The chemical synthesis of nanographene molecules constitutes the bottom-up approach toward graphene, simultaneously providing rational chemical design, structure-property control and exploitation of their semiconducting and luminescence properties. Here, we report nanographene-based lasers from three zigzag-edged polycyclic aromatics. The devices consist of a passive polymer film hosting the nanographenes and a top-layer polymeric distributed feedback resonator. Both the active material and the laser resonator are processed from solution, key for the purpose of obtaining low-cost devices with mechanical flexibility. The prepared lasers show narrow linewidth ( < 0.13 nm) emission at different spectral regions covering a large segment of the visible spectrum, and up to the vicinity of the near-infrared. They show outstandingly long operational lifetimes (above 105 pump pulses) and very low thresholds. These results represent a significant step forward in the field of graphene and broaden its versatility in low-cost devices implying light emission, such as lasers.
The search of compounds emitting in the near‐infrared (NIR) has been accelerated owing to their use in biomedical and telecommunications applications. In this regard, nanographenes (NGs) are attractive materials adequate for integration with other technologies, which have recently demonstrated amplified spontaneous emission (ASE) and lasing across the visible spectrum. Here, the optical and ASE properties of four‐zigzag edged NGs of the [m,n]peri‐acenoacene family are reported, whose size is increased through conjugation extension by varying n (from 3 to 5) while keeping m = 2. Results show that such 1D conjugation extension method is more efficient in terms of shifting the photoluminescence (PL) to the infrared (PL at 710 nm in the larger compound, PP‐Ar) than through 2D conjugation extension as in previously reported NGs (PL at 676 nm with the largest compound FZ3, with n = 3 and m = 4). Additionally, PP‐Ar shows dual‐ASE (at 726 and 787 nm), whose origin is elucidated through Raman and transient absorption spectroscopies. These compounds’ potential for red and NIR lasing is demonstrated through the fabrication of distributed feedback lasers with top‐layer resonators. This study paves the way towards the development of stable low‐cost all‐plastic NIR lasers.
11 October 2018 in The Journal of Physical Chemistry C
High-transparency polymers, called optical polymers (OPs), are used in many thin-film devices, for which the knowledge of film thickness (h) and refractive index (n) is generally required. Spectrophotometry is a cost-effective, simple and fast non-destructive method often used to determine these parameters simultaneously, but its application is limited to films where h > 500 nm. Here, a simple spectrophotometric method is reported to obtain simultaneously the n and h of a sub-micron OP film (down to values of a few tenths of a nm) from its transmission spectrum. The method is valid for any OP where the n dispersion curve follows a two-coefficient Cauchy function and complies with a certain equation involving n at two different wavelengths. Remarkably, such an equation is determined through the analysis of n data for a wide set of commercial OPs, and its general validity is demonstrated. Films of various OPs (pristine or doped with fluorescent compounds), typically used in applications such as thin-film organic lasers, are prepared, and n and h are simultaneously determined with the proposed procedure. The success of the method is confirmed with variable-angle spectroscopic ellipsometry.
7 March 2025 in Journal of the American Chemical Society
Charge/energy separation across interfaces of plasmonic materials is vital for minimizing plasmonic losses and enhancing their performance in photochemical and optoelectronic applications. While heterostructures combining plasmonic two-dimensional transition metal carbides/nitrides (MXenes) and semiconducting transition metal dichalcogenides (TMDs) hold significant potential, the mechanisms governing plasmon-induced carrier dynamics at these interfaces remain elusive. Here, we uncover a distinctive secondary excitation phenomenon and an ultrafast charge/energy transfer process in heterostructure films composed of macro-scale Ti3C2Tx and MoS2 films. Using Rayleigh-Bénard convection and Marangoni effect-induced self-assembly, we fabricate large-scale (square centimeters) Ti3C2Tx and MoS2 films composed of edge-connected monolayer nanoflakes. These films are flexibly stacked in a controlled sequence to form macroscopic heterostructures, enabling the investigation and manipulation of excited-state dynamics using transient absorption and optical pump-terahertz probe spectroscopy. In the Ti3C2Tx-MoS2 heterostructure, we observe a secondary excitation in MoS2 driven by the surface plasmon resonance of Ti3C2Tx. This phenomenon, with a characteristic rise time constant of ∼70 ps, is likely facilitated by acoustic phonon recycling across the interface. Further interfacial thermal transport engineering─achieved by tailoring the sequence and combination of interfaces in trilayer heterostructures─allows extending the characteristic time to ∼175 ps. Furthermore, we identify a sub-150 fs ultrafast charge/energy transfer process from Ti3C2Tx to MoS2. The transfer efficiency is strongly dependent on the excitation photon energy, resulting in amplified photoconductivity in MoS2 by up to ∼180% under 3.10 eV excitation. These insights are crucial for developing plasmonic MXene-based heterostructures, paving the way for advancements in photochemical and optoelectronic applications.