the morphology of solution-

ACS Paragon Plus Environment

2

Page 3 of 24

1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21 22 23 24 25 26 27 28 29 30 31 32 33 34 35 36 37 38 39 40 41 42 43 44 45 46 47 48 49 50 51 52 53 54 55 56 57 58 59 60

ACS Applied Materials & Interfaces

processed films. For luminescent materials, some of these interchain excited states lead to low photoluminescence (PL) efficiency, poor color purity, and poor spectral stability, which are undesirable for applications in polymer light-emitting diodes (PLEDs) and polymer lasers.8-10 Therefore, rational molecular design of LCPs remains an essential strategy for the precise control of molecular aggregation and film morphology. In the design of high performance LCPs, an effective method for suppressing chain aggregation in the solid state is to isolate the backbone chains.11-13 For red and green LCPs, sufficient progress has been made over the last few decades for applications in organic light-emitting diodes (OLED),14-16 polymer lasers,17-18 and thin film transistors19. However, blue LCPs that show both long-term stability and high efficiency remain a challenge due to the high energy levels and wide band-gaps.20-21 It has been demonstrated that polyfluorenes (PFs) are promising candidates for blue light-emitting materials, with the advantages of easy modification, deep blue emission, and high quantum efficiency.16, 22-23 However, for PFs in the solid state, green band emission due to chain aggregation or the ketone at the C-9 position limits commercial application.24-26 Many approaches have been developed to decrease the tendency of aggregation and avoid the this detrimental excimer emission, including substitution of C-9 with bulky groups,27-30 inducing quasi-planar conformation,31-33 copolymerization with steric hindrance,34 and use of configurations of starburst oligomers.35-37 The planar conformation of PFs (β-phase) can also enhance the charge carrier mobility, spectral purity of the blue emission, and efficiency of amplified spontaneous emission (ASE).33, 38 Compared to the quasi-planar conformation of chains in the robust spiro-bridged ladder-type poly(p-phenylene),33 the β-phase in PFs stems from an intriguing “planar zigzag” (21 helix) chain conformation stabilized by the balance between interchain steric interaction and molecular aggregation in the solid state in thin films,

ACS Paragon Plus Environment

3

ACS Applied Materials & Interfaces

1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21 22 23 24 25 26 27 28 29 30 31 32 33 34 35 36 37 38 39 40 41 42 43 44 45 46 47 48 49 50 51 52 53 54 55 56 57 58 59 60

Page 4 of 24

which can induce an enhanced effective conjugation length, close molecular chain packing, and a larger Förster radius for excitation transfer. In our previous work, the β-phase in a bulky polydiarylfluorene was obtained by regulating the interplay between bulky groups using steric hindrance and between alkoxy side chains using van der Waals forces.27 Recently, a series of blue light-emitting materials equipped with spirofluorenes were developed, whose orthogonal configuration with large steric hindrance endowed the materials with enhanced thermal stability and spectral stability.23, 39-41 To combine the advantages of spirofluorenes and the β-phase, we designed and compared three kinds of polydiarylfluorenes by copolymerization with spirofluorene

derivatives

(Spiro[fluorene-9,9’-xanthene]

(SFX),

6,6-Diphenyl-6H-

benzo[c]chromene (SFSO), and 6,6-Diphenyl-6H-benzo[c]chromene (DPOF)) (Scheme 1).31, 42 A systematic investigation was carried out using UV-vis absorption spectroscopy, fluorescence spectroscopy, and Raman spectroscopy to understand the influence of steric hindrance on the behavior of the main chain conformation. Thermal treatment and PLEDs based on these copolymers were used to explore the morphology and electroluminescent spectral stability, respectively. We successfully obtained a novel copolymer P1 that, while being amorphous in the thin film state, retains the capability of β-phase formation. These copolymers, functionalized with steric hindrance, demonstrate a low threshold for amplified spontaneous emission (EthASE) showing great potential for application in optoelectronic devices.

ACS Paragon Plus Environment

4

Page 5 of 24

1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21 22 23 24 25 26 27 28 29 30 31 32 33 34 35 36 37 38 39 40 41 42 43 44 45 46 47 48 49 50 51 52 53 54 55 56 57 58 59 60

ACS Applied Materials & Interfaces

Scheme 1. Scheme illustration and chemical structures of the steric-hindrance-functionalized polydiarylfluorenes. RESULTS AND DISCUSSION Synthesis and Structural Characterization of Four Polymers All polymers were prepared via Yamamoto-type polymerization following our previous work (Scheme 1).27, 43 The SFX/SFSO steric groups were synthesized according to previous reports.40, 43

The DPOF unit was prepared by a BF3·Et2O-catalyzed Friedel-Crafts reaction; the synthetic

steps are detailed in our previously reported work (Figure S1).27 1H-NMR spectra were used here to calculate the SFX/SFSO/DPOF fraction linked to the copolymer backbone; the copolymerization ratio was calculated to be approximately 20% for all polymers (Figure S2). The number-average molecular weight (Mn) and polydispersity index (PDI) of each polymer were determined by gel permeation chromatography (GPC) to be approximately 24-45 kDa and 1.7-2.2, respectively (Table 1 and Figure S3). Thermal analyses, i.e., differential scanning calorimetry (DSC) and thermogravimetric analysis (TGA), revealed an inconspicuous glass

ACS Paragon Plus Environment

5

ACS Applied Materials & Interfaces

1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21 22 23 24 25 26 27 28 29 30 31 32 33 34 35 36 37 38 39 40 41 42 43 44 45 46 47 48 49 50 51 52 53 54 55 56 57 58 59 60

Page 6 of 24

transition temperature (Tg) for P1 and P2 (Figure S4), all the polymers showed a high decomposition temperature (Td) of greater than 400 °C, corresponding to a 5% weight loss (Figure S5). The highest occupied molecular orbital (HOMO) and the lowest unoccupied molecular orbital (LUMO) energy levels were estimated using the energy level of a ferrocene redox couple (4.8 eV below vacuum) as reference: HOMO/LUMO = -[Eonset –E(Fc/Fc+)+ 4.8] eV (Figure S12). All the results are listed in Table 1. Table 1. Physical, Optical, and Electrochemical Properties of the Polymers Polymers

Mn

PDI

Tg (°C)

Td (°C)

λabsa (nm)

λema (nm)

HOMOb/LUMOb (eV)

P1

2.85×104

1.76

-

412

396, 443

437, 454, 482, 517

-5.85/-2.15

P2

2.41×104

2.23

-

410

396

440, 466

-5.70/-2.31

P3

3.04×104

2.06

200

414

396

440, 466

-5.77/-2.31

P4

4.54×104

1.77

210

417

400, 412, 443

454, 485, 518

-5.73/-2.14

a

Films were drop cast from toluene solutions of 1 mg/ml. bEstimated from the onset of oxidation

and reduction potentials.

ACS Paragon Plus Environment

6

Page 7 of 24

1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21 22 23 24 25 26 27 28 29 30 31 32 33 34 35 36 37 38 39 40 41 42 43 44 45 46 47 48 49 50 51 52 53 54 55 56 57 58 59 60

ACS Applied Materials & Interfaces

Figure 1. Optical and Raman spectra. (a) UV-vis and PL spectra of the polymer films drop cast from toluene solutions (1 mg/mL). (b) Comparison of the P1 PL spectra obtained for a drop-cast film with the spectra from the individual β-phase and amorphous states. (c) Raman spectra of the four polymer films prepared by spin-coating (blue lines) and drop-casting (orange lines) from toluene solutions. Conformational Behavior of Four Polymers Optical spectroscopy was used to investigate the photophysical properties of the four polymers in various states. The formation of the β-phase can strongly depend on the solvents used and postdeposition treatment.44 In dilute toluene solution, a weak shoulder peak was observed at 443 nm for P1 and P4 (10-5 mg/ml), indicating the formation of the β-phase (Figure S6). In thin films spin-coated from toluene solutions, no characteristic β-phase absorption peak was identified at 443 nm, with the emission peaks at 435, 462, and 500 nm were all attributed to emission from

ACS Paragon Plus Environment

7

ACS Applied Materials & Interfaces

1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21 22 23 24 25 26 27 28 29 30 31 32 33 34 35 36 37 38 39 40 41 42 43 44 45 46 47 48 49 50 51 52 53 54 55 56 57 58 59 60

Page 8 of 24

the amorphous state (Figure S7). We infer that the balancing of intermolecular forces (van der Waals forces) and steric interaction is destroyed in the polymer films due to the centripetal force and fast solvent evaporation experienced during film formation.27 Typically, the β-phase can be induced by exposing the thin film to solvents with moderate solubility or slowing down the kinetic process of film formation during solution processing. Therefore, drop-casting can be used to promote polymer chain rearrangement and further facilitate the efficient formation of the βphase conformation. As shown in Figure 1a, distinct shoulder absorption peaks are observed at 443 nm for the drop-cast films of P1 and P4, but these peaks are absent for P2 and P3 (Figure 1a and Table 1). This observation indicates the formation of the β-phase conformation in the thin films, consistent with measurements of the excitation PL spectra (Figure S8). The β-phase was further confirmed by identification of the emission peak features at 454, 482, and 517 nm, which are assigned to the 0-0, 0-1, and 0-2 vibrational transitions of polyfluorene in a planar conformation (Figure 1a). Moreover, the characteristic emission peaks at 454, 482, and 517 nm become much more distinguishable for P1 when tuning the excitation wavelength from 390 to 440 nm (Figure S9). By comparison with the PL spectrum obtained in the amorphous state, we speculate that the spectral response contains contributions from a mix of two types of chromophores present in the amorphous state and the β-phase. We deducted the amorphous emission spectrum from the mixed spectrum of P1 to obtain the individual β-phase emission (Figure 1b). Through analysis of the optical spectra of the three copolymers, we found the typical β-phase only exists in the P1 polymer film. In addition, the PL quantum yields (ΦPLQY) of P1, P2, and P3 films are approximately 55%, 50%, and 47%, respectively, which are all higher than that of P4 (ΦPLQY = 43%). That is because the steric hindrance in the copolymers could effectively reduce the aggregation, and additional the stronger crystallization of P4 was unfavorable for the

ACS Paragon Plus Environment

8

Page 9 of 24

1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21 22 23 24 25 26 27 28 29 30 31 32 33 34 35 36 37 38 39 40 41 42 43 44 45 46 47 48 49 50 51 52 53 54 55 56 57 58 59 60

ACS Applied Materials & Interfaces

luminescence efficiency (Figure S11).so that the ΦPLQY of these copolymers higher than that of P4. The supramolecular effects of the sulfone units in P2 made the chain interaction stronger than that of P1, so that the ΦPLQY of P2 was lower than P1. As to P3, the copolymerized moiety was biphenyl embedded by oxygen atoms and the effective conjugation length was shorter than those of fluorine monomer, so that the ΦPLQY of P3 was lower than P1 and P2. Raman spectroscopy was also used as an effective tool to probe the conformational transition and molecular rotation/vibration. To some degree, the β-phase of PFs is a type of quasi-planar conformation resulting from the conformational change of the polymer chain, characterized by high intrachain order, and with a fixed rotational angle of 165o between the monomer units.45 According to our previous report,31 the planar conformation can be detected by measurement of the relative Raman intensity at 1304 cm-1 and the frequency shift at 1600 cm-1. As shown in Figure 1c, the main Raman peaks were observed in the range of 1200 to 1700 cm-1, correlated to the stretching models of carbon bonds in conjugated structures. The data show a distinct enhancement in the Raman intensity of the drop-cast P1 and P4 films in the spectral region from 1290 to 1305 cm-1, which is assigned to the planarization of the polymer backbone. In addition, approximately 3 and 6 cm-1 frequency shifts are observed at approximately 1600 cm-1 for the P1 and P4 polymer films, respectively, attributed to the enhanced planarity of the backbone that increases the delocalization of π-electrons. However, no frequency shift was observed at 1600 cm-1 for the P2 and P3 polymer films. Consequently, we propose that the strong molecular interactions deriving from the sulfur and oxygen atoms in P2 destroy the formation of the βphase, as does the asymmetric steric hindrance of the DPOF unit in P3. The Raman results are consistent with the optical spectroscopy measurements. Therefore, we consider that only by

ACS Paragon Plus Environment

9

ACS Applied Materials & Interfaces

1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21 22 23 24 25 26 27 28 29 30 31 32 33 34 35 36 37 38 39 40 41 42 43 44 45 46 47 48 49 50 51 52 53 54 55 56 57 58 59 60

Page 10 of 24

copolymerization with appropriate conjugated steric units can one generate planar segments in polymer films.

Figure 2. AFM images of the P1 (a), P2 (b), P3 (c), and P4 (d) pristine films (top) and films annealed at 250 oC in a nitrogen atmosphere (bottom). Time-dependent PL spectra of the P1 (e), P2 (f), P3 (g), and P4 (h) films annealed at 200 oC in air.

ACS Paragon Plus Environment

10

Page 11 of 24

1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21 22 23 24 25 26 27 28 29 30 31 32 33 34 35 36 37 38 39 40 41 42 43 44 45 46 47 48 49 50 51 52 53 54 55 56 57 58 59 60

ACS Applied Materials & Interfaces

Morphological and Spectral Stability of the Four Polymers To investigate the effect of steric hindrance on the thermal stability of LCPs, atomic force microscopy (AFM) was used to study variation in the detailed film morphology before and after the annealing treatment (Figure 2). Uniform and smooth pristine films were deposited by spincoating from toluene solutions; the polymer films showed root mean square (RMS) roughness of 0.51, 0.52, 0.43, and 0.90 nm for P1-P4, respectively. No distinct granular domains appeared in the copolymer films after annealing treatment at 250 oC, indicating good thermal stability of the copolymer morphology. In contrast, P4 showed a relatively large increase in the RMS roughness (1.70 nm) and the formation of granular domains, which can be derived from chain aggregationinduced crystalline structures.31 By thermal annealing at 200 oC in air, no spectral variation was observed, as shown in Figure 2d, which demonstrates the excellent spectral stability for the four polymers. As expected, a small amount of β-phase was found in the annealed P4 film, but none for the copolymers. The PL spectra of all polymer films were stable after thermal annealing in air for 10 min at various temperatures (Figure S10). Moreover, no diffraction peaks were observed in the copolymer films as measured by one-dimensional X-ray diffraction (1D-XRD) (Figure S11). Therefore, the crystallization induced by chain aggregation was effectively suppressed in P1, P2 and P3 due to copolymerization with high rigidity spirofluorene derivatives. These results demonstrate that the incorporation of a moiety, with appropriate steric hindrance, can improve morphological stability as well as suppress crystallization induced by chain aggregation.

ACS Paragon Plus Environment

11

ACS Applied Materials & Interfaces

1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21 22 23 24 25 26 27 28 29 30 31 32 33 34 35 36 37 38 39 40 41 42 43 44 45 46 47 48 49 50 51 52 53 54 55 56 57 58 59 60

Page 12 of 24

Figure 3. (a) Energy level diagram of the PLEDs with the structure of ITO/PEDOT:PSS (40 nm)/emissive layer (50 nm)/TPBi (20 nm)/LiF (0.8 nm)/Al (100 nm). (b) Electroluminescence (EL) spectra of the P1-P4 devices. (c) Current density-voltage-luminance (J-V-L) characteristics and (d) current efficiency versus current density curves of the devices. Electroluminescent Properties As discussed above, the four polymers show deep blue emission, high fluorescence quantum yield, and excellent stability. To investigate the influence of steric hindrance on the electroluminescence (EL) properties, particularly the color stability under electrical bias, PLEDs with a simple device configuration of ITO/PEDOT:PSS (40 nm)/emissive layer (50 nm)/TPBi (20 nm)/LiF (0.8 nm)/Al (100 nm) were fabricated using the four polymers (Figure 3a). At low applied voltage, the EL spectra (Figure 3b) of all the devices were similar to the corresponding

ACS Paragon Plus Environment

12

Page 13 of 24

1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21 22 23 24 25 26 27 28 29 30 31 32 33 34 35 36 37 38 39 40 41 42 43 44 45 46 47 48 49 50 51 52 53 54 55 56 57 58 59 60

ACS Applied Materials & Interfaces

PL spectra (Figure 2) and consisted of three emission peak features at 430, 460, and 485 nm. Upon increasing the applied voltage from 5 V (> 40 mA cm-2) to 9 V (> 500 mA cm-2), the EL spectra of the P1 devices showed little change, with a turn-on voltage (Von) of 3.8 V. Moreover, the value for the Commission Internationale de L’Eclairage (CIE) coordinate showed negligible variation (Table 2), suggesting a voltage-independent EL for the P1 devices. However, the 0-1 emission in the EL spectra of the three other polymer devices (especially P4) showed a slight enhancement with increased voltage, consistent with our previous work.31 Furthermore, no green band emission (due to energy transfer or aggregation) was observed in these three copolymers with film thicknesses of approximately 50 nm. Therefore, use of the steric-hindrancefunctionalized polymers to suppress polymer chain aggregation in the solid state leads to negligible low-energy band emission during device operation. Figure 3c and Figure 3d shows the current density-voltage-luminance (J-V-L) characteristics and the current efficiency versus current density curves of the devices, respectively. The P1 and P4 polymers show the best device performances with a maximum luminous efficiency of 1856 cd m-2 (0.70 cd A-1) and 1899 cd m-2 (0.95 cd A-1), respectively (Table 2). The steric hindrance-functionalized polydiarylfluorenes show pure blue emission with superior EL stability and high luminance with comparable current efficiency, and thus have great potential for application in light-emitting devices. Table 2. Summary of the Device Performances and ASE Characteristics

EM

Vona (V)

ASE threshold

Lmaxb (cd m-2)

ηc.maxc (cd A-1)

CIE (x, y)d

λASE (nm)

µJ/cm2

nJ/pulse

Thicknesse (nm)

P1

3.75

1856

0.70

(0.15, 0.10)

459

1.02

12.3

155

P2

3.57

1780

0.75

(0.15, 0.12)

461

3.24

38.3

160

P3

3.46

1548

0.64

(0.16, 0.13)

462

5.13

61.5

150

ACS Paragon Plus Environment

13

ACS Applied Materials & Interfaces

1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21 22 23 24 25 26 27 28 29 30 31 32 33 34 35 36 37 38 39 40 41 42 43 44 45 46 47 48 49 50 51 52 53 54 55 56 57 58 59 60

P4 a

d

3.58

1899

0.95

(0.16, 0.14)

461

Page 14 of 24

8.10

94.4

148

Turn-on voltage at a brightness of 1 cd/m2. bMaximum luminance. cMaximum current efficiency. Measured at 7 V. eSpin-coated films from toluene solution (10 mg/mL).

Figure 4. (a) Normalized PL and ASE spectra (excited at 380 nm) of the spin-coated films, and temperature dependence of the ASE threshold (inset). (b) ASE output intensity versus pump energy density for P1-P4; inset shows the same data near the threshold of ASE. ASE Properties High PLQY and good thermal and spectral stability are key factors for LCPs utilized as the gain medium in an organic solid-state laser. The polymer chemical structure can significantly affect the optical gain properties.18,

46-47

The influence of the polymer steric groups on the ASE

characteristics were studied using a Q-switched Nd3+:YAG laser operating as the pump source at a wavelength near the polymer absorption maximum. As shown in Figure 4a, upon optical pumping, all samples show prominent ASE from the 0-1 vibration transition, with the peak wavelength centered at approximately 460 nm. Moreover, the ASE threshold of steric hindrance-

ACS Paragon Plus Environment

14

Page 15 of 24

1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21 22 23 24 25 26 27 28 29 30 31 32 33 34 35 36 37 38 39 40 41 42 43 44 45 46 47 48 49 50 51 52 53 54 55 56 57 58 59 60

ACS Applied Materials & Interfaces

functionalized polydiarylfluorenes was found to be lower than the threshold of P4 under the same experimental conditions (Figure 4b), which suggests superior optical amplifying properties for the copolymers with steric groups. Notably, the P1 sample showed an ultralow ASE threshold of 12.3 nJ pulse-1 (1.02 µJ cm-2) compared to other three polymers, which is among the best reported for a fluorine-based polymer or macromolecule (similar ASE peaks). The ASE characteristics were measured as a function of gradient annealing temperature to investigate the thermal stability of the gain property. The film samples were annealed for 10 minutes in a N2 filled glovebox at each temperature gradient (Figure 4a, inset). Only a nominal change in the threshold for all samples is observed for increasing annealing temperature from room temperature to 150 oC, indicating no drastic change in the material morphology or chemical structure. However, a further increase in the temperature up to 220 oC led to a significant increase in the ASE threshold for P4 due to the presence of crystalline aggregates with a rough surface (Figure 2d). Consequently, P4 shows lower ASE stability compared to the copolymers. From these control experiments using reference polymers, we speculate that the introduction of steric spirofluorenes can effectively suppress the energy loss caused by molecular vibration and promote higher radiation transition efficiency, while the orthogonal bulky structure can reduce aggregation leading to superior ASE performance. The results show that copolymerization with appropriate steric hindrance units can be used to realize a significantly reduced EthASE. CONCLUSION In

this

work,

we

designed

and

synthesized

three

steric-hindrance-functionalized

polydiarylfluorenes with varying degrees of steric effect and systemically investigated their conformational behavior and optoelectronic properties. The β-phase conformation forming ability of copolymer P1 was verified by UV-vis absorbance and fluorescence spectroscopies,

ACS Paragon Plus Environment

15

ACS Applied Materials & Interfaces

1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21 22 23 24 25 26 27 28 29 30 31 32 33 34 35 36 37 38 39 40 41 42 43 44 45 46 47 48 49 50 51 52 53 54 55 56 57 58 59 60

Page 16 of 24

with a typical absorption peak at 443 nm and red shifted emission curve. The Raman spectra showed enhanced intensity at 1304 cm-1 and a soft shift of approximately 3 cm-1 at 1600 cm-1, which further confirmed the quasi-planar conformation of the P1 chain in the drop-cast film. The reduced roughness transformation and spectral change following thermal annealing treatment revealed the enhanced morphology stability for the copolymers. Furthermore, the EL spectral stability over an applied voltage range from 5 V to 9 V was more stable for the copolymers than for P4. Finally, the EthASE of the steric copolymers was demonstrated to be lower than that of P4. P1 showed the lowest EthASE among all reported fluorene-based materials. Therefore, considering the morphological, EL, and ASE spectral stability of the thin films, copolymerization with steric hindrance groups is an effective strategy to improve the properties of LCPs for use in optoelectronic devices. ASSOCIATED CONTENT Supporting Information. Experimental conditions and methods, materials characteristics, 1H NMR, DSC, TGA, CV data, and additional data. AUTHOR INFORMATION *E-mail: [email protected] *E-mail: [email protected] *E-mail: [email protected] Author Contributions ⊥

Lubing Bai and Bin Liu equally contributed to this work.

Notes

ACS Paragon Plus Environment

16

Page 17 of 24

1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21 22 23 24 25 26 27 28 29 30 31 32 33 34 35 36 37 38 39 40 41 42 43 44 45 46 47 48 49 50 51 52 53 54 55 56 57 58 59 60

ACS Applied Materials & Interfaces

The authors declare no competing financial interest ACKNOWLEDGMENT The project was supported by the National Key Basic Research Program of China (973) (2015CB932200), National Natural Science Foundation of China (21504041, 21502091, 21404057), Synergetic Innovation Center for Organic Electronics and Information Displays, Priority Academic Program Development of Jiangsu Higher Education Institutions, PAPD (YX03001), Natural Science Foundation of Jiangsu Province for Young Scholars (BK20140948), Open Project from State Key Laboratory of Supramolecular Structure and Materials at Jilin University (sklssm201710). REFERENCES 1. Oh, J. Y.; Rondeau-Gagne, S.; Chiu, Y. C.; Chortos, A.; Lissel, F.; Wang, G. N.; Schroeder, B. C.; Kurosawa, T.; Lopez, J.; Katsumata, T.; Xu, J.; Zhu, C.; Gu, X.; Bae, W. G.; Kim, Y.; Jin, L.; Chung, J. W.; Tok, J. B.; Bao, Z. Intrinsically Stretchable and Healable Semiconducting Polymer for Organic Transistors. Nature 2016, 539, 411-415. 2. Liu, C.; Li, Y.; Li, Y.; Yang, C.; Wu, H.; Qin, J.; Cao, Y. Efficient Solution-Processed DeepBlue Organic Light-Emitting Diodes Based on Multibranched Oligofluorenes with a Phosphine Oxide Center. Chem. Mater. 2013, 25, 3320-3327. 3. Gomez-Bombarelli, R.; Aguilera-Iparraguirre, J.; Hirzel, T. D.; Duvenaud, D.; Maclaurin, D.; Blood-Forsythe, M. A.; Chae, H. S.; Einzinger, M.; Ha, D. G.; Wu, T.; Markopoulos, G.; Jeon, S.; Kang, H.; Miyazaki, H.; Numata, M.; Kim, S.; Huang, W.; Hong, S. I.; Baldo, M.; Adams, R. P.; Aspuru-Guzik, A. Design of Efficient Molecular Organic Light-Emitting Diodes by a HighThroughput Virtual Screening and Experimental Approach. Nat. Mater. 2016, 15, 1120-1127.

ACS Paragon Plus Environment

17

ACS Applied Materials & Interfaces

1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21 22 23 24 25 26 27 28 29 30 31 32 33 34 35 36 37 38 39 40 41 42 43 44 45 46 47 48 49 50 51 52 53 54 55 56 57 58 59 60

Page 18 of 24

4. Donley, C. L.; Zaumseil, J.; Andreasen, J. W.; Nielsen, M. M.; Sirringhaus, H.; Friend, R. H.; Kim, J.-S. Effects of Packing Structure on the Optoelectronic and Charge Transport Properties in Poly(9,9-di-n-octylfluorene-alt-benzothiadiazole). J. Am. Chem. Soc. 2005, 127, 12890. 5. Zhou, Y.; Li, M.; Guo, Y.; Lu, H.; Song, J.; Bo, Z.; Wang, H. Dibenzopyran-Based Wide Band Gap Conjugated Copolymers: Structural Design and Application for Polymer Solar Cells. ACS Appl. Mater. Interfaces, 2016, 8, 31348-31358. 6. Lombeck, F.; Di, D.; Yang, L.; Meraldi, L.; Athanasopoulos, S.; Credgington, D.; Sommer, M.; Friend, R. H.PCDTBT: From Polymer Photovoltaics to Light-Emitting Diodes by SideChain-Controlled Luminescence. Macromolecules 2016, 49, 9382-9387. 7. Unger, T.; Panzer, F.; Consani, C.; Koch, F.; Brixner, T.; Bässler, H.; Köhler A. Ultrafast Energy Transfer between Disordered and Highly Planarized Chains of Poly[2-methoxy-5-(2ethylhexyloxy)-1,4-phenylenevinylene] (MEH-PPV). ACS Macro. Lett. 2015, 4, 412-416. 8. Yap, B. K.; Xia, R.; Campoy-Quiles, M.; Stavrinou, P. N.; Bradley, D. D. Simultaneous Optimization of Charge-Carrier Mobility and Optical Gain in Semiconducting Polymer Films. Nat. Mater. 2008, 7, 376-380. 9. Yu, W. L.; Pei, J.; Huang, W.; Heeger, A. Spiro-Functionalized Polyfluorene Derivatives as Blue Light-Emitting Materials. Adv. Mater. 2000, 12, 828-831. 10. Schelkle, K. M.; Bender, M.; Jeltsch, K.; Buckup, T.; Mullen, K.; Hamburger, M.; Bunz, U. H., Light-Induced Solubility Modulation of Polyfluorene to Enhance the Performance of OLEDs. Angew. Chem. Int. Ed. 2015, 54, 14545-14548. 11. Bridges, C. R.; Ford, M. J.; Popere, B. C.; Bazan, G. C.; Segalman, R. A. Formation and Structure of Lyotropic Liquid Crystalline Mesophases in Donor−Acceptor Semiconducting Polymers. Macromolecules 2016, 49, 7220-7229.

ACS Paragon Plus Environment

18

Page 19 of 24

1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21 22 23 24 25 26 27 28 29 30 31 32 33 34 35 36 37 38 39 40 41 42 43 44 45 46 47 48 49 50 51 52 53 54 55 56 57 58 59 60

ACS Applied Materials & Interfaces

12. Cacialli, F.; Wilson, J. S.; Michels, J. J.; Clement, D.; Silva, C.; Friend, R. H.; Severin, N.; Samorì, P.; Rabe, J. P.; O’Connell, M. J. Cyclodextrin-Threaded Conjugated Polyrotaxanes as Insulated Molecular Wires with Reduced Interstrand Interactions. Nat. Mater. 2002, 1, 160-164. 13. Swager, T. Polymer light-emitting Devices: Light from Insulated Organic Wires. Nat. Mater. 2002, 1, 151-152. 14. Prachumrak, N.; Pojanasopa, S.; Namuangruk, S.; Kaewin, T.; Jungsuttiwong, S.; Sudyoadsuk, T.; Promarak, V. Novel Bis[5-(fluoren-2-yl)thiophen-2-yl]benzothiadiazoleEndCapped with Carbazole dendrons as Highly Efficient Solution-Processed Nondoped Red Emitters for Organic Light-Emitting Diodes. ACS. Appl. Mater. Interfaces, 2013, 5, 8694-8703. 15. Chiang, C. L.; Wu, M. F.; Dai, D. C.; Wen, Y. S.; Wang, J. K.; Chen, C. T. Red-Emitting Fluorenes as Efficient Emitting Hosts for Non-Doped, Organic Red-Light-Emitting Diodes. Adv. Funct. Mater.2005, 15, 231-238. 16. Deng, C.; Ling, J. Amphiphilic Copolymers of Polyfluorene Methacrylates Exhibiting Tunable Emissions for Ink-Jet Printing. Macromol. Rapid Commun. 2016,37, 1352-1356. 17. Rabe, T.; Hoping, M.; Schneider, D.; Becker, E.; Johannes, H. H.; Kowalsky, W.; Weimann, T.; Wang, J.; Hinze, P.; Nehls, B. S.; Scherf, U.; Farrell, T.; Riedl, T. Threshold Reduction in Polymer Lasers Based on Poly(9,9-dioctylfluorene) with Statistical Binaphthyl Units. Adv. Funct. Mater. 2005, 15, 1188-1192. 18. Yu, Z.; Guo, X.; Zhang, Q.; Chi, L.; Chen, T.; Xia, R.; Wu, L.; Lüer, L.; CabanillasGonzalez, J. Novel Fluorene-Based Copolymers Containing Branched 2-Methyl-butylSubstituted Fluorene-co-benzothiadiazole Units for Remarkable Optical Gain Enhancement in Green-Yellow Emission Range. J. Phys. Chem. C 2016, 120, 11350-11358.

ACS Paragon Plus Environment

19

ACS Applied Materials & Interfaces

1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21 22 23 24 25 26 27 28 29 30 31 32 33 34 35 36 37 38 39 40 41 42 43 44 45 46 47 48 49 50 51 52 53 54 55 56 57 58 59 60

Page 20 of 24

19. Zaumseil, J.; Donley, C. L.; Kim, J. S.; Friend, R. H.; Sirringhaus, H. Efficient Top-Gate, Ambipolar, Light-Emitting Field-Effect Transistors Based on a Green-Light-Emitting Polyfluorene. Adv. Mater. 2006, 18, 2708-2712. 20. Gu, C.; Dong, W.; Yao, L.; Lv, Y.; Zhang, Z.; Lu, D.; Ma, Y. Cross-linked multifunctional Conjugated Polymers Prepared by in Situ Electrochemical Deposition for a Highly-Efficient Blue-Emitting and Electron-Transport Layer. Adv. Mater. 2012, 24, 2413-2417. 21. Yang, X.; Xu, X.; Zhou, G. Recent Advances of the Emitters for High Performance DeepBlue Organic Light-Emitting Diodes. J. Mater. Chem. C 2015, 3, 913-944. 22. Xie, L.-H.; Yin, C.-R.; Lai, W.-Y.; Fan, Q.-L.; Huang, W. Polyfluorene-Based Semiconductors Combined with Various Periodic Table Elements for Organic Electronics. Prog. Polym. Sci. 2012, 37, 1192-1264. 23. Wang, X.; Zhao, L.; Shao, S.; Ding, J.; Wang, L.; Jing, X.; Wang, F. Poly(spirobifluorene)s Containing Nonconjugated Diphenylsulfone Moiety: Toward Blue Emission Through a Weak Charge Transfer Effect. Macromolecules 2014, 47, 2907-2914. 24. Xin, Y.; Wen, G.-A.; Zeng, W.-J.; Zhao, L.; Zhu, X.-R.; Fan, Q.-L.; Feng, J.-C.; Wang, L.H.; Wei, W.; Peng, B. Hyperbranched Oxadiazole-Containing Polyfluorenes: Toward Stable Blue Light PLEDs. Macromolecules 2005, 38, 6755-6758. 25. Romaner, L.; Pogantsch, A.; Scandiucci de Freitas, P.; Scherf, U.; Gaal, M.; Zojer, E.; List, E. J. The Origin of Green Emission in Polyfluorene-Based Conjugated Polymers: On-Chain Defect fluorescence. Adv. Funct. Mater. 2003, 13, 597-601. 26. Gaal, M.; List, E. J.; Scherf, U. Excimers or Emissive On-Chain defects? Macromolecules 2003, 36, 4236-4237.

ACS Paragon Plus Environment

20

Page 21 of 24

1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21 22 23 24 25 26 27 28 29 30 31 32 33 34 35 36 37 38 39 40 41 42 43 44 45 46 47 48 49 50 51 52 53 54 55 56 57 58 59 60

ACS Applied Materials & Interfaces

27. Lin, J.-Y.; Zhu, W.-S.; Liu, F.; Xie, L.-H.; Zhang, L.; Xia, R.; Xing, G.-C.; Huang, W. A Rational Molecular Design of β-Phase Polydiarylfluorenes: Synthesis, Morphology, and Organic Lasers. Macromolecules 2014, 47, 1001-1007. 28. Tang, S.; Liu, M. R.; Lu, P.; Xia, H.; Li, M.; Xie, Z. Q.; Shen, F. Z.; Gu, C.; Wang, H. P.; Yang, B.; Ma, Y. G. A Molecular Glass for Deep-Blue Organic Light-Emitting Diodes Comprising a 9,9′-Spirobifluorene Core and Peripheral Carbazole Groups. Adv. Funct. Mater. 2007, 17, 2869-2877. 29. Yu, L.; Liu, J.; Hu, S.; He, R.; Yang, W.; Wu, H.; Peng, J.; Xia, R.; Bradley, D. D. C. Red, Green, and Blue Light-Emitting Polyfluorenes Containing a Dibenzothiophene-S,S-Dioxide Unit and Efficient High-Color-Rendering-Index White-Light-Emitting Diodes Made Therefrom. Adv. Funct. Mater. 2013, 23, 4366-4376. 30. Wu, Y.; Li, J.; Fu, Y.; Bo, Z. Synthesis of Extremely Stable Blue Light Emitting Poly(spirobifluorene)s with Suzuki Polycondensation. Org. Lett. 2004, 6, 3485-3487. 31. Liu, B.; Lin, J.; Liu, F.; Yu, M.; Zhang, X.; Xia, R.; Yang, T.; Fang, Y.; Xie, L.; Huang, W. A Highly Crystalline and Wide-Bandgap Polydiarylfluorene with Beta-Phase Conformation toward Stable Electroluminescence and Dual Amplified Spontaneous Emission. ACS Appl. Mater. Interfaces, 2016, 8, 21648-21655. 32. He, J.; Du, L.; Wang, C.; Jiang, M.; Liu, L.; Mo, Y.; Xie, Z.; Yang, B.; Ma, Y. Conformation Pre-Organization in Fluorene-Based Conjugated Polymer for Simultaneous Enhancement of Luminescence and Charge Mobility. Polym. Chem. 2017, 8, 1255-1262. 33. Wu, Y.; Zhang, J.; Fei, Z.; Bo, Z. Spiro-Bridged Ladder-Type Poly(p-phenylene)s: Towards Structurally Perfect Light-Emitting Materials. J. Am. Chem. Soc. 2008, 130, 7192-7193.

ACS Paragon Plus Environment

21

ACS Applied Materials & Interfaces

1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21 22 23 24 25 26 27 28 29 30 31 32 33 34 35 36 37 38 39 40 41 42 43 44 45 46 47 48 49 50 51 52 53 54 55 56 57 58 59 60

Page 22 of 24

34. Herguth, P.; Jiang, X.; Liu, M. S.; Jen, A. K.-Y. Highly Efficient Fluorene- and Benzothiadiazole-Based

Conjugated

Copolymers

for

Polymer

Light-Emitting

Diodes.

Macromolecules 2002, 35, 6094-6100. 35.Liu, C.; Fu, Q.; Zou, Y.; Yang, C.; Ma, D.; Qin, J. Low Turn-on Voltage, High-PowerEfficiency, Solution-Processed Deep-Blue Organic Light-Emitting Diodes Based on Starburst Oligofluorenes with Diphenylamine End-Capper to Enhance the HOMO Level. Chem. Mater. 2014, 26, 3074-3083. 36. Jiang, Y.; Fang, M.; Chang, S. J.; Huang, J. J.; Chu, S. Q.; Hu, S. M.; Liu, C. F.; Lai, W. Y.; Huang, W. Towards Monodisperse Star-Shaped Ladder-Type Conjugated Systems: Design, Synthesis, Stabilized Blue Electroluminescence, and Amplified Spontaneous Emission. Chem. Eur. J. 2017, 23, 5448-5458. 37. Xu, W.; Yi, J.; Lai, W.-Y.; Zhao, L.; Zhang, Q.; Hu, W.; Zhang, X.-W.; Jiang, Y.; Liu, L.; Huang, W. Pyrene-Capped Conjugated Amorphous Starbursts: Synthesis, Characterization, and Stable Lasing Properties in Ambient Atmosphere. Adv. Funct. Mater. 2015, 25, 4617-4625. 38. Rothe, C.; Galbrecht, F.; Scherf, U.; Monkman, A. The β-Phase of Poly(9,9-dioctylfluorene) as a Potential System for Electrically Pumped Organic Lasing. Adv. Mater. 2006, 18, 2137-2140. 39. Li, J.; Ding, D.; Tao, Y.; Wei, Y.; Chen, R.; Xie, L.; Huang, W.; Xu, H. A Significantly Twisted Spirocyclic Phosphine Oxide as a Universal Host for High-Efficiency Full-Color Thermally Activated Delayed Fluorescence Diodes. Adv. Mater. 2016, 28, 3122-3130. 40. Chan, C. Y.; Wong, Y. C.; Chan, M. Y.; Cheung, S. H.; So, S. , K.; Yam, V. W. Bifunctional Heterocyclic Spiro Derivatives for Organic Optoelectronic Devices. ACS Appl. Mater. Interfaces, 2016, 8, 24782-24792.

ACS Paragon Plus Environment

22

Page 23 of 24

1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21 22 23 24 25 26 27 28 29 30 31 32 33 34 35 36 37 38 39 40 41 42 43 44 45 46 47 48 49 50 51 52 53 54 55 56 57 58 59 60

ACS Applied Materials & Interfaces

41. Karim, M. A.; Cho, Y.-R.; Park, J. S.; Yoon, K.-J.; Lee, S. J.; Jin, S.-H.; Lee, G.-D.; Gal, Y.S. Synthesis and Characterization of Spirobifluorene-Based Polymers for Organic Light-Emitting Diode Applications. Macromol. Res. 2008, 16, 337-344. 42. Lin, J.; Li, W.; Yu, Z.; Yi, M.; Ling, H.; Xie, L.; Li, S.; Huang, W. π-ConjugationInterrupted Hyperbranched Polymer Electrets for Organic Nonvolatile Transistor Memory Devices. J. Mater. Chem. C 2014, 2, 3738. 43. Xie, L.-H.; Liu, F.; Tang, C.; Hou, X.-Y.; Hua, Y.-R.; Fan, Q.-L.; Huang, W. Unexpected One-Pot Method to Synthesize Spiro[fluorene-9,9’ -xanthene] Building Blocks for Blue-LightEmitting Materials. Org. Lett. 2006, 8, 2787-2790. 44. Liu, B.; Lin, J.; Lei, Z.; Sun, M.; Xie, L.; Xue, W.; Yin, C.; Zhang, X.; Huang, W. Solvent and Steric Hindrance Effects of Bulky Poly(9,9-diarylfluorene)s on Conformation, Gelation, Morphology, and Electroluminescence. Macromol. Chem. Phys. 2015, 216, 1043-1054. 45. Chunwaschirasiri, W.; Tanto, B.; Huber, D.; Winokur, M. Chain Conformations and Photoluminescence of Poly(di-n-octylfluorene). Phys. Rev. Lett. 2005, 94, 107402. 46. Laquai, F.; Mishra, A. K.; Müllen, K.; Friend, R. H. Amplified Spontaneous Emission of Poly(ladder-type phenylene)s - The Influence of Photophysical Properties on ASE Thresholds. Adv. Funct. Mater., 2008, 18, 3265-3275. 47. Smirnov, J. R.; Zhang, Q.; Wannemacher, R.; Wu, L.; Casado, S.; Xia, R.; Rodriguez, I.; Cabanillas-Gonzalez, J. Flexible All-Polymer Waveguide for Low Threshold Amplified Spontaneous Emission. Sci. Rep. 2016, 6, 34565.

ACS Paragon Plus Environment

23

ACS Applied Materials & Interfaces

1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21 22 23 24 25 26 27 28 29 30 31 32 33 34 35 36 37 38 39 40 41 42 43 44 45 46 47 48 49 50 51 52 53 54 55 56 57 58 59 60

Page 24 of 24

Table of Contents Graphic

ACS Paragon Plus Environment

24