Synthetic approach to thin films of metal-free polyphthalocyanine

Sedlovets, Daria M.; Shuvalov, Maxim V.; Khodos, I. I.; Trofimov, O.V.; Korepanov, Vitaly I.

doi:10.1088/2053-1591/aaa8c2

Cited by 4 publications

(5 citation statements)

References 17 publications

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“…The vapor/solid synthesis of MePPCs was done according to the previously reported procedure [8,9]. Briefly, a thin layer (few nm) of metal was deposited on a substrate and placed in a reactor for chemical vapor deposition (CVD).…”

Section: Methodsmentioning

confidence: 99%

“…The molybdate catalyst for H 2 PPC is necessary only for the vapor/solid regime. In this case, the polymer film grows selectively only on the molybdate-doped surface [8]. The role of Mo 6+ ion is to coordinate the PMTN molecules; is a common catalyst for industrial synthesis of monomeric PCs (see [19] and references therein).…”

Section: Continuity Conductivity and The Growth Mechanismmentioning

confidence: 99%

“…Despite the long study history of PPCs [6,7], there is a controversy in the literature regarding the structure and characterization of these materials. Several groups reported significantly different spectra of the materials produced by different techniques [1,[8][9][10][11][12]. It has been shown recently that the IR, Raman and UV-vis spectra of PPCs strongly depend on the polymerization degree, and products, obtained in many preceding works, should be assigned to either monomeric PPCs or to material of low polymerization degree (oligomers) [13].…”

Section: Introductionmentioning

confidence: 99%

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2D polyphthalocyanines of cross-linked and ordered structures from different growth regimes

Sedlovets

Волков

Khodos

et al. 2019

J. Phys. D: Appl. Phys.

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2D conjugated polyphthalocyanines can be obtained as two distinctly different types of material with specific molecular structures and different morphological properties. It was believed that the temperature is the key factor affecting the chemical reaction, but we show that even at the optimal temperature (420 °C), the reaction on vapor/solid interface and liquid/solid interface yields different products: while the former is well-polymerized and ordered, the latter is amorphous and cross-linked with the typical conjugation scale of single phthalocyanine (PC) ring. Infrared spectroscopy is most sensitive tool for identifying the molecular structure, providing the information on polymerization degree, structural uniformity and content of terminal groups. We show that, unlike the ordered polyphthalocyanines, the cross-linked product can be reproducibly obtained as continuous conductive material.

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Section: Methodsmentioning

confidence: 99%

Section: Continuity Conductivity and The Growth Mechanismmentioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

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2D polyphthalocyanines of cross-linked and ordered structures from different growth regimes

Sedlovets

Волков

Khodos

et al. 2019

J. Phys. D: Appl. Phys.

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“…For H 2 PPC, instead of metal, we used pre-coating with molybdate catalyst. [17] This procedure was recently used by Guo's group [5] to obtain CuPPC for non-volatile memory device. Crystallinity and high polymerization degree of the film were confirmed using TEM, XPS and UV-Vis spectra.…”

Section: Recent Work On the Cvd Growth Of Thin Filmsmentioning

confidence: 99%

Recent Advances in 2D Polymeric Phthalocyanines: Synthesis, Characterization, Applications and New Challenges

Korepanov¹,

Sedlovets²

2019

MHC

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This article is dedicated to Prof. Dieter Wöhrle, whose works for a long time have been the highest standard and a source of inspiration for us 2D polyphthalocyanines (PPCs) are actively studied as advanced materials for new generation energy and microelectronics. Some time ago such compounds were dubbed "just a dream of synthetic chemists", what was a perfect reflection of, on the one hand, high promise, and, on the other hand, experimental difficulties faced with the 2D polymers. Despite a long history of PPCs (since late 1950s), it was shown recently that in many works the reaction products were misinterpreted , and the studied compounds should be assigned to a low degree of the polymerization. Recent years, the discovery of graphene has inspired a new wave of interest to PPCs. From the graphene point of view, the questions are: whether we can make other graphene-like materials with modified properties? Can we use metal atoms to tune its electronic properties? Can we make a magnetic 2D material? From the polymer chemistry point of view, the major problem is why the common synthetic approaches and characterization techniques didn't work for this polymer as expected? And how to identify the reaction products? This review covers evolution of the synthetic approaches, establishment of the reliable characterization techniques, as well as the promising applications of 2D PPCs and the "new dreams" in science and technology of these materials.

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“…Molecular solids also can give asymmetric Raman bands. In this work, we take the 551 cm -1 band of pyromellitic tetranitrile (PMTN), a practically valuable precursor for 2D polymers 24 . The origins of the asymmetry may include grain boundaries different phases and other reasons.…”

Section: Fitting Of Experimental Spectramentioning

confidence: 99%

An asymmetric fitting function for condensed-phase Raman spectroscopy

Korepanov

Sedlovets

2018

Analyst

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Asymmetric lineshapes are experimentally observed in the Raman spectra of different classes of condensed matter. Determination of the peak parameters, typically done with symmetric pseudo-Voigt functions, in such situations yields unreliable results. While a wide choice of asymmetric fitting functions is possible, for the function to be practically useful, it should satisfy several criteria: simple analytic form, minimum parameters, description of the symmetric shape as "zero case", estimation of the desired peak parameters in a straightforward way and, above all, adequate description of the experimental data. In this work we formulate the asymmetric pseudo-Voigt function by damped perturbation of the original symmetric shapes with one asymmetry-related parameter. The damped character of the perturbation ensures by construction consistent behavior of the line tails. We test the asymmetric function by fitting the experimental Raman spectra. The results show that the function is able to describe a wide range of experimentally observed asymmetries for different natures of asymmetric broadening, including 3D and 2D crystals, nanoparticles, polymers, and molecular solids and liquids.

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Synthetic approach to thin films of metal-free polyphthalocyanine

Cited by 4 publications

References 17 publications

2D polyphthalocyanines of cross-linked and ordered structures from different growth regimes

2D polyphthalocyanines of cross-linked and ordered structures from different growth regimes

Recent Advances in 2D Polymeric Phthalocyanines: Synthesis, Characterization, Applications and New Challenges

An asymmetric fitting function for condensed-phase Raman spectroscopy

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