The ability to modulate optical and electrical properties of two-dimensional (2D) semiconductors has sparked considerable interest in transition metal dichalcogenides (TMDs). Herein, we introduce a facile strategy for modulating optoelectronic properties of monolayer MoSe2with external light. Photochromic diarylethene (DAE) molecules formed a 2-nm-thick uniform layer on MoSe2, switching between its closed- and open-form isomers under UV and visible irradiation, respectively. We have discovered that the closed DAE conformation under UV has its lowest unoccupied molecular orbital energy level lower than the conduction band minimum of MoSe2, which facilitates photoinduced charge separation at the hybrid interface and quenches photoluminescence (PL) from monolayer flakes. In contrast, open isomers under visible light prevent photoexcited electron transfer from MoSe2to DAE, thus retaining PL emission properties. Alternating UV and visible light repeatedly show a dynamic modulation of optoelectronic signatures of MoSe2. Conductive atomic force microscopy and Kelvin probe force microscopy also reveal an increase in conductivity and work function of MoSe2/DAE with photoswitched closed-form DAE. These results may open new opportunities for designing new phototransistors and other 2D optoelectronic devices.
Non‐volatile resistive switching (NVRS) is a widely available effect in transitional metal oxides, colloquially known as memristors, and of broad interest for memory technology and neuromorphic computing. Until recently, NVRS was not known in other transitional metal dichalcogenides (TMDs), an important material class owing to their atomic thinness enabling the ultimate dimensional scaling. Here, various monolayer or few‐layer 2D materials are presented in the conventional vertical structure that exhibit NVRS, including TMDs (MX2, M
- Award ID(s):
- 1809017
- NSF-PAR ID:
- 10452600
- Publisher / Repository:
- Wiley Blackwell (John Wiley & Sons)
- Date Published:
- Journal Name:
- Advanced Materials
- Volume:
- 33
- Issue:
- 7
- ISSN:
- 0935-9648
- Format(s):
- Medium: X
- Sponsoring Org:
- National Science Foundation
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Abstract 2D materials have been of considerable interest as new materials for device applications. Non‐volatile resistive switching applications of MoS2and WS2have been previously demonstrated; however, these applications are dramatically limited by high temperatures and extended times needed for the large‐area synthesis of 2D materials on crystalline substrates. The experimental results demonstrate a one‐step sulfurization method to synthesize MoS2and WS2at 550
° C in 15 min on sapphire wafers. Furthermore, a large area transfer of the synthesized thin films to SiO2/Si substrates is achieved. Following this, MoS2and WS2memristors are fabricated that exhibit stable non‐volatile switching and a satisfactory large on/off current ratio (103–105) with good uniformity. Tuning the sulfurization parameters (temperature and metal precursor thickness) is found to be a straightforward and effective strategy to improve the performance of the memristors. The demonstration of large‐scale MoS2and WS2memristors with a one‐step low‐temperature sulfurization method with simple strategy to tuning can lead to potential applications such as flexible memory and neuromorphic computing. -
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Neurotransmitters are small molecules involved in neuronal signaling and can also serve as stress biomarkers.1Their abnormal levels have been also proposed to be indicative of several neurological diseases such as Alzheimer’s disease, Parkinson’s disease, Huntington disease, among others. Hence, measuring their levels is highly important for early diagnosis, therapy, and disease prognosis. In this work, we investigate facile functionalization methods to tune and enhance sensitivity of printed graphene sensors to neurotransmitters. Sensors based on direct laser scribing and screen-printed graphene ink are studied. These printing methods offer ease of prototyping and scalable fabrication at low cost.
The effect of functionalization of laser induced graphene (LIG) by electrodeposition and solution-based deposition of TMDs (molybdenum disulfide2and tungsten disulfide) and metal nanoparticles is studied. For different processing methods, electrochemical characteristics (such as electrochemically active surface area: ECSA and heterogenous electron transfer rate: k0) are extracted and correlated to surface chemistry and defect density obtained respectively using X-ray photoelectron spectroscopy (XPS) and Raman spectroscopy. These functionalization methods are observed to directly impact the sensitivity and limit of detection (LOD) of the graphene sensors for the studied neurotransmitters. For example, as compared to bare LIG, it is observed that electrodeposition of MoS2on LIG improves ECSA by 3 times and k0by 1.5 times.3Electrodeposition of MoS2also significantly reduces LOD of serotonin and dopamine in saliva, enabling detection of their physiologically relevant concentrations (in pM-nM range). In addition, chemical treatment of LIG sensors is carried out in the form of acetic acid treatment. Acetic acid treatment has been shown previously to improve C-C bonds improving the conductivity of LIG sensors.4In our work, in particular, acetic acid treatment leads to larger improvement of LOD of norepinephrine compared to MoS2electrodeposition.
In addition, we investigate the effect of plasma treatment to tune the sensor response by modifying the defect density and chemistry. For example, we find that oxygen plasma treatment of screen-printed graphene ink greatly improves LOD of norepinephrine up to three orders of magnitude, which may be attributed to the increased defects and oxygen functional groups on the surface as evident by XPS measurements. Defects are known to play a key role in enhancing the sensitivity of 2D materials to surface interactions, and have been explored in tuning/enhancing the sensor sensitivity.5Building on our previous work,3we apply a custom machine learning-based data processing method to further improve that sensitivity and LOD, and also to automatically benchmark different molecule-material pairs.
Future work includes expanding the plasma chemistry and conditions, studying the effect of precursor mixture in laser-induced solution-based functionalization, and understanding the interplay between molecule-material system. Work is also underway to improve the machine learning model by using nonlinear learning models such as neural networks to improve the sensor sensitivity, selectivity, and robustness.
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Abstract 2D materials have attracted much interest over the past decade in nanoelectronics. However, it was believed that the atomically thin layered materials are not able to show memristive effect in vertically stacked structure, until the recent discovery of monolayer transition metal dichalcogenide (TMD) atomristors, overcoming the scaling limit to sub‐nanometer. Herein, the nonvolatile resistance switching (NVRS) phenomenon in monolayer hexagonal boron nitride (h‐BN), a typical 2D insulator, is reported. The h‐BN atomristors are studied using different electrodes and structures, featuring forming‐free switching in both unipolar and bipolar operations, with large on/off ratio (up to 107). Moreover, fast switching speed (<15 ns) is demonstrated via pulse operation. Compared with monolayer TMDs, the one‐atom‐thin h‐BN sheet reduces the vertical scaling to ≈0.33 nm, representing a record thickness for memory materials. Simulation results based on ab‐initio method reveal that substitution of metal ions into h‐BN vacancies during electrical switching is a likely mechanism. The existence of NVRS in monolayer h‐BN indicates fruitful interactions between defects, metal ions and interfaces, and can advance emerging applications on ultrathin flexible memory, printed electronics, neuromorphic computing, and radio frequency switches.
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Abstract We report the isolation and characterization of a series of trinickel complexes with 2,3,6,7,10,11‐hexaoxytriphenylene (HOTP), [(Me3TPANi)3(HOTP)](BF4)
n (Me3TPA=N ,N ,N ‐tris[(6‐methyl‐2‐pyridyl)methyl]amine) (n =2, 3, 4 for complexes1 ,2 ,3 ). These complexes comprise a redox ladder whereby the HOTP core displays increasingly quinoidal character as its formal oxidation state changes from −4, to −3, and −2 in1 ,2 , and3 , respectively. No formal oxidation state changes occur on Ni, allowing the isolation of singlet diradical, monoradical, and closed‐shell configurations for HOTP in1 ,2 , and3 , respectively, with a concomitant decrease in the spin coupling strength upon oxidation. Because the three complexes can be considered models of the smallest building blocks of 2D conductive metal‐organic frameworks such as Ni9HOTP4, these results serve as possible inspiration for the construction of extended materials with targeted electric and magnetic properties.
