Optically Encodable and Erasable Multilevel Nonvolatile Flexible Memory Device Based on Metal-Organic Frameworks.

Multilevel and flexible nonvolatile memory (NVM) is a promising candidate for data storage in next-generation devices but its high bias and low mobility of conducting channels are often its drawbacks. In this study, we demonstrate a low bias of smaller than 0.1 V and a high-mobility graphene layer as a conducting channel for flexible optoelectronic NVM based on a composite thin film of indium-based MOF-derived InCl3 and 4,4-oxydiphthalic anhydride (odpta), Na[In3(odpt)2(OH)2(H2O)2](H2O)4, and reduced graphene oxide (rGO). The optoelectronic NVM device can be encoded and erased optically by ultraviolet (UV) light and visible light, respectively. Our device also achieves memory states over 192 (6-bit storage) distinct levels, which can emerge as mass data storage. It also shows an excellent endurance of write-erase cycles under irradiation with a laser of varying wavelengths, the mechanical stability of more than 1000 bending cycles, and stable retention for longer than 10 000 s. These results open an alternative route for developing low bias and innovative optoelectronic technologies.

Regimented Charge Transport Phenomena in Semiconductive Self-Assembled Rhenium Nanotubes.

Photoconductivity, a crucial property, determines the potential of semiconductor materials for use in optoelectronic and photocatalytic device applications. The one-dimensional metal-organic nanotube semiconducting material [{Re(CO)3}6(bho)(phpy)6]n (MBT 1, where bho is benzene-1,2,3,4,5,6-hexaoate and phpy is 4-phenylpyridine) reported herein exhibits record photocurrent responses at a broad spectral range. MBT 1 is comprised of a unique nanotube structure that is composed of six rhenium sites, six 4-phenylpyridine ligands, and a benzene-1,2,3,4,5,6-hexaoate unit. The highly organized self-assembled molecular bamboo tube MBT 1 displays semiconducting characteristics with a low activation energy of 1.63 meV. The alternating current (AC) and direct current (DC) conductivities of pellet devices are approximately 10-4 S/cm. For a single-crystal device, DC conductivity was found to be 1.5 S/cm, an unprecedented 10 000 times higher. The bandgap of MBT 1 was determined to be 1.03 eV, consistent with the theoretically estimated value of 1.2 eV. Theoretical calculations suggest that the unique structural architecture of MBT 1 allows for effective charge transport, which is facilitated by the spatial separation of electrons and holes that MBT 1 contains. This also eliminates fast charge recombination. The findings are not only chemically and fundamentally important but also have great potential for applications in innovative nano-optoelectronics.

Functional Groups Assisted Tunable Dielectric Permittivity of Guest-Free Zn-Based Coordination Polymers for Gate Dielectrics.

The dielectric properties of coordination polymers has been a topic of recent interest, but the role of different functional groups on the dielectric properties of these polymers has not yet been fully addressed. Herein, the effects of electron-donating (R=NH2 ) and electron-withdrawing (R=NO2 ) groups on the dielectric behavior of such materials were investigated for two thermally stable and guest-free Zn-based coordination polymers, [Zn(L1 )(L2 )]n (1) and [Zn(L1 )(L3 )]n (2) [L1 =2-(2-pyridyl) benzimidazole (Pbim), L2 =5-aminoisophthalate (Aip), and L3 =5-nitroisophthalate (Nip)]. The results of dielectric studies of 1 revealed that it possesses a high dielectric constant (κ=65.5 at 1 kHz), while compound 2 displayed an even higher dielectric constant (κ=110.3 at 1 kHz). The electron donating and withdrawing effects of the NH2 and NO2 substituents induce changes in the polarity of the polymers, which is due to the inductive effect from the aryl ring for both NO2 and NH2 . Theoretical results from density functional theory (DFT) calculations, which also support the experimental findings, show that both compounds have a distinct electronic behavior with diverse wide bandgaps. The significance of the current work is to provide information about the structure-dielectric property relationships. So, this study promises to pave the way for further research on the effects of different functional groups on coordination polymers on their dielectric properties.

Thin Film Growth of 3D Sr-based Metal-Organic Framework on Conductive Glass via Electrochemical Deposition.

Integration of metal-organic frameworks (MOFs) as components of advanced electronic devices is at a very early phase of development and the fundamental issues related to their crystal growth on conductive substrate need to be addressed. Herein, we report on the structural characterization of a newly synthesized Sr-based MOF {[Sr(2,5-Pzdc)(H2 O)2 ] ⋅ 3 H2 O}n (1) and the uniform crystal growth of compound 1 on a conducting glass (fluorine doped tin oxide (FTO)) substrate using electrochemical deposition techniques. The Sr-based MOF 1 was synthesized by the reaction of Sr(NO3 )2 with 2,5-pyrazinedicarboxylic acid dihydrate (2,5-Pzdc) under solvothermal conditions. A single-crystal X-ray diffraction analysis revealed that 1 has a 3D structure and crystallizes in the triclinic P 1 ‾ space group. In addition, the uniform crystal growth of this MOF on a conducting glass (FTO) substrate was successfully achieved using electrochemical deposition techniques. Only a handful of MOFs have been reposed to grown on conductive surfaces, which makes this study an important focal point for future research on the applications of MOF-based devices in microelectronics.

Water-assisted spin-flop antiferromagnetic behaviour of hydrophobic Cu-based metal-organic frameworks.

Solvent-dependent magnetism in Cu-based metal-organic frameworks (MOFs) is reported. Spin-flop magnetic behaviour occurs at different dehydrated states of MOFs. The oxygens of guest and coordinated water molecules are responsible as water removal tunes the coordination geometry around the Cu centre and the electronic structure of the framework.

Intrinsic Ultralow-Threshold Laser Action from Rationally Molecular Design of Metal-Organic Framework Materials.

Metal-organic frameworks (MOFs) are superior for multiple applications including drug delivery, sensing, and gas storage because of their tunable physiochemical properties and fascinating architectures. Optoelectronic application of MOFs is difficult because of their porous geometry and conductivity issues. Recently, a few optoelectronic devices have been fabricated by a suitable design of integrating MOFs with other materials. However, demonstration of laser action arising from MOFs as intrinsic gain media still remains challenging, even though some studies endeavor on encapsulating luminescence organic laser dyes into the porous skeleton of MOFs to achieve laser action. Unfortunately, the aggregation of such unstable laser dyes causes photoluminescence quenching and energy loss, which limits their practical application. In this research, unprecedently, we demonstrated ultralow-threshold (∼13 nJ/cm2) MOF laser action by a judicious choice of metal nodes and organic linkers during synthesis of MOFs. Importantly, we also demonstrated that the white random lasing from the beautiful microflowers of organic linkers possesses a porous network, which is utilized to synthesize the MOFs. The highly luminescent broad-band organic linker 1,4-NDC, which itself exhibits a strong white random laser, is used not only to achieve the stimulated emission in MOFs but also to reduce the lasing threshold. Such white lasing has multiple applications from bioimaging to the recently developed versatile Li-Fi technology. In addition, we showed that the smooth facets of MOF microcrystals can show Fabry-Perot resonant cavities having a high quality factor of ∼103 with excellent photostability. Our unique discovery of stable, nontoxic, high-performance MOF laser action will open up a new route for the development of new optoelectronic devices.