2D Organic Materials Research Articles

Chemiresistive Materials for Alcohol Vapor Sensing at Room Temperature

The development of efficient sensors able to detect alcoholic compounds has great relevance in many fields including medicine, pharmaceuticals, food and beverages, safety, and security. In addition, the measurements of alcohols in air are significant for environmental protection because volatile alcohols can have harmful effects on human health not only through ingestion, but also through inhalation or skin absorption. The analysis of alcohols in breath is a further expanding area, being employed for disease diagnoses. The analyses performed by using chromatography, mass-spectrometry, nuclear magnetic resonance, ultraviolet-visible spectroscopy, Fourier-transform infrared spectroscopy, or Raman spectroscopy often require complex sampling and procedures. As a consequence, many research groups have focused their efforts on the development of efficient portable sensors to replace conventional methods and bulky equipment. The ability to operate at room temperature is a key factor in designing portable light devices suitable for in situ real-time monitoring. In the present review, we provide a survey of the recent literature on the most efficient chemiresistive materials for alcohol sensing at room temperature. Remarkable gas-sensing performances have mainly been obtained by using metal oxides semiconductors (MOSs), metal organic frameworks (MOFs), 2D materials, and polymers. Among 2D materials, we mainly consider graphene-based materials, graphitic carbon nitride, transition metal chalcogenides, and MXenes. We discuss scientific advances and innovations published in the span of the last five years, focusing on sensing mechanisms.

A General Synthesis Method for Covalent Organic Framework and Inorganic 2D Materials Hybrids.

Two-dimensional (2D) inorganic/organic hybrids provide a versatile platform for diverse applications, including electronic, catalysis, and energy storage devices. The recent surge in 2D covalent organic frameworks (COFs) has introduced an organic counterpart for the development of advanced 2D organic/inorganic hybrids with improved electronic coupling, charge separation, and carrier mobility. However, existing synthesis methods have primarily focused on few-layered film structures, which limits scalability for practical applications. Herein, we present a general synthesis approach for a range of COF/inorganic 2D material hybrids, utilizing 2D inorganic materials as both catalysts and inorganic building blocks. By leveraging the intrinsic Lewis acid sites on the inorganic 2D materials such as hexagonal boron nitride (hBN) and transition metal dichalcogenides, COFs with diverse functional groups and topologies can grow on the surface of inorganic 2D materials. The controlled 2D morphology and excellent solution dispersibility of the resulting hybrids allow for easy processing into films through vacuum filtration. As proof of concept, hBN/COF films were employed as filters for Rhodamine 6G removal under flow-through conditions, achieving a removal rate exceeding 93%. The present work provides a simple and versatile synthesis method for the scalable fabrication of COF/inorganic 2D hybrids, offering exciting opportunities for practical applications such as water treatment and energy storage.

P-Toluenesulfonic Acid Modified Two-Dimensional ZrSe2 as a Hole Transport Layer for High-Performance Organic Solar Cells.

Two-dimensional (2D) materials have attracted attention due to their excellent optoelectronic properties, but their applications are limited by their defects and vacancies. Surface modification is an effective method to restore their performance. Here, ZrSe2 is modified with conductive polymer p-toluenesulfonic acid (PTSA). It is found that PTSA can obtain electrons of ZrSe2 through the combination of -SO3H and ZrSe2, thus forming interfacial dipoles, which improve the work function of ZrSe2. In addition, -OH in PTSA can effectively fill the Se vacancy in ZrSe2 to form P-type doping, thereby improving its conductivity. ZrSe2 modified by the PTSA material is first used as a hole transport layer (HTL) in organic solar cells (OSCs). The efficiency of OSCs based on the PBDB-T:ITIC and PM6:L8-BO binary active layer with ZrSe2:PTSA as the novel HTL reaches 10.66 and 18.14%, which are obviously higher than the efficiency of OSCs with pure ZrSe2 as the HTL (8.48 and 15.64%). More interestingly, the stability of the device with ZrSe2:PTSA as HTL is significantly better than that of PEDOT:PSS. This study shows that the modification of the organic material can effectively improve the photoelectric performance of ZrSe2 and explores the physical mechanism of the interaction between the organic modifier and 2D materials.

A Concise Overview of Ultrasound-Assisted Techniques for the Production of 2D Materials

The production of low-dimensional materials is the key topic of nanoscience. The development of new routes to downsize organic and inorganic materials has focused the attention of a great part of the scientific community that is still debating on the best route to pursue. Among nanostructures, 2D species have been investigated since the discovery of graphene. Nonetheless, the production of 2D materials is very complex, and the discussion on which is the most profitable way is still open. Ultrasound-assisted techniques represent one of the best routes for the production of 2D materials with minimum consumption of energy and best performances. Accordingly, we present a concise and exhaustive discussion about the use of ultrasound-assisted techniques for the production of both organic and inorganic 2D materials, also providing a theoretical overview of the mechanism behind the use of ultrasounds in synthetic material science.

Self‐Assembled 2D Sheets of an Amphiphilic Sexiphenyl Exhibit Intense Polarized Blue Emission in the Solid State

AbstractDistinct from inorganic 2D nanomaterials (e.g., graphene, MoS2, etc,), self‐assembled organic 2D materials are significant due to the unique advantages of fine structure tunability and functionality. Electronically and photofunctionally‐active compounds (e.g., pentacene, p‐sexiphenyl) are highly attractive for applications but are limited by difficult handling and the existence of only a few native structures of the compounds. Here, it is shown that a p‐sexiphenyl derivative incorporated into 2D multilamellar sheets with chromophores oriented in the layers exhibits a significant polarization of photoluminescence. Highly emissive, amphiphilic sexiphenyl with hydrophilic/hydrophobic groups self‐assembles at air–water interface with chromophore orientation in the resulting films being controlled by monolayer compression. Large‐area multilamellar structures with p‐sexiphenyl chromophores highly oriented against the 2D plane are prepared by consecutive film transfers. The 2D sheets exhibit significant polarization of photoluminescence with polarization ratio 0.8 between orthogonal in‐plane axes. Notably, multilamellar structures cannot be established for the same p‐sexiphenyl using thermotropic processing thus emphasizing the importance of the 2D sheet multilayer synthesis process. Amphiphile design can be applied for the tailored synthesis of large‐area multilayered 2D sheets and used to construct highly efficient light‐emitting devices.

A Cu3BHT-Graphene van der Waals Heterostructure with Strong Interlayer Coupling for Highly Efficient Photoinduced Charge Separation.

Two-dimensional van der Waals heterostructures (2D vdWhs) are of significant interest due to their intriguing physical properties critically defined by the constituent monolayers and their interlayer coupling. Synthetic access to 2D vdWhs based on chemically tunable monolayer organic 2D materials remains challenging. Herein, the fabrication of a novel organic-inorganic bilayer vdWh by combining π-conjugated 2D coordination polymer (2DCP, i.e., Cu3BHT, BHT = benzenehexathiol) with graphene is reported. Monolayer Cu3BHT with detectable µm2-scale uniformity and atomic flatness is synthesized using on-water surface chemistry. A combination of diffraction and imaging techniques enables the determination of the crystal structure of monolayer Cu3BHT with atomic precision. Leveraging the strong interlayer coupling, Cu3BHT-graphene vdWh exhibits highly efficient photoinduced interlayer charge separation with a net electron transfer efficiency of up to 34% from Cu3BHT to graphene, superior to those of reported bilayer 2D vdWhs and molecular-graphene vdWhs. This study unveils the potential for developing novel 2DCP-based vdWhs with intriguing physical properties.

Effect of self and extrinsic encapsulation on electron resilience of porous 2D polymer nanosheets

Despite the exceptional resolution in aberration-corrected high-resolution transmission electron microscope (AC-HRTEM) images of inorganic two-dimensional (2D) materials, achieving high-resolution imaging of organic 2D materials remains a daunting challenge due to their low electron resilience. Optimizing the critical dose (the electron exposure, the material can accept before it is noticeably damaged) is vital to mitigate this challenge. An understanding of electron resilience in porous crystalline 2D polymers including the effect of sample thickness has not been derived thus far. It is assumed, that additional layers of the sample form a cage around inner layers, which are preventing fragments from escaping into the vacuum and enabling recombination. In the literature this so called caging effect has been reported for perylene and pythalocyanine. In this work we determine the critical dose of a porous, triazine-based 2D polymer as function of the sample thickness. The results show that the caging effect should not be generalized to more sophisticated polymer systems. We argue that pore channels in the framework structure serve as escape routes for free fragments preventing the caging effect and thus showing surprisingly a thickness-independent critical dose. Moreover, we demonstrate that graphene encapsulation prevents fragment escape and results in an increase in the critical electron dose and unit-cell image resolution.

Field and Thermal Emission Limited Charge Injection in Au-C60-Graphene van der Waals Vertical Heterostructures for Organic Electronics.

Among the family of 2D materials, graphene is the ideal candidate as top or interlayer electrode for hybrid van der Waals heterostructures made of organic thin films and 2D materials due to its high conductivity and mobility and its inherent ability of forming neat interfaces without diffusing in the adjacent organic layer. Understanding the charge injection mechanism at graphene/organic semiconductor interfaces is therefore crucial to develop organic electronic devices. In particular, Gr/C60 interfaces are promising building blocks for future n-type vertical organic transistors exploiting graphene as tunneling base electrode in a two back-to-back Gr/C60 Schottky diode configuration. This work delves into the charge transport mechanism across Au/C60/Gr vertical heterostructures fabricated on Si/SiO2 using a combination of techniques commonly used in the semiconductor industry, where a resist-free CVD graphene layer functions as a top electrode. Temperature-dependent electrical measurements show that the transport mechanism is injection limited and occurs via Fowler-Nordheim tunneling at low temperature, while it is dominated by a nonideal thermionic emission at room and high temperatures, with energy barriers at room temperature of ca. 0.58 and 0.65 eV at the Gr/C60 and Au/C60 interfaces, respectively. Impedance spectroscopy confirms that the organic semiconductor is depleted, and the energy band diagram results in two electron blocking interfaces. The resulting rectifying nature of the Gr/C60 interface could be exploited in organic hot electron transistors and vertical organic permeable-base transistors.

A Space‐Confined Polymerization Templated by Ice Enables Large‐Scale Synthesis of Two‐Dimensional Polymer Sheets

AbstractDespite significant progress in the preparation and characterization of two‐dimensional (2D) materials, the synthesis of 2D organic materials remains challenging. Here, we report a novel space‐confined polymerization method that enables the large‐scale synthesis of 2D sheets of a functional conjugated polymer, namely, poly(3,4‐ethylenedioxythiophene) (PEDOT). A key step in this method is the confinement of monomer to the boundaries of ice crystals using micelles. This spatial confinement directs the polymerization to form 2D PEDOT sheets with high crystallinity and controlled morphology. Supercapacitors prepared from the 2D PEDOT sheets exhibit outstanding performance metrics. In aqueous electrolyte, a high areal specific capacitance of 898 mF cm−2 at 0.2 mA cm−2 along with an excellent rate capability is achieved (e.g., capacitance retention of 67.6 % at a 50‐fold higher current). Moreover, the 2D PEDOT‐based supercapacitors exhibit outstanding cycling stability (capacitance retention of 98.5 % after 30,000 cycles). Device performance is further improved when an organic electrolyte is used.

A Space-Confined Polymerization Templated by Ice Enables Large-Scale Synthesis of Two-Dimensional Polymer Sheets.

Despite significant progress in the preparation and characterization of many two-dimensional (2D) materials, the synthesis of 2D organic materials remains challenging. Here, we report a novel space-confined polymerization method that enables the large-scale synthesis of 2D sheets of a functional conjugated polymer, namely, poly(3,4-ethylenedioxythiophene) (PEDOT). A key step in this method is the confinement of monomer to the boundaries of ice crystals using micelles. This spatial confinement directs the polymerization to form 2D PEDOT sheets with high crystallinity and controlled morphology. Supercapacitors prepared from the 2D PEDOT sheets exhibit outstanding performance metrics. In aqueous electrolyte, a high areal specific capacitance of 898 mF cm-2 at 0.2 mA cm-2 along with an excellent rate capability is achieved (e.g., capacitance retention of 67.6% at a 50-fold higher current). Moreover, the 2D PEDOT-based supercapacitors exhibit outstanding cycling stability (capacitance retention of 98.5% after 30,000 cycles). Device performance is further improved when an organic electrolyte is used.

Carbazolylene-Ethynylene Macrocycle based Conductive Covalent Organic Frameworks.

Two covalent organic frameworks consisting of carbazolylene-ethynylene shape-persistent macrocycles with azine (MC-COF-1) or imine (MC-COF-2) linkages were synthesized via imine condensation. The obtained 2D frameworks are fully conjugated which imparts semiconducting properties. In addition, the frameworks showed high porosity with aligned accessible porous channels along the z axis, serving as an ideal platform for post-synthetic incorporation of I2 into the channels to enable electrical conductivity. The resulting MC-COF-1 showed an electrical conductivity up to 7.8 × 10-4 S/cm at room temperature upon I2 doping with the activation energy as low as 0.09 eV. Furthermore, we demonstrated that the electrical properties of both MC-COFs are switchable between electron-conducting and insulating states by simply implementing doping-regenerating cycles. The knowledge gained in this study opens new possibilities for the future development of tunable conductive 2D organic materials.

Carbazolylene‐Ethynylene Macrocycle based Conductive Covalent Organic Frameworks

AbstractTwo covalent organic frameworks consisting of carbazolylene‐ethynylene shape‐persistent macrocycles with azine (MC‐COF‐1) or imine (MC‐COF‐2) linkages were synthesized via imine condensation. The obtained 2D frameworks are fully conjugated which imparts semiconducting properties. In addition, the frameworks showed high porosity with aligned accessible porous channels along the z axis, serving as an ideal platform for post‐synthetic incorporation of I2 into the channels to enable electrical conductivity. The resulting MC‐COF‐1 showed an electrical conductivity up to 7.8×10−4 S cm−1 at room temperature upon I2 doping with the activation energy as low as 0.09 eV. Furthermore, we demonstrated that the electrical properties of both MC‐COFs are switchable between electron‐conducting and insulating states by simply implementing doping‐regenerating cycles. The knowledge gained in this study opens new possibilities for the future development of tunable conductive 2D organic materials.

Gas Transport Mechanisms through Molecular Thin Carbon Nanomembranes.

Molecular thin carbon nanomembranes (CNMs) synthesized by electron irradiation induced cross-linking of aromatic self-assembled monolayers (SAMs) are promising 2D materials for the next generation of filtration technologies. Their unique properties including ultimately low thickness of ≈1nm, sub-nanometer porosity, mechanical and chemical stability are attractive for the development of innovative filters with low energy consumption, improved selectivity, and robustness. However, the permeation mechanisms through CNMs resulting in, e.g., an ≈1000 times higher fluxes of water in comparison to helium have not been yet understood. Here, a study of the permeation of He, Ne, D2 , CO2 , Ar, O2 and D2 O using mass spectrometry in the temperature range from room temperature to ≈120°C is studied. As a model system, CNMs made from [1″,4',1',1]-terphenyl-4-thiol SAMs are investigated. It is found out that all studied gases experience an activation energy barrier upon the permeation which scales with their kinetic diameters. Moreover, their permeation rates are dependent on the adsorption on the nanomembrane surface. These findings enable to rationalize the permeation mechanisms and establish a model, which paves the way toward the rational design not only of CNMs but also of other organic and inorganic 2D materials for energy-efficient and highly selective filtration applications.

Emergent Spin Frustration in Neutral Mixed-Valence 2D Conjugated Polymers: A Potential Quantum Materials Platform

Two-dimensional conjugated polymers (2DCPs)─organic 2D materials composed of arrays of carbon sp2 centers connected by π-conjugated linkers─are attracting increasing attention due to their potential applications in device technologies. This interest stems from the ability of 2DCPs to host a range of correlated electronic and magnetic states (e.g., Mott insulators). Substitution of all carbon sp2 centers in 2DCPs by nitrogen or boron results in diamagnetic insulating states. Partial substitution of C sp2 centers by B or N atoms has not yet been considered for extended 2DCPs but has been extensively studied in the analogous neutral mixed-valence molecular systems. Here, we employ accurate first-principles calculations to predict the electronic and magnetic properties of a new class of hexagonally connected neutral mixed-valence 2DCPs in which every other C sp2 nodal center is substituted by either a N or B atom. We show that these neutral mixed-valence 2DCPs significantly energetically favor a state with emergent superexchange-mediated antiferromagnetic (AFM) interactions between C-based spin-1/2 centers on a triangular sublattice. These AFM interactions are surprisingly strong and comparable to those in the parent compounds of cuprate superconductors. The rigid and covalently linked symmetric triangular AFM lattice in these materials thus provides a highly promising and robust basis for 2D spin frustration. As such, extended mixed-valence 2DCPs are a highly attractive platform for the future bottom-up realization of a new class of all-organic quantum materials, which could host exotic correlated electronic states (e.g., unusual magnetic ordering, quantum spin liquids).

2D Organic Materials: Status and Challenges.

In the past few decades, 2D layer materials have gradually become a central focus in materials science owing to their uniquely layered structural qualities and good optoelectronic properties. However, in the development of 2D materials, several disadvantages, such as limited types of materials and the inability to synthesize large-scale materials, severely confine their application. Therefore, further exploration of new materials and preparation methods is necessary to meet technological developmental needs. Organic molecular materials have the advantage of being customizable. Therefore, if organic molecular and 2D materials are combined, the resulting 2D organic materials would have excellent optical and electrical properties. In addition, through this combination, the free design and large-scale synthesis of 2D materials can be realized in principle. Furthermore, 2D organic materials exhibit excellent properties and unique functionalities along with great potential for developing sensors, biomedicine, and electronics. In this review, 2D organic materials are divided into five categories. The preparation methods and material properties of each class of materials are also described in detail. Notably, to comprehensively understand each material's advantages, the latest research applications for each material are presented in detail and summarized. Finally, the future development and application prospects of 2D organic materials are briefly discussed.

Two-dimensional Dirac materials: Tight-binding lattice models and material candidates

The discovery of graphene has led to the devotion of intensive efforts, theoretical and experimental, to produce two-dimensional (2D) materials that can be used for developing functional materials and devices. This work provides a brief review of the recent developments in the lattice models of 2D Dirac materials and their relevant real material counterparts that are crucial for understanding the origins of 2D Dirac cones in electronic band structures as well as their material design and device applications. We focus on the roles of lattice symmetry, atomic orbital hybridization, and spin–orbit coupling in the presence of a Dirac cone. A number of lattice models, such as honeycomb, kagome, ruby, star, Cairo, and line-centered honeycomb, with different symmetries are reviewed based on the tight-binding approach. Inorganic and organic 2D materials, theoretically proposed or experimentally synthesized to satisfy these 2D Dirac lattice models, are summarized.

Multi-Dimensional Molecular Self-Assembly Strategy for the Construction of Two-Dimensional Mesoporous Polydiaminopyridine and Carbon Materials.

Two-dimensional (2D) mesoporous polymers, combining the advantages of organic polymers, porous materials, and 2D materials, have received great attention in adsorption, catalysis, and energy storage. However, the synthesis of 2D mesoporous polymers is not only challenged by the complex 2D structure construction, but also by the low yield and difficulty in controlling the dynamics of the assembly during the generation of mesopores. Herein, a facile multi-dimensional molecular self-assembly strategy is reported for the preparation of 2D mesoporous polydiaminopyridines (MPDAPs), which features tunable pore sizes (17-35nm) and abundant N content up to 18.0at%. Benefitting from the abundant N sites, 2D nanostructure, and uniform-large mesopores, the 2D MPDAPs exhibit excellent catalytic performance for the Knoevenagel condensation reaction. After calcination under N2 atmosphere, the obtained 2D N-doped mesoporous carbon (NMCs) with large and uniform pore sizes, high surface areas, abundant N content (up to 23.1%), and a high ratio of basic N species (57.0% pyridinic N and 35.9% pyrrolic N) can show an excellent CO2 uptake density (11.7µmolm-2 at 273K), higher than previously reported porous materials.

Recent advances in 2D organic−inorganic heterostructures for electronics and optoelectronics

AbstractTwo‐dimensional (2D) materials show outstanding properties such as dangling bond‐free surfaces, strong in‐plane while weak out‐of‐plane bonding, layer‐dependent electronic structures, and tunable electronic and optoelectronic properties, making them promising for numerous applications. Integrating 2D inorganics with organic materials to make van der Waals heterostructures at the 2D thickness limit has created new platforms for fabricating on‐demand multifunctional devices. To further broaden the limited choices of 2D inorganic‐based heterostructures, a wide range of available 2D organic materials with tunable properties have opened new opportunities for designing large numbers of heterostructures with 2D inorganic materials. This review aims to attract the attention of researchers toward this emerging 2D organic−inorganic field. We first highlight recent progress in organic−inorganic heterostructures and their synthesis and then discuss their potential applications, such as field‐effect transistors, photodetectors, solar cells, and neuromorphic computing devices. In the end, we present a summary of challenges and opportunities in this field.

Insight into the Nanotribological Mechanism of Two-Dimensional Covalent Organic Frameworks.

Two-dimensional (2D) materials are promising in reducing friction-induced energy loss and wear in automotive and electronics industries because of their superior tribological performance. As a kind of organic 2D materials, the structure and functionality of covalent organic frameworks (COFs) are much easier to tailor compared to other inorganic 2D materials, which expand their potential application in a Micro-Electro-Mechanical System (MEMS). In this manuscript, several kinds of COFs are synthesized and characterized on the surface of highly oriented pyrolytic graphite (HOPG) to investigate the nanotribological mechanism of organic 2D materials. It is surprisingly revealed that the friction coefficients of surface COFs are positively correlated with the pore sizes of honeycomb networks. The COFs with smaller pores would have a smoother potential energy surface and exhibit a lower friction coefficient. Besides, the porous structures of surface COFs make them good candidates to be host templates. The host-guest assembly structures are successfully constructed after introducing coronene molecules, and these host-guest systems display higher friction coefficients because the assembly structure of the guest molecules would be perturbed during the friction process and bring additional slip energy barriers, but the capacity of COFs to form composite assembly with functional guest molecules greatly promotes their further application in the MEMS.

Synthesis and Characterization of Graphene oxide for Gas Sensing Applications

Organic 2D materials have gained extensive attraction in the field of the gas sensor. Because of their critical role in environmental monitoring, chemical manufacturing industries, and human health safety. In recent years most of the research groups have been interested, to fabricate the Graphene oxide-based chemi-resistive gas sensor, owing to its superior structural, mechanical, and electrical properties. Excellent mechanical strength (Young modulus ∼0.05 TPA), the potentiality of ultrafast electron transport (highest mobility ∼200,000 cm2/V s) along with the best surface to volume ratio. In this paper, we have prepared Graphene oxide nanosheets by the modified hummers method. Structural properties of the as-prepared sample were confirmed by XRD and RAMAN spectroscopy. morphological analyses were done by FE-SEM analysis.