Reduced Graphene Oxide Chemically Modified with Aggregation‐Induced Emission Polymer for Solid‐State Optical Limiter

Abstract

Aggregation-induced emission (AIE) materials are usually not suitable for constructing solid nonlinear optical (NLO) devices because strong solid-state aggregation behavior would shorten the excited-state lifetime, add relaxation pathways, and thereby reduce effective NLO absorption. To address this problem a newly synthesized AIE material, poly{[9,9-bis(6-azidohexyl)-9H-fluorene]-alt-(1,1,2,2-tetraphenylethene)} (PAHFTP), was treated with reduced graphene oxide (RGO) to give the soluble derivative of poly[(9,9-dihexyl-9H-fluorene)-alt-(1,1,2,2-tetraphenylethene)] (PFTP) covalently grafted onto RGO (PFTP-RGO). Upon covalent grafting of PAHFTP onto the RGO surface, about 91.89 % of the fluorescence intensity of the PAHFTP film was quenched due to electron transfer from PFTP to RGO, which yielded PFTP -RGO radical-ion pairs. The as-prepared PFTP-RGO was embedded into a non-optically active poly(methyl methacrylate) (PMMA) matrix to produce the PFTP-RGO/PMMA film with good optical quality. As expected, the PAHFTP/PMMA film did not show any NLO response. In contrast to the PFTP-RGO/PMMA and RGO/PMMA films, the annealed PFTP-RGO/PMMA exhibited superior OL performance, with low OL thresholds of 0.24 GW cm (1.44 J cm ) at 532 nm and 0.18 GW cm (1.08 J cm ) at 1064 nm. The damage thresholds of the annealed PFTP-RGO/PMMA film are around 33.88 J cm at 900 μJ at 532 nm and 37.32 J cm at 1000 μJ at 1064 nm, respectively.

Advanced Properties and Applications of AIEgens-Inspired Smart Materials

“…As a result, the effective absorption of NLO device reduces. 76 To address the above problem, Liu et al developed nonaggregated functional materials with AIEgens for developing solid optical-linear (OL) and NLO devices. They synthesized a TPE-based polymer, poly[(9,9-bis(6-azidohexyl)-9H-fluorene)-alt-(1,1,2,2-tetraphenylethene)] (PAHFTP), which reacts with rGO to form poly[(9,9-dihexyl-9H-fluorene)-alt-(1,1,2,2-tetraphenylethene)] (PFTP-rGO).…”

Recent Progress in Two-Dimensional Nanomaterials for Laser Protection

“…Figure 2 displays the typical graphene-like ultrathin 2D nanomaterials. These atomic-scale thick materials have a large surface area and outstanding thermal and electrical conductivity, superior flexibility, and superior nonlinear optical response, endowing it with the promising application scope in the field of supercapacitors [31][32][33][34], energy storage devices [35][36][37][38], organic light-emitting diodes (OLEDs) [39][40][41], information storage devices [42][43][44][45], optical limiters, [46][47][48][49][50][51][52][53] and others. Due to the extended conjugate sp 2 π-system and linear dispersion relation of its electronic band structure, graphene, the most representative 2D nanomaterial, and its derivatives, possesses the ultra-broadband resonate NLO response and the ultrafast carrier relaxation dynamics, which make it suitable for the preparation of solution-or solid-state optical limiters.…”

“…Nonlinear scattering plays the most common role for the NLO response in the dispersion of nanomaterials. Graphene and its derivatives, the most representative materials in the ultrathin two-dimensional (2D) nanomaterials family, have been extensively studied as OL materials [48,49]. So, here we take graphene and its derivatives as examples to illustrate the NLS mechanism in detail.…”

“…This lack of stability under ambient conditions severely undermines the application of BP, which is still a formidable challenge for researchers to conquer. Most recently, Chen et al innovatively designed and synthesized the chemically modified reduced graphene oxide materials with aggregation-induced emission (AIE) polymer for solid-state optical limiters [49]. As shown in Figure 7a, the AIE-active polymer PBFTB was synthesized with Suzuki coupling reaction.…”

“…The tested data fitted well with the TPA and the largest achieved TPA coefficient was 74.84 cm/GW at the peak intensity of 0.02 GW/cm (Figure 14b). From a practical application point of view, it is better to fabricate solid-state optical limiters by embedding the NLO materials as inclusions in a suitable non-optically active host and/or polymerizing the NLO chromophore-based monomers to form composite functional materials [49]. Hao et al investigated the NLO response of h-BN nanosheets (BNNSs) in both solution and solid state [106].…”