Microspacing In-Air Sublimation Growth of Organic Crystals

Ye, Xin; Liu, Yang; Han, Qi; Ge, Chao; Cui, Shuangyue; Zhang, Leilei; Zheng, Xiaojiao; Liu, Guangfeng; Liu, Jie; Liu, Duo; Tao, Xutang

doi:10.1021/acs.chemmater.7b04170

Cited by 95 publications

(108 citation statements)

References 43 publications

(69 reference statements)

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“…An efficient buoyancy-driven molecular flow vapor transport mode would be generated within the confined space between two substrates, which on one side facilitates the evaporation of the starting materials although the temperature is much lower than the melting point of TCNB (268 °C), and on the other hand protects the molecules from oxidation or decomposition. More detailed discussions about the stability of the organic materials during the sublimation process refer to our last work 29 . The identity and purity characterizations of the grown FTCs are shown in Supplementary Fig.…”

Section: Resultsmentioning

confidence: 99%

“…Whereas, the morphology of the grown cocrystals, which are inherited from their intrinsic crystal habit 28 , is hardly to be altered. Recently we developed a microspacing in-air sublimation (MAS) to grow organic crystals directly on the substrate 29 . The method can be conducted totally in air, avoiding costly vacuum system and time-consuming procedures in common PVT.…”

Section: Introductionmentioning

confidence: 99%

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1D versus 2D cocrystals growth via microspacing in-air sublimation

et al. 2019

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Organic cocrystals possess valuable properties owing to the synergistic effect of the individual components. However, the growth of molecular cocrystals is still in its primary stage. Here we develop a microspacing in-air sublimation method to grow organic cocrystals, and furthermore to realize morphology control on them, which is essential for structure–property relations. A series of polycyclic aromatic hydrocarbon (PAH)‒1,2,4,5-tetracyanobenzene (TCNB) complexes cocrystals are grown directly on the substrate, with the morphology tunable from 1D needle-like to 2D plate-like on demand. Spatially resolved photoluminescence spectra analyses on different cocrystals display morphology dependent and anisotropic optical waveguiding properties. In situ observation and energy calculations of the crystallization processes reveal the formation mechanism being from a competition between growth kinetics-defined crystal habit and the thermodynamics driving force. This growth technique may serve the future demand for tunable morphology organic cocrystals in different functional applications.

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Section: Resultsmentioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

1D versus 2D cocrystals growth via microspacing in-air sublimation

et al. 2019

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“…For example, solvent‐assisted self‐assembly techniques require surfactants and lead to the formation of thin‐film deposition on the substrate along with microstructures . In a recent study, though, air‐sublimation of perylene could yield only the α‐phase, no systematic optimization of temperature was performed to achieve the vital β perylene phases . In another report, organic molecular beam deposition of perylene onto silicone‐oil‐covered substrates allows the fabrication of both polymorphs .…”

Section: Methodsmentioning

confidence: 99%

Ambient Pressure Sublimation Technique Provides Polymorph‐Selective Perylene Nonlinear Optical Microcavities

Pradeep

Mitetelo

Annadhasan

et al. 2019

Advanced Optical Materials

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Highly pure, organic, crystalline materials with nonlinear optical (NLO) properties are in great demand due to their potential to be utilized in miniaturized nanophotonic device applications. Perylene dye is one of the celebrated near‐direct bandgap NLO materials. It crystallizes in two distinctive polymorphic forms (square‐shaped, α, and rhombus‐shaped, β) emitting yellow and green fluorescence, respectively. However, selective access to any one of the polymorphic microcrystals possessing qualities such as smooth‐surface and mirror‐like light‐reflecting sharp edges is a challenging task. On the other hand, these qualities are indispensable for a microcrystal to operate as an optical cavity. Here, a cost‐effective and straightforward, yet promising sublimation technique to grow microscale perylene crystals with the above qualities in a polymorph‐selective manner at ambient pressure is presented. As a result, both polymorphic microcrystals act as whispering gallery mode (WGM) cavities in the linear and notably, NLO regime as well. In agreement with the experiments, finite difference time domain numerical calculations support the WGM‐cavity‐type and also reveal the intricate localization of electric‐field within these cavities. Further, the quadratic dependence of emission intensity as a function of laser power establishes the two‐photon absorption nature of the optical cavities pumped by infrared lasers.

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“…The cocrystals based on vapor phase growth have the characteristics of high quality and solvent free, so the enrichment and development of vapor‐based methods is favored over PVT. For example, Tao and coworkers reported an unprecedented vapor‐to‐melt‐to‐crystal mechanism to grow organic single crystals by a microspacing in‐air sublimation method, avoiding the costly vacuum system and time‐consuming procedures in common PVT . Subsequently, they successfully prepared organic cocrystals by using this method, and the morphology of the cocrystals can be tunable from 1D needle‐like to 2D plate‐like on demand…”

Section: Rational Design and Controllable Preparation Of Organic Cocrmentioning

confidence: 99%

Cocrystal Engineering: A Collaborative Strategy toward Functional Materials

et al. 2019

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materials, [9][10][11][12] which are crystalline singlephase materials composed of two or more different compounds generally in a stoichiometric ratio, [13] providing a platform for unveiling the structure-property relationships at a molecular level. [14] The building blocks are assembled via noncovalent interactions, offering the opportunity to achieve noncovalent synthesis of functional molecules. [15] Compared with the traditional covalent synthesis, cocrystal engineering offers numerous advantages, including: 1) avoiding complicated synthesis procedures, and cocrystal assemblies have been successfully fabricated by the vapor methods and solution-processing methods in a facile and low-cost way; 2) manipulating intermolecular interactions through selecting suitable conformers from a plentiful supply of raw materials, resulting in tunable structures, morphologies, and sizes; 3) achieving rare and multifunctional properties through a collaborative strategy in distinct constituent units, which are difficult to realize for individual components. [16][17][18] Cocrystal engineering began to draw much attention since the exploration of the metal conductive tetrathiafulvalene-7,7,8,8-tetracyanoquinodimethane (TTF-TCNQ) cocrystals in 1973. [19] The peculiar conductivity in organic materials makes it possible for cocrystals to serve as organic electrodes, which can effectively lower the contact resistance and further improve device performance. Encouraged by this, cocrystals can serve as a breakthrough and provide an opportunity to discover novel physicochemical properties, which are far beyond the performance of single materials. In this respect, dielectric response [20] and nonlinear optics [21,22] are also realized through rational design of each component, which is absent in their constitute components. Even more, the bottom-up supramolecular assembly provides the opportunity to equip them with the individual properties of the donor or acceptor to create multifunctional materials. [23] Typically, ambipolar charge transport can be generated by coassembling p-type semiconductors and n-type ones, and the charge-carrier mobility is now up to 1.57 cm 2 V −1 s −1 for holes and 0.47 cm 2 V −1 s −1 for electrons. [24] To date, these exciting results accelerate the investigations of organic functional cocrystals, such as room-temperature ferroelectricity, [25][26][27] optical waveguide properties, [28,29] pure organic room-temperature phosphorescent properties, [30][31][32] stimulusresponse (e.g., mechanical stress, [33,34] heat, [35,36] or solvent [37] ) characteristics, photovoltaics, [38] and near-infrared photothermal (PT) conversion and imaging, [39] etc.Cocrystal engineering with a noncovalent assembly feature by simple constituent units has inspired great interest and has emerged as an efficient and versatile route to construct functional materials, especially for the fabrication of novel and multifunctional materials, due to the collaborative strategy in the distinct constituent units. Meanwhile, the precise crystal a...

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Microspacing In-Air Sublimation Growth of Organic Crystals

Cited by 95 publications

References 43 publications

1D versus 2D cocrystals growth via microspacing in-air sublimation

1D versus 2D cocrystals growth via microspacing in-air sublimation

Ambient Pressure Sublimation Technique Provides Polymorph‐Selective Perylene Nonlinear Optical Microcavities

Cocrystal Engineering: A Collaborative Strategy toward Functional Materials

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