The low dielectric constant and relaxation dielectric behavior in hydrogen-bonding metal–organic frameworks

Yu, Shanshan; Yuan, Guo-Jun; Duan, Hai‐Bao

doi:10.1039/c5ra08074f

Cited by 14 publications

(12 citation statements)

References 35 publications

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“…The MPACs η S σ Sn of ZJU-28⊃MAPbBr 3 can be calculated from Equation (1) where the multiphoton absorption cross-section results σ Rn of lead bromide perovskite NCs are from the reference. [38] Our tests were carried out in air without additional protection and the humidity was as high as 60%. ρ R is the molar concentration of MAPbBr 3 -NCs dispersed in toluene (≈1.5 × 10 −6 m), and ρ S is the molar concentration of MAPbBr 3 -QDs dispersed in the ZJU-28 crystal (≈20 × 10 −6 m).…”

Section: Multiphoton Excitationmentioning

confidence: 99%

“…[32,34] In addition, according to the existing literature, [35,36] the local field effect caused by the relatively large difference between the dielectric constant of the medium and the matrix may also be a cause of the improvement in nonlinear optical performance, given that the dielectric constant of MAPbBr 3 is 25.5, [37] and the dielectric constant of the matrix of the nonferroelectric MOF is generally less than 2 by theoretical calculation. [38] Our tests were carried out in air without additional protection and the humidity was as high as 60%. Under this condition, the luminescent properties and nonlinear optical properties of unprotected MAPbBr 3 quantum dots are significantly reduced upon exposure to air ( Figure S6, Supporting Information), due to moisture and other factors [18] ; while the MAPbBr 3 quantum dots protected by the ZJU-28 framework remain excellent multiphoton absorption emission performance, which can be attributed to the protection by ZJU-28.…”

Section: Multiphoton Excitationmentioning

confidence: 99%

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Confinement of Perovskite‐QDs within a Single MOF Crystal for Significantly Enhanced Multiphoton Excited Luminescence

et al. 2018

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and then generate a high-energy photon through radiation transitions from the excited state. Compared with single photon excited luminescence, MPE luminescence has the advantages of stronger spatial confinement, longer penetration depth, smaller biological damage, and less Rayleigh scattering, so the high-order MPE luminescence materials have great potential applications in bioimaging, 3D optical data storage, sensing, and so on, but basically have not been fulfilled yet, [1][2][3][4][5] mainly because of the big challenge and difficulty to realize high-order MPE luminescence. Even for those materials exhibiting such MPE luminescence, the five-photon excited luminescence phenomena can be only observed in the dispersed solutions of either organic chromophore molecules or core-shell halide perovskite semiconductor nanocrystals (MAPbBr 3 /(OA) 2 PbBr 4 ) in order to diminish the aggregation-caused quenching (ACQ) while still with quite low multiphoton action cross-sections (MPACs), or have poor stability without any encapsulation approaches (The MPAC (ησ n ) is the product of photoluminescence quantum yield (PLQY, η) and multiphoton absorption cross-section (σ n ), the parameter to evaluate the multiphoton excited luminescence brightness). [6,7] The deficiency of bulky high-order MPE luminescence solid single crystals with low excitation threshold have further limited the exploration and implementation of such MPE materials into miniaturization and device, and thus their practical applications.Some porous materials such as mesoporous silica and porous alumina have been utilized to confine dye molecules and perovskite nanoparticles and thus to diminish the ACQ and to develop the solid-state luminescence. [4,[8][9][10][11] The emergence of a new type of porous materials, metal-organic frameworks (MOFs), has provided the significant promise to provide much better confinement for the potentially luminescent dye molecules and perovskite nanoparticles because of their more tunable pores/cages and specific sites to introduce strong recognitions. Indeed, we have recently realized a three-photon excited emissive material ZJU-68⊃DMASM through an exact match of a dye molecule with the pores of the metal-organic framework although high-order MPE luminescence solid single The development of the photostable higher-order multiphoton-excited (MPE) upconversion single microcrystalline material is fundamentally and technologically important, but very challenging. Here, up to five-photon excited luminescence in a host-guest metal-organic framework (MOF) and perovskite quantum dot (QD) hybrid single crystal ZJU-28⊃MAPbBr 3 is shown via an in situ growth approach. Such a MOF strategy not only results in a high QD loading concentration, but also significantly diminishes the aggregationcaused quenching (ACQ) effect, provides effective surface passivation, and greatly reduces the contact of the QDs with the external bad atmosphere due to the confinement effect and protection of the framework. These advantages make the resulting ZJU-28⊃MAPb...

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Section: Multiphoton Excitationmentioning

confidence: 99%

Section: Multiphoton Excitationmentioning

confidence: 99%

Confinement of Perovskite‐QDs within a Single MOF Crystal for Significantly Enhanced Multiphoton Excited Luminescence

et al. 2018

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“…[74] Theoretical studies using the Clausius-Mossotti model have estimated the possible applica-tions of MOFs as gap-filling low-k dielectrics in advanced onchip interconnects. [26,29,71,75,76] Despite these encouraging results, however, high thermal stability, diverse mechanical response, long periods of stability, low-voltage insulation, high elastic modulus (> 3 GPa), reduced pore size (< 5 nm), hydrophobicity and superior adhesion on solid supports are required for the successful engineering of effective functional devices. [4,77] The hydrophobic properties of MOFs have attracted considerable interest in fundamental research and practical applications in the area of hydrocarbon separation, oil spill separation, selfcleaning recycling bio-alcohols and proton conductivity.…”

Section: Chemistry-a European Journalmentioning

confidence: 99%

Hydrophobic Metal−Organic Frameworks and Derived Composites for Microelectronics Applications

Thanasekaran

Liu

et al. 2021

Chemistry A European J

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The extraordinary characteristic features of metal−organic frameworks (MOFs) make them applicable for use in a variety of fields but their conductivity in microelectronics over a wide relative humidity (RH) range has not been extensively explored. To achieve good performance, MOFs must be stable in water, i. e., under humid conditions. However, the design of ultrastable hydrophobic MOFs with high conductivity for use in microelectronics as conducting and dielectric materials remains a challenge. In this Review, we discuss applications of an emerging class of hydrophobic MOFs with respect to their use as active sensor coatings, tunable low‐κ dielectrics and conductivity, which provide high‐level roadmap for stimulating the next steps toward the development and implementation of hydrophobic MOFs for use in microelectronic devices. Several methodologies including the incorporation of long alkyl chain and fluorinated linkers, doping of redox‐active 7,7,8,8‐tetracyanoquinodimethane (TCNQ), the use of guest molecules, and conducting polymers or carbon materials in the pores or surface of MOFs have been utilized to produce hydrophobic MOFs. The contact angle of a water droplet and a coating can be used to evaluate the degree of hydrophobicity of the surface of a MOF. These unique advantages enable hydrophobic MOFs to be used as a highly versatile platform for exploring multifunctional porous materials. Classic representative examples of each category are discussed in terms of coordination structures, types of hydrophobic design, and potential microelectronic applications. Lastly, a summary and outlook as concluding remarks in this field are presented. We envision that future research in the area of hydrophobic MOFs promise to provide important breakthroughs in microelectronics applications.

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“…Polarization chemistry has been established to be intrinsically correlated with the dielectric behavior of CPs, and is attributed to inductive effects, and resonance effects, which are thought to be transmitted via σ and π bonding and generate interfacial polarization effects that can result in very high dielectric constants at room temperature. The electron‐withdrawing inductive effect from the aryl ring for both NO 2 and NH 2 substituents is more pronounced for NO 2 because of the combined electronegativity of the nitrogen and oxygen atoms [35–40] . Herein, we report on the successful design of two zinc‐based coordination polymers, [Zn(L 1 )(L 2 )] n ( 1 ) and [Zn(L 1 )(L 3 )] n ( 2 ) adopting highly thermally stable core structures with electron withdrawing or donating groups (Scheme 1).…”

Section: Introductionmentioning

confidence: 99%

“…The electron-withdrawing inductive effect from the aryl ring for both NO 2 and NH 2 substituents is more pronounced for NO 2 because of the combined electronegativity of the nitrogen and oxygen atoms. [35][36][37][38][39][40] Herein, we report on the successful design of two zinc-based coordination polymers, [Zn(L 1 )(L 2 )] n (1) and [Zn-(L 1 )(L 3 )] n (2) adopting highly thermally stable core structures with electron withdrawing or donating groups (Scheme 1). The unambiguous dielectric tuning of the model compounds with the withdrawing and donating groups is highlighted.…”

Section: Introductionmentioning

confidence: 99%

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

Kamal

Inamdar

et al. 2022

Chemistry A European J

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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.

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The low dielectric constant and relaxation dielectric behavior in hydrogen-bonding metal–organic frameworks

Abstract: A 3D hydrogen-bonding metal–organic framework shows a low dielectric constant and relaxation dielectric behavior at high temperature.

Cited by 14 publications

References 35 publications

Confinement of Perovskite‐QDs within a Single MOF Crystal for Significantly Enhanced Multiphoton Excited Luminescence

Confinement of Perovskite‐QDs within a Single MOF Crystal for Significantly Enhanced Multiphoton Excited Luminescence

Hydrophobic Metal−Organic Frameworks and Derived Composites for Microelectronics Applications

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

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