Project description:Among spin-crossover complexes, Fe-porphyrin (FeP) stands out for molecular spintronic applications: an intricate, yet favourable balance between ligand fields, charge transfer, and the Coulomb interaction makes FeP highly manipulable, while its planar structure facilitates device integration. Here, we theoretically design a mechanical spin-switch device in which external strain triggers the intrinsic magneto-structural coupling of FeP through a purely organic embedding. Exploiting the chemical compatibility and stretchability of graphene nanoribbon electrodes, we overcome common reliability and reproducibility issues of conventional inorganic setups. The competition between the Coulomb interaction and distortion-induced changes in ligand fields requires methodologies beyond the state-of-the-art: combining density functional theory with many-body techniques, we demonstrate experimentally feasible tensile strain to trigger a low-spin (S = 1) to high-spin (S = 2) crossover. Concomitantly, the current through the device toggles by over an order of magnitude, adding a fully planar mechanical current-switch unit to the panoply of molecular spintronics.
Project description:The control of spins and spin to charge conversion in organics requires understanding the molecular spin-orbit coupling (SOC), and a means to tune its strength. However, quantifying SOC strengths indirectly through spin relaxation effects has proven difficult due to competing relaxation mechanisms. Here we present a systematic study of the g-tensor shift in molecular semiconductors and link it directly to the SOC strength in a series of high-mobility molecular semiconductors with strong potential for future devices. The results demonstrate a rich variability of the molecular g-shifts with the effective SOC, depending on subtle aspects of molecular composition and structure. We correlate the above g-shifts to spin-lattice relaxation times over four orders of magnitude, from 200 to 0.15 μs, for isolated molecules in solution and relate our findings for isolated molecules in solution to the spin relaxation mechanisms that are likely to be relevant in solid state systems.
Project description:Engineering a low singlet-triplet energy gap (ΔEST) is necessary for efficient reverse intersystem crossing (rISC) in delayed fluorescence (DF) organic semiconductors but results in a small radiative rate that limits performance in LEDs. Here, we study a model DF material, BF2, that exhibits a strong optical absorption (absorption coefficient = 3.8 × 105 cm-1) and a relatively large ΔEST of 0.2 eV. In isolated BF2 molecules, intramolecular rISC is slow (delayed lifetime = 260 μs), but in aggregated films, BF2 generates intermolecular charge transfer (inter-CT) states on picosecond timescales. In contrast to the microsecond intramolecular rISC that is promoted by spin-orbit interactions in most isolated DF molecules, photoluminescence-detected magnetic resonance shows that these inter-CT states undergo rISC mediated by hyperfine interactions on a ~24 ns timescale and have an average electron-hole separation of ≥1.5 nm. Transfer back to the emissive singlet exciton then enables efficient DF and LED operation. Thus, access to these inter-CT states, which is possible even at low BF2 doping concentrations of 4 wt%, resolves the conflicting requirements of fast radiative emission and low ΔEST in organic DF emitters.
Project description:Noncollinear spin textures in low-dimensional magnetic systems have been studied for decades because of their extraordinary properties and promising applications derived from the chirality and topological nature. However, material realizations of topological spin states are still limited. Employing first-principles and Monte Carlo simulations, we propose that monolayer chromium trichloride (CrCl3) can be a promising candidate for observing the vortex/antivortex type of topological defects, so-called merons. The numbers of vortices and antivortices are found to be the same, maintaining an overall integer topological unit. By perturbing with external magnetic fields, we show the robustness of these meron pairs and reveal a rich phase space to tune the hybridization between the ferromagnetic order and meron-like defects. The signatures of topological excitations under external magnetic field also provide crucial information for experimental justifications. Our study predicts that two-dimensional magnets with weak spin-orbit coupling can be a promising family for realizing meron-like spin textures.
Project description:Quantum spin liquids (QSLs) are in a quantum disordered state that is highly entangled and has fractional excitations. As a highly sought-after state of matter, QSLs were predicted to host spinon excitations and to arise in frustrated spin systems with large quantum fluctuations. Here we report on the experimental observation and theoretical modeling of QSL signatures in monolayer 1T-NbSe2, which is a newly emerging two-dimensional material that exhibits both charge-density-wave (CDW) and correlated insulating behaviors. By using scanning tunneling microscopy and spectroscopy (STM/STS), we confirm the presence of spin fluctuations in monolayer 1T-NbSe2 by observing the Kondo resonance as monolayer 1T-NbSe2 interacts with metallic monolayer 1H-NbSe2. Subsequent STM/STS imaging of monolayer 1T-NbSe2 at the Hubbard band energy further reveals a long-wavelength charge modulation, in agreement with the spinon modulation expected for QSLs. By depositing manganese-phthalocyanine (MnPc) molecules with spin S = 3/2 onto monolayer 1T-NbSe2, new STS resonance peaks emerge at the Hubbard band edges of monolayer 1T-NbSe2. This observation is consistent with the spinon Kondo effect induced by a S = 3/2 magnetic impurity embedded in a QSL. Taken together, these experimental observations indicate that monolayer 1T-NbSe2 is a new promising QSL material.
Project description:A two-dimensional (2D) topological insulator exhibits the quantum spin Hall (QSH) effect, in which topologically protected conducting channels exist at the sample edges. Experimental signatures of the QSH effect have recently been reported in an atomically thin material, monolayer WTe2. Here, we directly image the local conductivity of monolayer WTe2 using microwave impedance microscopy, establishing beyond doubt that conduction is indeed strongly localized to the physical edges at temperatures up to 77 K and above. The edge conductivity shows no gap as a function of gate voltage, and is suppressed by magnetic field as expected. We observe additional conducting features which can be explained by edge states following boundaries between topologically trivial and nontrivial regions. These observations will be critical for interpreting and improving the properties of devices incorporating WTe2. Meanwhile, they reveal the robustness of the QSH channels and the potential to engineer them in the monolayer material platform.
Project description:The microstructure of the organic semiconductor (OSC) active layer is one of the crucial topics to improve the sensing performance of gas sensors. Herein, we introduce a simple solvent vapor annealing (SVA) process to control 6,13-bis(triisopropylsilylethynyl)-pentacene (TIPS-pentacene) OSC films morphology and thus yields high-sensitivity nitrogen organic thin-film transistor (OTFT)-based nitrogen dioxide (NO2) sensors. Compared to pristine devices, the toluene SVA-treated devices exhibit an order of magnitude responsivity enhancement to 10 ppm NO2, further with a limit of detection of 148 ppb. Systematic studies on the microstructure of the TIPS-pentacene films reveal the large density grain boundaries formed by the SVA process, improving the capability for the adsorption of gas molecules, thus causing high-sensitivity to NO2. This simple SVA processing strategy provides an effective and reliable access for realizing high-sensitivity OTFT NO2 sensors.
Project description:Intrinsic antiferromagnetism in van der Waals (vdW) monolayer (ML) crystals enriches our understanding of two-dimensional (2D) magnetic orders and presents several advantages over ferromagnetism in spintronic applications. However, studies of 2D intrinsic antiferromagnetism are sparse, owing to the lack of net magnetisation. Here, by combining spin-polarised scanning tunnelling microscopy and first-principles calculations, we investigate the magnetism of vdW ML CrTe2, which has been successfully grown through molecular-beam epitaxy. We observe a stable antiferromagnetic (AFM) order at the atomic scale in the ML crystal, whose bulk is ferromagnetic, and correlate its imaged zigzag spin texture with the atomic lattice structure. The AFM order exhibits an intriguing noncollinear spin reorientation under magnetic fields, consistent with its calculated moderate magnetic anisotropy. The findings of this study demonstrate the intricacy of 2D vdW magnetic materials and pave the way for their in-depth analysis.
Project description:The emerging field of valleytronics aims to exploit the valley pseudospin of electrons residing near Bloch band extrema as an information carrier. Recent experiments demonstrating optical generation and manipulation of exciton valley coherence (the superposition of electron-hole pairs at opposite valleys) in monolayer transition metal dichalcogenides (TMDs) provide a critical step towards control of this quantum degree of freedom. The charged exciton (trion) in TMDs is an intriguing alternative to the neutral exciton for control of valley pseudospin because of its long spontaneous recombination lifetime, its robust valley polarization, and its coupling to residual electronic spin. Trion valley coherence has however been unexplored due to experimental challenges in accessing it spectroscopically. In this work, we employ ultrafast two-dimensional coherent spectroscopy to resonantly generate and detect trion valley coherence in monolayer MoSe2 demonstrating that it persists for a few-hundred femtoseconds. We conclude that the underlying mechanisms limiting trion valley coherence are fundamentally different from those applicable to exciton valley coherence.
Project description:Organic molecular semiconductors are solution processable, enabling the growth of large-area single-crystal semiconductors. Improving the performance of organic semiconductor devices by increasing the charge mobility is an ongoing quest, which calls for novel molecular and material design, and improved processing conditions. Here we show a method to increase the charge mobility in organic single-crystal field-effect transistors, by taking advantage of the inherent softness of organic semiconductors. We compress the crystal lattice uniaxially by bending the flexible devices, leading to an improved charge transport. The mobility increases from 9.7 to 16.5 cm(2) V(-1) s(-1) by 70% under 3% strain. In-depth analysis indicates that compressing the crystal structure directly restricts the vibration of the molecules, thus suppresses dynamic disorder, a unique mechanism in organic semiconductors. Since strain can be easily induced during the fabrication process, we expect our method to be exploited to build high-performance organic devices.