Persistent Conductivity in TPyP:TSPP Organic Nanorods Induced by Ion Bombardment

Zijll, Marshall van; Borders, Bryan; Mazur, Ursula; Hipps, K. W.

doi:10.1021/acs.jpcc.6b04689

Cited by 5 publications

(8 citation statements)

References 24 publications

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“…Persistent photoconductivity is not observed in all porphyrin nanostructures. Interestingly, we recently observed persistent conduction (nA to μA) in TPyP:TSPP nanorods after exposure to an Ar + ion beam (in UHV) with low ion energies . This behavior has not been shown for any known organic nanomaterial.…”

Section: Photoseponse Sensing and Mechanical Propertiesmentioning

confidence: 86%

“…Interestingly, we recently observed persistent conduction (nA to μA) in TPyP:TSPP nanorods after exposure to an Ar + ion beam (in UHV) with low ion energies. 91 This behavior has not been shown for any known organic nanomaterial. It has, however, been recently demonstrated in ZnO nanowires and termed persistent ion beam induced conduction (PIC).…”

Section: ■ Synthesis and Controlled Growthmentioning

confidence: 93%

“…The PIC and PPC of ZnO nanostructures (bombarded with noble gas ions) have similar excitation efficiencies, decay rates, and chemical sensitivities . PIC in TPyP:TSPP nanorods also exhibits the same characteristics as its PPC. , Johannes and co-workers have predicted that materials which display PPC should also show PIC …”

Section: Photoseponse Sensing and Mechanical Propertiesmentioning

confidence: 99%

“…92 PIC in TPyP:TSPP nanorods also exhibits the same characteristics as its PPC. 48,91 Johannes and co-workers have predicted that materials which display PPC should also show PIC. 92 There are a few likely explanations for the origin of the PPC.…”

Section: ■ Synthesis and Controlled Growthmentioning

confidence: 99%

“…7,23,36,41,47−49 In addition, some of these BPs show persistent ion beam induced conductivity. 91 Critical to the commercial application of these materials is precise control of their composition and structure through synthetic strategies and processing, since those factors determine the useful behavior of these materials. The work reported to date has had little success in producing commercially viable materials because the dearth of crystal structures of the active material We have demonstrated that determination of nucleation and growth kinetics of a particular BP can allow one to tailor growth conditions to produce crystals of a desired size and size distribution.…”

Section: ■ Conclusion and Outlookmentioning

confidence: 99%

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A Systematic Approach toward Designing Functional Ionic Porphyrin Crystalline Materials

Mazur

Hipps

2018

J. Phys. Chem. C

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Synthetic ionic porphyrin self-assembled structures possess remarkable optoelectronic properties that are useful for energy and sensor related technological application, and there is a continued interest in tailoring their molecular structure and interactions in order to control their various functions. Central to these efforts is the fundamental understanding of the structure, the chemical and physical properties, and the relationship between the structural organization of the chromophores and their functions. In this Feature Article, we demonstrate the capability of a nucleation and growth algorithm to reproducibly synthesize nano- to millimeter size single crystals of several different ionic binary porphyrin (BP) systems under chemically controlled conditions. Single crystal X-ray diffraction analysis, morphology, sensing, and mechanical measurements are presented. UV–vis and X-ray photoelectron spectroscopy of these materials is also discussed. The crystalline porphyrin assemblies have varying degrees of dark conductivity (depending on their chemical and structural composition) but all appear to be sensitive to light; i.e., they absorb radiation and become conductive and/or persistently photoconductive (PPC). In addition, some of these crystalline porphyrins show persistent ion beam induced conductivity. This rich photo and ion response provides opportunities for the selective light control of these semiconductors. Exposure of the BP crystals to small gas molecules such as O2 strongly modifies their photocurrent in sensing experiments. The range of the Young’s modulus values extracted from nanoindentation experiments indicates that the BP crystals have a Young’s modulus intermediate between “soft” polymers and composite materials, making them excellent candidates for deformable optoelectronic devices. Both the experimental photoconductive and mechanical properties of the porphyrin self-assembled structures can be correlated with their molecular organization and morphology. In addition, quantum mechanical calculations provide the electronic band structure and the density of states and help explain experimental prompt photoconductivity measurements. Theory was also used to develop strategies for precise manipulation of the photoresponse of the BP crystals by selective structure modification. This work shows that combining the results from structural and theoretical studies and correlating them with electronic and optoelectronic properties can assist in engineering highly organized functional materials from organic π-conjugated molecules.

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Section: Photoseponse Sensing and Mechanical Propertiesmentioning

confidence: 86%

Section: ■ Synthesis and Controlled Growthmentioning

confidence: 93%

Section: Photoseponse Sensing and Mechanical Propertiesmentioning

confidence: 99%

Section: ■ Synthesis and Controlled Growthmentioning

confidence: 99%

Section: ■ Conclusion and Outlookmentioning

confidence: 99%

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A Systematic Approach toward Designing Functional Ionic Porphyrin Crystalline Materials

Mazur

Hipps

2018

J. Phys. Chem. C

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Porphyrin Nanowire Bundles for Efficient Photoconductivity, Photoemission, and Generation of Singlet Oxygens toward Photodynamic Therapy

Sakurai

Sakaguchi

Takeshita

et al. 2020

ACS Appl. Nano Mater.

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Energy released from an accelerated high-energy single/cluster particle triggers solid-state polymerization and cross-linking reactions of porphyrin-based π-conjugated monomers within a nanometer-scaled one-dimensional spatial area along the ion trajectory, resulting in the formation of an insoluble nanowire with a precise diameter and length. The nanowires are isolated by the development processimmersion of the irradiated film in organic solventsand their shape and geometry are clearly characterized by atomic force microscopy. The obtained nanowire bundles, reflecting precisely the number of incident particles, show characteristic absorption spectra originating from porphyrin chromophores without significant degradation of the molecular cores. These porphyrin-based nanowires can be further functionalized into metallocomplexes by immersing the nanowires into solutions containing metal ion sources. The remarkable finding on the monomer structural parameters is that terminal alkyne groups are preferentially reacted and thus highly effective as a monomer structure for the present single particle-triggered linear polymerization method. The porphyrin-based nanowires show much higher photoconductivity than the precursor porphyrin films and enhanced fluorescence on silver nanoparticle layers via surface plasmon resonance. The porphyrin nanowires serve as photosensitizers mediating the generation of singlet oxygens, which is attractive for the use as a controlled nanosystem toward photocatalysis and photodynamic therapy.

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Comprehensive structure–function correlation of photoactive ionic π-conjugated supermolecular assemblies: an experimental and computational study

et al. 2016

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Persistent Conductivity in TPyP:TSPP Organic Nanorods Induced by Ion Bombardment

Cited by 5 publications

References 24 publications

A Systematic Approach toward Designing Functional Ionic Porphyrin Crystalline Materials

A Systematic Approach toward Designing Functional Ionic Porphyrin Crystalline Materials

Porphyrin Nanowire Bundles for Efficient Photoconductivity, Photoemission, and Generation of Singlet Oxygens toward Photodynamic Therapy

Comprehensive structure–function correlation of photoactive ionic π-conjugated supermolecular assemblies: an experimental and computational study

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