The Prospect of Dimensionality in Porous Semiconductors

With the advent of silicon-based semiconductors, a plethora of previously unknown technologies became possible. The development of lightweight low-dimensional organic semiconductors followed soon after. However, the efficient charge/electron transfers enabled by the non-porous 3D structure of silicon is rather challenging to be realized by their (metal-)organic counterparts. Nevertheless, the demand for lighter, more efficient semiconductors is steadily increasing resulting in a growing interest in (metal-)organic semiconductors. These novel materials are faced with a variety of challenges originating from their chemical design, their packing and crystallinity. Although the effect of molecular design is quite well understood, the influence of dimensionality and the associated change in properties (porosity, packing, conjugation) is still an uncharted area in (metal-)organic semiconductors, yet highly important for their practical utilization. In this Minireview, an overview on the design and synthesis of porous semiconductors, with a particular emphasis on organic semiconductors, is presented and the influence of dimensionality is discussed.     

Solar-Powered Organic Semiconductor–Bacteria Biohybrids for CO2 Reduction into Acetic Acid

An organic semiconductor–bacteria biohybrid photosynthetic system is used to efficiently realize CO₂ reduction to produce acetic acid with the non-photosynthetic bacteria Moorella thermoacetica. Perylene diimide derivative (PDI) and poly(fluorene-co-phenylene) (PFP) were coated on the bacteria surface as photosensitizers to form a p-n heterojunction (PFP/PDI) layer, affording higher hole/electron separation efficiency. The π-conjugated semiconductors possess excellent light-harvesting ability and biocompatibility, and the cationic side chains of organic semiconductors could intercalate into cell membranes, ensuring efficient electron transfer to bacteria. Moorella thermoacetica can thus harvest photoexcited electrons from the PFP/PDI heterojunction, driving the Wood–Ljungdahl pathway to synthesize acetic acid from CO₂ under illumination. The efficiency of this organic biohybrid is about 1.6 %, which is comparable to those of reported inorganic biohybrid systems.     

Solar‐Powered Organic Semiconductor–Bacteria Biohybrids for CO2 Reduction into Acetic Acid

An organic semiconductor–bacteria biohybrid photosynthetic system is used to efficiently realize CO₂ reduction to produce acetic acid with the non‐photosynthetic bacteria Moorella thermoacetica. Perylene diimide derivative (PDI) and poly(fluorene‐co‐phenylene) (PFP) were coated on the bacteria surface as photosensitizers to form a p‐n heterojunction (PFP/PDI) layer, affording higher hole/electron separation efficiency. The π‐conjugated semiconductors possess excellent light‐harvesting ability and biocompatibility, and the cationic side chains of organic semiconductors could intercalate into cell membranes, ensuring efficient electron transfer to bacteria. Moorella thermoacetica can thus harvest photoexcited electrons from the PFP/PDI heterojunction, driving the Wood–Ljungdahl pathway to synthesize acetic acid from CO₂ under illumination. The efficiency of this organic biohybrid is about 1.6 %, which is comparable to those of reported inorganic biohybrid systems.     

A Three-Dimensional Porous Organic Semiconductor Based on Fully sp2-Hybridized Graphitic Polymer

Dimensionality plays an important role in the charge transport properties of organic semiconductors. Although three-dimensional semiconductors, such as Si, are common in inorganic materials, imparting electrical conductivity to covalent three-dimensional organic polymers is challenging. Now, the synthesis of a three-dimensional π-conjugated porous organic polymer (3D p-POP) using catalyst-free Diels–Alder cycloaddition polymerization followed by acid-promoted aromatization is presented. With a surface area of 801 m² g⁻¹, full conjugation throughout the carbon backbone, and an electrical conductivity of 6(2)×10⁻⁴ S cm⁻¹ upon treatment with I₂ vapor, the 3D p-POP is the first member of a new class of permanently porous 3D organic semiconductors.     

Flexible electronics based on one-dimensional inorganic semiconductor nanowires and two-dimensional transition metal dichalcogenides

Flexible electronics technology is considered as a revolutionary technology to unlock the bottleneck of traditional rigid electronics that prevalent for decades, thereby fueling the next-generation electronics. In the past few decades, the research on flexible electronic devices based on organic materials has witnessed rapid development and substantial achievements, and inorganic semiconductors are also now beginning to shine in the field of flexible electronics. As validated by the latest research, some of the inorganic semiconductors, particularly those at low dimension, unexpectedly exhibited excellent mechanical flexibility on top of superior electrical properties. Herein, we bring together a comprehensive analysis on the recently burgeoning low-dimension inorganic semiconductor materials in flexible electronics, including one-dimensional (1D) inorganic semiconductor nanowires (NWs) and two-dimensional (2D) transition metal dichalcogenides (TMDs). The fundamental electrical properties, optical properties, mechanical properties and strain engineering of materials, and their performance in flexible device applications are discussed in detail. We also propose current challenges and predict future development directions including material synthesis and device fabrication and integration.     

A Three‐Dimensional Porous Organic Semiconductor Based on Fully sp2‐Hybridized Graphitic Polymer

Dimensionality plays an important role in the charge transport properties of organic semiconductors. Although three‐dimensional semiconductors, such as Si, are common in inorganic materials, imparting electrical conductivity to covalent three‐dimensional organic polymers is challenging. Now, the synthesis of a three‐dimensional π‐conjugated porous organic polymer (3D p‐POP) using catalyst‐free Diels–Alder cycloaddition polymerization followed by acid‐promoted aromatization is presented. With a surface area of 801 m² g^?1, full conjugation throughout the carbon backbone, and an electrical conductivity of 6(2)×10^?4 S cm^?1 upon treatment with I₂ vapor, the 3D p‐POP is the first member of a new class of permanently porous 3D organic semiconductors.     

Photoelectrochemical studies on aqueous suspensions of 3‐dodecyl 2–5 di‐thionyl pyrrole/metal oxide photoactive interfaces

Colloidal ZnO, Fe₂O₃ and Cu₂O solutions were used to explore photonic activities at metal oxides/organic semiconductors interfaces. Fluorescence spectroscopic and dynamic electrochemical techniques were performed on colloidal metal oxides articles modified with 3‐dodecyl 2–5 di‐thionyl pyrrole (3‐DODTh‐Py) to investigate the quantum absorbance efficiency at this inorganic/organic interface (IOI). The IOI assemblies were p‐n junction‐type interfaces, where 3‐DODTh‐Py) functions as electron donor. Results were interpreted using the optical and electrochemical parameters of the organic monomer such as IP (ionization potential), EA (electron affinity), and E_g (Energy band gap), and the barrier height at the IOI interface. One of the driving forces for great absorption at IOI was the great difference in electronegativity between inorganic and organic interface. Copyright © 2011 John Wiley & Sons, Ltd.     

Low-Dimensional Organic Tin Bromide Perovskites and Their Photoinduced Structural Transformation

Hybrid organic–inorganic metal halide perovskites possess exceptional structural tunability, with three- (3D), two- (2D), one- (1D), and zero-dimensional (0D) structures on the molecular level all possible. While remarkable progress has been realized in perovskite research in recent years, the focus has been mainly on 3D and 2D structures, with 1D and 0D structures significantly underexplored. The synthesis and characterization of a series of low-dimensional organic tin bromide perovskites with 1D and 0D structures is reported. Using the same organic and inorganic components, but at different ratios and reaction conditions, both 1D (C₄N₂H₁₄)SnBr₄ and 0D (C₄N₂H₁₄Br)₄SnBr₆ can be prepared in high yields. Moreover, photoinduced structural transformation from 1D to 0D was investigated experimentally and theoretically in which photodissociation of 1D metal halide chains followed by structural reorganization leads to the formation of a more thermodynamically stable 0D structure.     

Semiconductor/Covalent‐Organic‐Framework Z‐Scheme Heterojunctions for Artificial Photosynthesis

A strategy to covalently connect crystalline covalent organic frameworks (COFs) with semiconductors to create stable organic–inorganic Z‐scheme heterojunctions for artificial photosynthesis is presented. A series of COF–semiconductor Z‐scheme photocatalysts combining water‐oxidation semiconductors (TiO₂, Bi₂WO₆, and α‐Fe₂O₃) with CO₂ reduction COFs (COF‐316/318) was synthesized and exhibited high photocatalytic CO₂‐to‐CO conversion efficiencies (up to 69.67 μmol g^?1 h^?1), with H₂O as the electron donor in the gas–solid CO₂ reduction, without additional photosensitizers and sacrificial agents. This is the first report of covalently bonded COF/inorganic‐semiconductor systems utilizing the Z‐scheme applied for artificial photosynthesis. Experiments and calculations confirmed efficient semiconductor‐to‐COF electron transfer by covalent coupling, resulting in electron accumulation in the cyano/pyridine moieties of the COF for CO₂ reduction and holes in the semiconductor for H₂O oxidation, thus mimicking natural photosynthesis.     

Ultralow-loss Optical Waveguides through Balancing Deep-Blue TADF and Orange Room Temperature Phosphorescence in Hybrid Antimony Halide Microstructures

Harnessing the potential of thermally activated delayed fluorescence (TADF) and room temperature phosphorescence (RTP) is crucial for developing light-emitting diodes (LEDs), lasers, sensors, and many others. However, effective strategies in this domain are still relatively scarce. This study presents a new approach to achieving highly efficient deep-blue TADF (with a PLQY of 25 %) and low-energy orange RTP (with a PLQY of 90 %) through the fabrication of lead-free hybrid halides. This new class of monomeric and dimeric 0D antimony halides can be facilely synthesized using a bottom-up solution process, requiring only a few seconds to minutes, which offer exceptional stability and nontoxicity. By leveraging the highly adaptable molecular arrangement and crystal packing modes, the hybrid antimony halides demonstrate the ability to self-assemble into regular 1D microrod and 2D microplate morphologies. This self-assembly is facilitated by multiple non-covalent interactions between the inorganic cores and organic shells. Notably, these microstructures exhibit outstanding polarized luminescence and function as low-dimensional optical waveguides with remarkably low optical-loss coefficients. Therefore, this work not only presents a pioneering demonstration of deep-blue TADF in hybrid antimony halides, but also introduces 1D and 2D micro/nanostructures that hold promising potential for applications in white LEDs and low-dimensional photonic systems.     

Self-assembly of C60, SWNTs and few-layer graphene and their binary composites at the organic-aqueous interface

Self-assembly of C(60), single-walled carbon nanotubes (SWNTs) and few-layer graphene at the toluene-water interface has been investigated, starting with different concentrations of the nanocarbons in the organic phase and carrying out the assembly to different extents. Morphologies and structures of the films formed at the interface have been investigated by electron microscopy and other techniques. In the case of C(60), the films exhibit hcp and fcc structures depending on the starting concentration in the organic phase, the films being single crystalline under certain conditions. Self-assembly of the composites formed by pairs of nanocarbons (C(60)-SWNT, C(60)-few-layer graphene and SWNT-few-layer graphene) at the interface has been studied by electron microscopy. Raman spectroscopy and electronic absorption spectroscopy of the films formed at the interface have revealed the occurrence of charge-transfer interaction between SWNTs and C(60) as well as between few-layer graphene and C(60).     

Electrochemical growth of highly oriented organic-inorganic superlattices using solid-supported multilamellar membranes as templates

Controllable depositing of relatively thick inorganic sublayers into organic templates to fabricate organic-inorganic superlattices is of great importance. We report a novel approach to fabricating phospholipid/Ni(OH)(2) superlattices by electrochemical deposition of the inorganic component into solid-supported multilamellar templates. The well-ordered and highly oriented multilamellar templates are produced by spreading small drops of lipid solution on silicon surfaces and letting the solvent evaporate slowly. The templates which are used as working electrodes preserve the lamellar structure in the electrolyte solution. The resulting superlattices are highly oriented. The thickness of the nickel hydroxide is controlled by the concentration of nickel ions in the electrolyte bath. The electron density profiles derived from the X-ray diffraction data reveal that the thickness of the nickel hydroxide sublayers increases from 15 to 27 A as the concentration of nickel nitrate increases from 0.005 mol/L to 0.08 mol/L. We expect that the new method can be extended to depositing a variety of inorganic components including metals, oxides, and semiconductors.     

Interpretation of electron diffusion coefficient in organic and inorganic semiconductors with broad distributions of states

The carrier transport properties in nanocrystalline semiconductors and organic materials play a key role for modern organic/inorganic devices such as dye-sensitized (DSC) and organic solar cells, organic and hybrid light-emitting diodes (OLEDs), organic field-effect transistors, and electrochemical sensors and displays. Carrier transport in these materials usually occurs by transitions in a broad distribution of localized states. As a result the transport is dominated by thermal activation to a band of extended states (multiple trapping), or if these do not exist, by hopping via localized states. We provide a general view of the physical interpretation of the variations of carrier transport coefficients (diffusion coefficient and mobility) with respect to the carrier concentration, or Fermi level, examining in detail models for carrier transport in nanocrystalline semiconductors and organic materials with the following distributions: single and two-level systems, exponential and Gaussian density of states. We treat both the multiple trapping models and the hopping model in the transport energy approximation. The analysis is simplified by thermodynamic properties: the chemical capacitance, C(mu), and the thermodynamic factor, chi(n), that allow us to derive many properties of the chemical diffusion coefficient, D(n), used in Fick's law. The formulation of the generalized Einstein relation for the mobility to diffusion ratio shows that the carrier mobility is proportional to the jump diffusion coefficient, D(J), that is derived from single particle random walk. Characteristic experimental data for nanocrystalline TiO(2) in DSC and electrochemically doped conducting polymers are discussed in the light of these models.     

All-in-one: a new approach toward robust and solution-processable copper halide hybrid semiconductors by integrating covalent,coordinate and ionic bonds in their structures

Conventional inorganic semiconductors are best known for their superior physical properties and chemical robustness, and their widespread use in optoelectronic devices. However, implementation of these materials in many other applications has been hindered by their poor solubility and/or solution-processability, a longstanding drawback that is largely responsible for issues such as high cost. While recent progress on hybrid perovskites, an important class of inorganic–organic hybrid materials, has shed light on the development of high-performance solution processable semiconductors, they rely heavily on toxic metals and generally suffer from framework instability. To address these issues, a new group of hybrid semiconductors based on anionic copper(i) halide and cationic organic ligands has been developed. These compounds are noted as All-In-One (AIO) structures as they consist of covalently bonded anionic CuX inorganic modules that form both coordinate and ionic bonds with cationic organic ligands. Studies demonstrate that framework stability and solution processibility of these materials are greatly enhanced as a result of such bonds. In the perspective, we highlight the development of this newly emerged type of materials including their crystal structures, chemical and physical properties and possible applications. The untapped potential that the AIO approach can offer for other hybrid families is also discussed.

This Perspective features the newly emerged AIO-type Cu(i)X-based hybrid semiconductors and showcases their structural diversity, solution-processability, framework stability, important photophysical properties and related potential applications.     

Solution-deposited organic-inorganic hybrid multilayer gate dielectrics. Design, synthesis, microstructures, and electrical properties with thin-film transistors

We report here on the rational synthesis, processing, and dielectric properties of novel layer-by-layer organic/inorganic hybrid multilayer dielectric films enabled by polarizable π-electron phosphonic acid building blocks and ultrathin ZrO(2) layers. These new zirconia-based self-assembled nanodielectric (Zr-SAND) films (5-12 nm thick) are readily fabricated via solution processes under ambient atmosphere. Attractive Zr-SAND properties include amenability to accurate control of film thickness, large-area uniformity, well-defined nanostructure, exceptionally large electrical capacitance (up to 750 nF/cm(2)), excellent insulating properties (leakage current densities as low as 10(-7) A/cm(2)), and excellent thermal stability. Thin-film transistors (TFTs) fabricated with pentacene and PDIF-CN(2) as representative organic semiconductors and zinc-tin-oxide (Zn-Sn-O) as a representative inorganic semiconductor function well at low voltages (<±4.0 V). Furthermore, the TFT performance parameters of representative organic semiconductors deposited on Zr-SAND films, functionalized on the surface with various alkylphosphonic acid self-assembled monolayers, are investigated and shown to correlate closely with the alkylphosphonic acid chain dimensions.     

Continuum of outer- and inner-sphere mechanisms for organic electron transfer. Steric modulation of the precursor complex in paramagnetic (ion-radical) self-exchanges

Transient 1:1 precursor complexes for intermolecular self-exchange between various organic electron donors (D) and their paramagnetic cation radicals (D+*), as well as between different electron acceptors (A) paired with their anion radicals (A-*), are spectrally (UV-NIR) observed and structurally (X-ray) identified as the cofacial (pi-stacked) associates [D, D+*] and [A-*, A], respectively. Mulliken-Hush (two-state) analysis of their diagnostic intervalence bands affords the electronic coupling elements (HDA), which together with the Marcus reorganization energies (lambda) from the NIR spectral data are confirmed by molecular-orbital computations. The HDA values are found to be a sensitive function of the bulky substituents surrounding the redox centers. As a result, the steric modulation of the donor/acceptor separation (rDA) leads to distinctive electron-transfer rates between sterically hindered donors/acceptors and their more open (unsubstituted) parents. The latter is discussed in the context of a continuous series of outer- and inner-sphere mechanisms for organic electron-transfer processes in a manner originally formulated by Taube and co-workers for inorganic (coordination) donor/acceptor dyads-with conciliatory attention paid to traditional organic versus inorganic concepts.     

Semiconductor/Covalent-Organic-Framework Z-Scheme Heterojunctions for Artificial Photosynthesis

A strategy to covalently connect crystalline covalent organic frameworks (COFs) with semiconductors to create stable organic–inorganic Z-scheme heterojunctions for artificial photosynthesis is presented. A series of COF–semiconductor Z-scheme photocatalysts combining water-oxidation semiconductors (TiO₂, Bi₂WO₆, and α-Fe₂O₃) with CO₂ reduction COFs (COF-316/318) was synthesized and exhibited high photocatalytic CO₂-to-CO conversion efficiencies (up to 69.67 μmol g⁻¹ h⁻¹), with H₂O as the electron donor in the gas–solid CO₂ reduction, without additional photosensitizers and sacrificial agents. This is the first report of covalently bonded COF/inorganic-semiconductor systems utilizing the Z-scheme applied for artificial photosynthesis. Experiments and calculations confirmed efficient semiconductor-to-COF electron transfer by covalent coupling, resulting in electron accumulation in the cyano/pyridine moieties of the COF for CO₂ reduction and holes in the semiconductor for H₂O oxidation, thus mimicking natural photosynthesis.     

A two‐dimensional organic–inorganic hybrid perovskite‐type semiconductor: poly[(2‐azaniumylethyl)trimethylphosphanium [tetra‐μ‐bromido‐plumbate(II)]]

Recently, with the prevalence of `perovskite fever', organic–inorganic hybrid perovskites (OHPs) have attracted intense attention due to their remarkable structural variability and highly tunable properties. In particular, the optical and electrical properties of organic–inorganic hybrid lead halides are typical of the OHP family. Besides, although three‐dimensional hybrid perovskites, such as [CH₃NH₃]PbX₃ (X = Cl, Br or I), have been reported, the development of new organic–inorganic hybrid semiconductors is still an area in urgent need of exploration. Here, an organic–inorganic hybrid lead halide perovskite is reported, namely poly[(2‐azaniumylethyl)trimethylphosphanium [tetra‐μ‐bromido‐plumbate(II)]], {(C₅H₁₆NP)[PbBr₄]}_n, in which an organic cation is embedded in inorganic two‐dimensional (2D) mesh layers to produce a sandwich structure. This unique sandwich 2D hybrid perovskite material shows an indirect band gap of ～2.700 eV. The properties of this compound as a semiconductor are demonstrated by a series of optical characterizations and indicate potential applications for optical devices.     

Conductance Switch of a Bromoplumbate Bistable Semiconductor by Electron‐Transfer Thermochromism

Electron‐transfer (redox) thermochromism was successfully used for switching the conductance of semiconductors, by introducing a thermally active organic component into an inorganic semiconducting framework. A moisture‐resistant semiconductor {(MV)₂[Pb₇Br₁₈]}_n (MV²⁺=methyl viologen cation) has been prepared through an in situ synthetic method for MV²⁺. It features a rare 3D haloplumbate open framework and unprecedented electron‐transfer thermochromic behavior in haloplumbates. The electrical conductivity of this compound dropped significantly after coloration and restored after decoloration, which was satisfactorily explained by valence band XPS and theoretical data. This work not only offers a new approach to modify electrical properties of semiconductors without altering components or structures, but may lead to the development of over‐temperature color indicators, circuit overload protectors or photovoltaic materials.     

Engineering of CH3NH3PbI3 Perovskite Crystals by Alloying Large Organic Cations for Enhanced Thermal Stability and Transport Properties

The number of studies on organic–inorganic hybrid perovskites has soared in recent years. However, the majority of hybrid perovskites under investigation are based on a limited number of organic cations of suitable sizes, such as methylammonium and formamidinium. These small cations easily fit into the perovskite's three‐dimensional (3D) lead halide framework to produce semiconductors with excellent charge transport properties. Until now, larger cations, such as ethylammonium, have been found to form 2D crystals with lead halide. Here we show for the first time that ethylammonium can in fact be incorporated coordinately with methylammonium in the lattice of a 3D perovskite thanks to a balance of opposite lattice distortion strains. This inclusion results in higher crystal symmetry, improved material stability, and markedly enhanced charge carrier lifetime. This crystal engineering strategy of balancing opposite lattice distortion effects vastly increases the number of potential choices of organic cations for 3D perovskites, opening up new degrees of freedom to tailor their optoelectronic and environmental properties.