Abstract
Conjugated polymers have emerged as ideal organic laser materials for the excellent optoelectrical properties and facile processability. During a typical lasing process, resonator configurations with specific geometry are essential to provide optical feedback and then amplified light. Herein, we summarized the geometry and working mechanism of several typical resonator configurations formed with conjugated polymers. Meanwhile, recent advances in fabrication techniques and lasing performance are also discussed to provide new ideas for the design and optimization of microcavity geometries. Followed by the advances of practical applications in fields of laser sensing, bioimaging, and laser illumination/display, we make a summary of the existing bottlenecks and future perspectives of electrically driven organic lasers toward laser display and illumination.
Introduction
In the past decades, lasers have led to great revolution in technology and industrial fields because of their unique and excellent properties, including high intensity, good monochromaticity, directionality, and strong coherence. The emergence of laser has greatly accelerated the development of technologies in industrial manufacturing, telecommunication, and biomedical science (). For instance, the scientific cognition is largely improved because of the ultra-high sensitivity and resolution in spectroscopy brought by lasers. Besides, lasers with low pumping thresholds hold promising applications in the display and lighting industry for their high brightness and monochromaticity that contribute to the highly vivid colors (). The development of new lasers depends mainly on the advances of gain materials. According to early reports, both inorganic emitter materials and organic gain materials were well applied in the generation of lasers. The former materials, mostly inorganic semiconductors, generally have stable properties but inherent brittleness, requiring sophisticated processing techniques and costly configurations. By contrast, organic gain materials are easily available and mechanically flexible, allowing convenient fabrication of integratable photonic devices with low-cost processing equipment (). Moreover, organic molecules are of wide tunability in spectroscopy, and the chemical structures can be easily modified to satisfy the requirement of specific lasing wavelength and low pumping threshold (). It has been found that various organic materials had high optical gain property and could be used as laser gain media, including some small organic dyes and conjugated polymers ().
Organic-conjugated polymer is an attractive gain material because of the excellent optoelectronic property and structural processability for device fabrication (Amarasinghe et al., 2009). Conjugated polymers usually comprise long chain units with alternate single and double C–C bonds, which are responsible for their semiconducting property (Figure 1A). The remarkable photoelectronic properties make conjugated polymers a good laser alternative for some inorganic materials (). The first observation of organic laser from conjugated polymers was reported in 1992 with poly[2-methoxy, 5-(2′ethyl-hexoxy)-p-phenylenevinylene] (MEH-PPV) solutions as gain media (). Then solid-state lasers based on semiconducting polymers attracted more attention and made remarkable advances for its practical prospects in integrated optoelectronic devices. Compared with some small organic laser molecules, conjugated polymers show unparalleled merits such as high absorption coefficients, broad spectra across the visible region, and most importantly, the resistance to light quenching at solid-state thanks to the long-chain barriers among each other, which make them an attractive low-threshold laser material for research (). In addition to the optical source, some conjugated polymers can also be electrically pumped to emit bright fluorescence and laser (), which greatly broaden their practical foreground in optical sensing and electrically driven laser display.
FIGURE 1
In this mini review, we summarize the recent advances of conjugated polymers emitting low-threshold organic lasers with focus on the resonator configurations and patterning strategies involved, and then typical applications of organic microlasers in biological/chemical sensing and organic laser display are discussed. Finally, we provide the perspectives on the existing challenges and future outlooks of conjugated polymer-induced organic lasers.
Optical feedback configurations and fabrication strategies
In a typical lasering process, pumping sources, gain materials, and resonator configurations are all essential to amplify light (
Distributed Bragg resonators
The first introduction of microcavity lasers was realized by the group of Tessler, who fabricated a planar cavity consisting of poly (para-phenylene vinylene) (PPV) interlayer between two mirrors (
Fabry–Pérot cavities
Most of one-dimensional microscopic wires/fibers present typical Fabry–Pérot feedback features with the body part of wire showing good waveguiding capacity and the tip parts acting as mirrors (
The self-assembly method is also a good choice to fabricate a nanofiber of conjugated polymers in low molecular weight. It has been reported that oligo (p-phenylenevinylene) (OPV) derivatives, exhibiting extended π-conjugated system, are prone to form ordered nanowire crystals with lasing action. An axially coupled microcavity system was constructed from two kinds of nanowires assembled by distinct OPV derivatives. Zhao group proposed a mutual mode selection strategy using the coupled microwires to obtain multicolor single-mode lasing generation and alternative output modulation (Zhang et al., 2017). When pumped by a proper light, gain materials can radiate laser from the microwire cavity facet, which can be coupled into the other cavity, and thus, the microwires mutually act as laser source as well as wavelength filter cavity, finally resulting in the laser mode selection and modulation (Figure 1C). A similar self-assembly method is employed to readily fabricate microbelts of another OPV derivative. Combined with the femtosecond laser processing technique, the microbelt can be perfectly tailored into the microfiber array along its length direction. The microfiber units are capable of presenting a similar lasing action simultaneously (
Distributed feedback configurations
DFB geometries with diffractive periodic structures have emerged as a highly popular resonator configuration for its high optical feedback efficiency, which can efficiently avoid the large reflectivity caused by mirror or facet parts in FP cavity. When pumped by proper light, low-threshold lasering action will be generated from gain media under the interfering effect of periodic geometry (usually grating or photonic structures). According to the Bragg equation,where neff is the effective refractive index of the active layer, Λ is the grating period, and m is the Bragg order. Constructive interference only occurs on lasers with specific wavelengths (λL).
Compared with other lasing systems, DFB configurations show special superiority in single-mode laser generation and broad-range spectral modulation by rational design of cavity parameters, such as grating period, refractive index, and thickness of gain layer (
The remarkable breakthrough on lasing threshold was achieved by the Bradley group, who intelligently proposed a mix-order (first and second order) grating strategy to reduce the lasing threshold of a polymer as low as 4 W/cm2 (
Distinct to optically driven organic lasers, electrically pumping lasers have attracted more and more attention because of its practicability and feasibility in the fields of organic laser diodes and full-color laser display. However, electrically driven laser is still confronted with serious challenges such as the extra additional loss and high lasing threshold. It has been validated that conjugated polymers with excellent charge transport capacity are ideally suitable for electrical pumping (
Whispering gallery mode cavities
Whispering gallery mode (WGM) resonator is a kind of typical cavity that has good optical confinement capacity for the total internal reflection effect near the structural boundary. A variety of micro-configurations has been developed to generate WGM lasers, including micro-spheres/hemispheres, microbubbles, microdisks, microrings, and microcapillaries (
Random lasing cavities
Conjugated polymers without specific feedback resonators can also present a lasing action, called random laser, when multiple scattering occurs in the irregular region. Random laser usually appears from gain medium with ill-defined and unordered geometries. Nanowires based on a typical π-conjugated oligophenyl material have been synthesized by the simple hot wall epitaxy method, and low-threshold random lasing action of nanowires (0.5 μJ/cm2) was measured at ∼425 nm under optical pumping (Quochi et al., 2005). Bongiovanni et al. further investigated the temperature-dependent nonlinear exciton process of the random lasing action from these nanofibers (
Applications
As an excellent laser material, conjugated polymers in proper resonator configurations can be pumped optically or electrically to generate intense organic lasers, which is expected to play important roles in diverse practical applications, such as chemosensing, biological sensing and imaging, organic laser diode, and electrically driven multicolor laser display (
Conclusion and outlook
In this minireview, we have focused on the organic lasing action and practical applications of conjugated polymers. Optical feedback configurations and relevant micro/nano-fabrication strategies are well summarized to provide an overall perspective on recent developments and existing problems toward polymer lasers. Even though considerable efforts have been made to simplify the fabrication techniques for resonator configurations and further reduce the lasing threshold, there still exist many bottlenecks urgently to be solved. First, it is expected that integratable lasing resonators in micro–nano scale can be further developed to ensure their practical applications in integrated laser source and full-color laser display. Besides, as a very appealing but intractable issue, electrically driven organic laser has not been totally realized in conjugated polymers due to the low carrier density and high additional losses associated with electrode absorption, polaron quenching, and triplet absorption. Even though diverse approaches focusing on the abovementioned problems have been attempted based on tailored gain material with increased carrier mobility, further efforts should be put on the optimization of resonator configurations to reduce the additional losses and achieve the electrically operated organic lasers with low threshold.
Statements
Author contributions
All authors listed have made a substantial, direct, and intellectual contribution to the work and approved it for publication.
Funding
This work is supported by the National Natural Science Foundation of China (Grant No. 62105096) and Doctoral Scientific Research Foundation of Henan Normal University (Grant Nos. 5101029170825 and 5101029470261).
Conflict of interest
The authors declare that the research was conducted in the absence of any commercial or financial relationships that could be construed as a potential conflict of interest.
Publisher’s note
All claims expressed in this article are solely those of the authors and do not necessarily represent those of their affiliated organizations, or those of the publisher, the editors, and the reviewers. Any product that may be evaluated in this article, or claim that may be made by its manufacturer, is not guaranteed or endorsed by the publisher.
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Summary
Keywords
organic-conjugated polymers, microlasers, resonator configurations, micro/nanofabrication techniques, optical sensing
Citation
Chen H, Qian M, Yu K and Liu Y (2021) Low Threshold Microlasers Based on Organic-Conjugated Polymers. Front. Chem. 9:807605. doi: 10.3389/fchem.2021.807605
Received
02 November 2021
Accepted
10 November 2021
Published
13 December 2021
Volume
9 - 2021
Edited by
Yun-Fei Li, Hebei University of Technology, China
Reviewed by
Xiaofeng Fang, Southern University of Science and Technology, China
Libo Zhou, University of Connecticut, United States
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© 2021 Chen, Qian, Yu and Liu.
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*Correspondence: Meng-dan Qian, qianmengdan@htu.edu.cn; Kun Yu, yukun@htu.edu.cn
This article was submitted to Nanoscience, a section of the journal Frontiers in Chemistry
Disclaimer
All claims expressed in this article are solely those of the authors and do not necessarily represent those of their affiliated organizations, or those of the publisher, the editors and the reviewers. Any product that may be evaluated in this article or claim that may be made by its manufacturer is not guaranteed or endorsed by the publisher.