Zinc and linkage effects of novel porphyrin-containing polyimides on resistor memory behaviors

Tsai, Chia-Liang; Reddy, Kamani Sudhir K.; Yeh, Chen‐Yu; Wang, Chin‐Li; Lin, Che; Yen, Hung‐Ju; Tsai, Mi Ching; Liou, Guey‐Sheng

doi:10.1039/c6ra18986e

Cited by 16 publications

(11 citation statements)

References 44 publications

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“…[1][2][3] In hybrid metalorganic materials, the oxidation state of metal ions provides a further handle to engineer new properties. [4][5][6][7][8][9][10][11] Manipulation of the metal oxidation state in such systems impacts their electrical properties: Switching of bulk resistivity in thin films has indeed been demonstrated via changing the oxidation state of the metal centers in metallopolymers. [7,9,10] In these reports, however, the metal ions are not organized into well-defined structures and are often separated from each other by organic moieties.…”

Section: Introductionmentioning

confidence: 99%

“…[7,9,10] In these reports, however, the metal ions are not organized into well-defined structures and are often separated from each other by organic moieties. [4][5][6][7][8][9][10][11] This results in limited metal-metal communication, and ultimately in poor nanoscale control of the metal system, due to the inherent disorder in polymer films. An appealing approach to create ordered structures at the nanoscale is to place the metal centers in direct communication with each other.…”

Section: Introductionmentioning

confidence: 99%

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Electrically Induced Mixed Valence Increases the Conductivity of Copper Helical Metallopolymers

et al. 2021

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Controlling the flow of electrical current at the nanoscale typically requires complex top‐down approaches. Here, a bottom‐up approach is employed to demonstrate resistive switching within molecular wires that consist of double‐helical metallopolymers and are constructed by self‐assembly. When the material is exposed to an electric field, it is determined that ≈25% of the copper atoms oxidize from CuI to CuII, without rupture of the polymer chain. The ability to sustain such a high level of oxidation is unprecedented in a copper‐based molecule: it is made possible here by the double helix compressing in order to satisfy the new coordination geometry required by CuII. This mixed‐valence structure exhibits a 104‐fold increase in conductivity, which is projected to last on the order of years. The increase in conductivity is explained as being promoted by the creation, upon oxidation, of partly filled orbitals aligned along the mixed‐valence copper array; the long‐lasting nature of the change in conductivity is due to the structural rearrangement of the double‐helix, which poses an energetic barrier to re‐reduction. This work establishes helical metallopolymers as a new platform for controlling currents at the nanoscale.

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Section: Introductionmentioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

Electrically Induced Mixed Valence Increases the Conductivity of Copper Helical Metallopolymers

et al. 2021

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“…Therefore, the donor feature and variable applications in optics and electronics provide an ideal platform to further investigate the mechanism of metal ions for memory behaviors and clarify the moderation effect of metal ions with various electron configurations. Though pioneer zinc-porphyrin based memory PIs and corresponding effects of Zn ion have been reported and proposed [42][43], the exact role of Zn ion in tailoring memory behaviors is not so precise and still not proved by experimental or theoretical results, which requires deeper and more accurate investigation.…”

Section: Introductionmentioning

confidence: 99%

Electron configurations at 3d orbital of metal ion determining charge transition process in memory devices

et al. 2021

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Functional polymeric materials with electrical bi-stable states possess significant potential for high-density data storage due to their nanoscale memory site, threedimensional-stacking ability and intrinsic flexibility. Aromatic polyimides bearing donor-acceptor (D-A) skeleton could form charge transfer complex (CTC) under electrical field, leading to their feasibility as memory materials. Three novel porphyrinated polyimides DATPP-DSDA, Zn-DATPP-DSDA and Mn-DATPP-DSDA were designed and synthesized for information memory applications. Metal ions with different electron configurations at 3d orbital have a determining influence on memory behaviors of polyimides: nonvolatile write-once-read-many-times memory (WORM) for DATPP-DSDA, volatile static random access memory (SRAM) for Zn-DATPP-DSDA, but no memory performance for Mn-DATPP-DSDA. By comparing the contribution of orbital transition and hole-electron distribution of charge-transfer excited states, roles of metal ions in regulating memory types were discussed. Molecular simulation results indicate that Zn ion could play a bridge role in paving the route for excited electrons from a D to A, while a trap role for Mn ion in hindering this process. This study proves the feasibility of the strategy for modulating the memory behaviors of porphyrinated polyimides by varying the central metal ion and provides the exact effects of various metal ions on regulating charge transfer processes.

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“…Therefore, porphyrin‐based materials have been widely employed in organic optoelectronic devices and sensors . In terms of electrical memory device, the unique electronic structure of porphyrin can promote the charge transfer in polyimide . Moreover, metalized porphyrin units as the terminal structure of HBPIs make it easy to tailor the memory performance of HBPIs.…”

Section: Introductionmentioning

confidence: 99%

Tunable memory performances of the porphyrin terminated hyperbranched polyimides

Tan

Yao

et al. 2018

J. Polym. Sci. Part A: Polym. Chem.

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Herein, a functional hyperbranched polyimide, denoted as ATPP-HBPI, was synthesized by termination of polyamic acid with 5-(4-aminophenyl)-10, 15, 20-triphenylporphyrin (ATPP) and chemical imidization. Subsequently, ATPP-HBPI was coordinated with Zn ion to give Zn-ATPP-HBPI. In the HBPIs, the porphyrin terminals acted as the electron donor (D) and the 6FDA moieties acted as the electron acceptor (A) to promote the electron transition. Both ATPP-HBPI and Zn-ATPP-HBPI exhibited good organo-solubility and high thermal stability. They were used as the electroactive layer to fabricate the memory device with a configuration of indium tin oxide (ITO)/HBPI/Al to evaluate their bistability. The devices exhibited different memory behaviors, WORM for ATPP-HBPI and SRAM for Zn-ATPP-HBPI, respectively. Optical and electrochemical experiments and molecular simulation were carried out to illustrate this phenomenon of performance transformation. The results show that the metallization of terminal of the HBPIs provides a strategy for tailoring the memory characteristics of the devices. V C 2018 Wiley Periodicals, Inc. J. ory characteristics of the devices.

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Zinc and linkage effects of novel porphyrin-containing polyimides on resistor memory behaviors

Abstract: The retention time of resistor type memory devices could be tuned by the linkage groups between porphyrin moiety and DSDA on the PIs. Moreover, the metal zinc also plays an important role in further tuning the memory behavior.

Cited by 16 publications

References 44 publications

Electrically Induced Mixed Valence Increases the Conductivity of Copper Helical Metallopolymers

Electrically Induced Mixed Valence Increases the Conductivity of Copper Helical Metallopolymers

Electron configurations at 3d orbital of metal ion determining charge transition process in memory devices

Tunable memory performances of the porphyrin terminated hyperbranched polyimides

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