Organic Single Crystals Research Articles

Synthesis, Structure, and Non‐Linear Optical Properties of New Metal Semi‐Organic Complex: 1,4‐diazabicyclo[2.2.2]octane‐1,4‐diium tris(nitrato)‐silver

AbstractOptically transparent metal semi organic single crystal of 1,4‐diazabicyclo[2.2.2]octane‐1,4‐diium tris(nitrato)‐silver (DTNS) is synthesized using slow evaporation solution technique. This single crystal is grown with dimension up to using 1,4‐diazabicyclo[2.2.2]octane (DABCO) as solute and water and methanol as solvent in the presence metal salt silver nitrate. Single crystal X‐ray diffraction (XRD) study showed a trigonal structure with space group P3c1 and the sum formula . The composition of metal Silver (Ag) in single crystal is confirmed through Energy Dispersive X‐Ray Analysis. The confirmation of various functional groups in DTNS molecular structure is characterized by Fourier Transform Infrared Spectroscopy (FT‐IR). UV–Visible absorption study showed the cut‐off wavelength at 250 nm with transparency 350–700 nm and the bandgap is about 3.3 eV. The thermal stability and melting point temperature is analyzed by Thermogravimetry‐Differential Scanning Calorimetry (TG/DSC). The third order Non Linear Optics (NLO) efficiency of the synthesized crystal is times greater than that of KDP. All of these analysis implies that DTNS crystal can be beneficial element for non‐linear optical applications.

Experimental and theoretical studies of a new NLO active organic salt of 2-amino-4-hydroxy-6-methylpyrimidine and 4-hydroxybenzoic acid

The new monohydrate organic salt (AHMPHB) of 2-amino-4-hydroxy-6-methylpyrimidine (AHMP) with 4-hydroxybenzoic acid (HBA) was successfully synthesized and grown as an organic single crystal with characteristic optical quality using the slow evaporation technique (SET). The structural study of the grown crystal was performed using single-crystal XRD. The XRD results revealed that AHMPHB belongs to the triclinic system with space group P-1. Various functional groups of AHMPHB were identified using Raman and FTIR spectroscopic analyses. The optimized geometry and other theoretical results were determined by the DFT/B3LYP method at the 6-311++G(d,p) basis set. The H⋅⋅⋅H and O⋅⋅⋅H intermolecular forces are dominated in the crystal packing and these were explored using Hirshfeld surface and fingerprint plot analyses. TG and DTA studies demonstrate that AHMPHB remains stable up to 140 ºC. According to UV-Vis spectral analysis, AHMPHB has exhibited high transparency in the visible region with a direct band gap of 4.10 eV. The NLO measurement of AHMPHB was done using the Z-scan method. The energy of the HOMO-LUMO gap of 4.37 eV was predicted using DFT calculations. NBO analysis was performed to represent the charge transfer between localized bonds and lone pairs. Moreover, the MEP maps, HOMO-LUMO profiles and theoretical NLO parameters of AHMPHB and its constituents are also obtained.

Growth of L-asparagine monohydrate organic single crystals: An experimental and DFT computational approach for nonlinear optical applications

Good optical quality of L-asparagine monohydrate (C4H8N2O3.H2O) organic single crystal has been grown by adopting natural slow evaporation process at room temperature from aqueous solutions. The lattice parameters obtained by powder X-ray diffraction data revealed orthorhombic crystal system of the harvested crystal. The morphology and planes of the crystal have been identified. The molecular vibrations and functional groups have been specified by Fourier transform infrared (FTIR) spectroscopy studies. Energy dispersive X-ray (EDX) study has been availed to find out the elements constituting the crystal. Scanning electron microscopy, (SEM), provided the surface morphology of the crystal. The dependence of dielectric properties on frequency and temperature have been investigated and the electronic polarizability (α) has been determined. UV–vis spectral analysis shows that the crystal possesses good optical transmittance in the visible part of the energy spectrum. The optical band gap and the Urbach energy have been determined from lower absorption edge. Third order nonlinear susceptibility χ(3), nonlinear refractive index (n2), and linear susceptibility χ(1) have been calculated by Miller's generalized rule. The first-principle computation of band structure of electrons and the electron density of states have been discussed, which suggest that the crystals possess direct band gap. Density Functional Theory (DFT) with B3LYP function by Gaussian09W software was utilized to calculate HOMO-LUMO energy gap as well as non-linear optical parameters namely, linear polarizability (α), hyperpolarizability (β and γ) and dipole moment (μ) of L-asparagine monohydrate crystal. All the findings prove that L-asparagine monohydrate is a promising NLO crystal.

An experimental insight into a promising novel organic nonlinear optical single crystal Guanidinium 2,4-dichlorobenzoate (G24DCB)

Guanidinium 2,4-dichlorobenzoate (G24DCB), a new chloro substituted benzoic acid based organic single crystal is synthesized, grown and added to the guanidinium family of single crystals. Such G24DCB crystal was obtained by a versatile slow evaporation solution growth technique. The analysis of single crystal X-ray diffraction examined the phase identification and determination of lattice parameters for the synthesized compound. The G24DCB crystal has monoclinic system and adopts space group P21/c. Powder X-ray diffraction explores the studied crystal's crystalline characteristics. The study of Fourier Transform-Infrared (FTIR) spectroscopy examined the necessary vibrational assignments for the formation of the structure of G24DCB. The UV–Visible-NIR analysis entails the determination of the cut-off wavelength of the G24DCB compound from its transmittance spectrum and the computation of other related optical parameter values. Photoluminescence analysis was employed to investigate the studied crystal's emission characteristics. The thermal stability of the G24DCB crystal was examined through thermogravimetric analysis and differential thermal analysis. The laser-induced damage threshold of the crystal was determined using a Nd:YAG laser. The various mechanical attributes exhibited by the synthesized compound were elucidated by microhardness studies and it corresponds to a soft material type. The various third order nonlinear optical characteristics were probed by Z scan study. The positive results of the aforementioned studies suggest the emerging significance possessed by the novel title crystal Guanidinium 2,4-dichlorobenzoate in nonlinear optical applications.

Flexible Organic Molecular Single Crystal-Based Triboelectric Device as a Self-Powered Tactile Sensor.

Triboelectric nanogenerators (TENGs) have proven to be effective at converting mechanical energy into electrical power, making them a viable technology for operating self-powered electronic devices used in medical diagnostics and environmental monitoring. In the present study, we demonstrate the utility of the flexible single crystals of an organic compound for the fabrication of a TENG as a self-powered tactile sensor. Triboelectrification was attained in single crystals as a result of surface functionalization with positively and negatively charged moieties, viz. Zn2+ and F-, respectively, which resulted in a variable surface potential and reversible adhesion through electrostatic interaction and induction phenomena. TENG incorporating the single crystals showed an output voltage of 2.4 V, a current density of ∼2.2 μA/m2, and a power density of ∼850 mW/m2 and was capable of charging commercial capacitors thereby ensuring its ability to be used as a self-powered touch sensor. Capitalizing on these features, a self-powered tactile sensor was fabricated to demonstrate limb movements. The excellent mechano-electric sensitivity (∼102 mV/kPa until 6 kPa range) and response time (∼38 ms) establish the viability of flexible organic single crystals for mechanical energy harvesting and biosensing applications that could pave the way for their utilization as biomedical wearable devices.

Liquid–liquid interface‐assisted growth of two‐dimensional organic semiconductor single crystals: Mechanisms, properties, and applications

AbstractTwo‐dimensional organic semiconductor single crystals (2D OSSCs) represent the promising candidates for the construction of high‐performance electronic and optoelectronic devices due to their ultrathin thicknesses, free of grain boundaries, and long‐range ordered molecular structures. In recent years, substantial efforts have been devoted to the fabrication of the large‐sized and layer‐controlled 2D OSSCs at the liquid‐liquid interface. This unique interface could act as the molecular flat and defect‐free substrate for regulating the nucleation and growth processes and enabling the formation of large‐sized ultrathin 2D OSSCs. Therefore, this review focuses on the liquid–liquid interface‐assisted growth methods for the controllable preparation of 2D OSSCs, with a particular emphasis on the advantages and limitations of the corresponding methods. Furthermore, the typical methods employed to control the crystal sizes, morphologies, structures, and orientations of 2D OSSCs at the liquid–liquid interface are discussed in detail. Then, the recent progresses on the 2D OSSCs‐based optoelectronic devices, such as organic field‐effect transistors, ambipolar transistors, and phototransistors are highlighted. Finally, the key challenges and further outlook are proposed in order to promote the future development of the 2D OSSCs in the field of the next‐generation organic optoelectronic devices.

Organic polaritonic light-emitting diodes with high luminance and color purity toward laser displays

Achieving high-luminescence organic light-emitting devices (OLEDs) with narrowband emission and high color purity is important in various optoelectronic fields. Laser displays exhibit outstanding advantages in next-generation display technologies owing to their ultimate visual experience, but this remains a great challenge. Here, we develop a novel OLED based organic single crystals. By strongly coupling the organic exciton state to an optical microcavity, we obtain polariton electroluminescent (EL) emission from the polariton OLEDs (OPLEDs) with high luminance, narrow-band emission, high color purity, high polarization as well as excellent optically pumped polariton laser. Further, we evaluate the potential for electrically pumped polariton laser through theoretical analysis and provide possible solutions. This work provides a powerful strategy with a material–device combination that paves the way for electrically driven organic single-crystal-based polariton luminescent devices and possibly lasers.

Exploring the impact of solvent on growth, morphology and photoluminescence properties of organic electro-optic OH1 single crystal

Exploring the impact of solvent on growth, morphology and photoluminescence properties of organic electro-optic OH1 single crystal

Evaluation of the optical, photoluminescence, and thermal characteristics of Barium thiourea chloride (BTCL), a metal–organic crystal for photonic applications

The development of crystal fabrication and characterization approaches makes it possible to study novel materials with enhanced linear and nonlinear optical properties. The solution growth method was adopted in the present investigation to create Barium thiourea chloride (BTCL), a metal–organic single crystal. Structural, optical, and thermal characteristics of the BTCL crystals were evaluated by XRD analysis, Fourier transform infrared spectroscopy, UV–Vis spectrometry, photoluminescence, SHG, and thermal analyses. The XRD method was applied to investigate the structural characteristics of the BTCL, which is related to the monoclinic structure. The FT-IR spectral investigation was conducted to observe the vibrational modes in BTCL. The optical measurements showed the transmittance in the near-UV and visible spectrums. Optical characteristics include bandgap, refractive index, extinction coefficient, optical, and electrical conductivities, and dielectric constants were obtained. The PL curve showed two notable emission peaks at 482.5[Formula: see text]nm and 491[Formula: see text]nm. The ability to generate second harmonics was investigated using the Kurtz and Perry method, and the SHG was more than 1.79 times the KDP sample. The thermal behavior of the BTCL was evaluated by TGA/DTA measurements. The Coats–Redfern relation was used to estimate the activation energy of the thermal system and the value was determined to be 9.48[Formula: see text]KJ/mol. The findings indicate that the BTCL crystals possess excellent optical transparency, higher SHG potency, and good thermal stability, which are suitable for use in photonic structures.

Tension Induced Photoluminescence Enhancement in an Organic Single Crystal.

Organic single crystals possess distinct advantages due to their highly ordered molecular structures, resulting in improved stability, enhanced carrier mobility, and superior optical characteristics. However, their mechanical rigidity and brittleness impede the applications in flexible and wearable optoelectronic devices. Here, photoluminescence (PL) emission from 2,6-diphenylanthracene (DPA) single crystals is studied under tensile strain, which shows PL enhancement by more than two times with a strain of ≈1.42%. Such a tension induced PL enhancement is reversible, exhibiting no clear optical degradations during 100 cycles of bending and recovery processes. Theoretical calculations reveal that the deformation of molecular structure under strain induces a decrease of the dihedral between anthracene and benzene moieties in DPA molecules. Further, the increased molecular conjugation enhances the molecular oscillator strength, leading to the brightened PL emission. Meanwhile, with the decreased dihedral, the molecular vibrations in DPA crystals are suppressed, which can reduce the non-radiative decay rate. In contrast, no tension induced PL enhancement is observed in polycrystalline DPA thin films as the strain can be released via the grain boundaries. This study highlights the superior optical performance of DPA single crystals under strain field, which will provide new possibilities for DPA-based flexible devices.

Organic-Inorganic Rubrene/WS2 Heterostructure for Broadband Detection and Polarization Imaging.

Organic single crystals exhibit improved carrier mobility, longer exciton diffusion length, anisotropic charge transport, and unique linear dichroism, while its high exciton binding energy seriously limits the free-carrier generation and photoelectric conversion efficiency. Layered van der Waals heterostructures, which integrate organic crystals with high mobility two-dimensional (2D) inorganic semiconductors, are promising for promoting exciton dissociation and boosting sensitivity by utilizing the interfacial potential and photogating effect. In this work, organic single-crystal rubrene is integrated with a few-layer WS2 to design the high-performance photodetector. The device exhibits an excellent responsivity of 1000 A W-1, and a fast speed of 180 μs, which is far superior to the individual WS2 device. Equally importantly, this device provides excellent polarization detection performance by virtue of the anisotropic properties of rubrene, and the dichroic ratios are 1.56, 1.5, and 1.7 for 375, 405, and 658 nm irradiation, respectively. Finally, several high-resolution single-pixel broadband polarization imaging was demonstrated. Our work shows that organic-inorganic heterostructure is an essential candidate for improving optoelectronics performance and has potential for polarization imaging.

Vacuum deposition of χ(2) nonlinear organic single crystal films on silicon

Integrating second order nonlinear (χ(2)) optical materials on chip is an ongoing challenge for Si photonics. Noncentrosymmetric molecular crystals have the potential to deliver high χ(2) nonlinearity with good thermal stability, but so far have been limited to growth from solution or the melt, which are both difficult to control and scale up in manufacturing. Here, we show that large (>100 μm) single crystal domains of the nonlinear molecule 2-[3-(4-hydroxystyryl)-5,5-dimethylcyclohex-2-enylidene] malononitrile (OH1) can be grown monolithically on either glass or Si via vacuum evaporation, followed by a short thermal annealing step. The crystallites are tens of nanometer thick and exhibit strong second harmonic generation with their primary χ(2) tensor component lying predominantly in plane. Remarkably, we find that a single domain can grow uninterrupted through nearby channels etched on a Si wafer, which may provide a path to integrate OH1 on Si or Si3N4 waveguides for a broad range of χ(2)-based photonic integrated circuit functionality.

Growth and characterization of organic 4-chloroaniline single crystals for nonlinear optical applications

Growth and characterization of organic 4-chloroaniline single crystals for nonlinear optical applications

Organic cocrystals: From high‐performance molecular materials to multi‐functional applications

AbstractAdvancements in organic electronics are propelling the development of new material systems, where organic materials stand out for their unique benefits, including tunability and cost‐effectiveness. Organic single crystals stand out for their ordered structure and reduced defects, enhancing the understanding of the relationship between structure and performance. Organic cocrystal engineering builds upon these foundations, exploring intermolecular interactions within multicomponent‐ordered crystalline materials to combine the inherent advantages of single‐component crystals. However, the path to realizing the full potential of organic cocrystals is fraught with challenges, including structural mismatches, unclear cocrystallization mechanisms, and unpredictable property alterations, which complicate the effective cocrystallization between different molecules. To deepen the understanding of this promising area, this review introduces the mechanism of organic cocrystal formation, the various stacking modes, and different growth techniques, and highlights the advancements in cocrystal engineering for multifunctional applications. The goal is to provide comprehensive guidelines for the cocrystal engineering of high‐performance molecular materials, thereby expanding the applications of organic cocrystals in the fields of optoelectronics, photothermal energy, and energy storage and conversion.

Fast growth of large-sized organic single crystals via spin coating

Spin-coating stands out as one of the fastest and simplest processes for material solidification. While it is commonly employed for producing polycrystalline thin films, recent endeavors have explored its potential for epitaxial growth, albeit primarily limited to inorganic materials. In this study, we demonstrate the spin-coating method enabling the rapid growth of large-sized organic single crystals (OSCs). Within 2 h, we successfully obtained OSCs with controlled lateral sizes of up to 2 mm, which conventionally takes several weeks using slow solvent evaporation. Raman mapping and UV–Vis absorption measurements confirmed the growths of the OSCs. We propose the growth mechanism by using the supersaturated dynamic fluid model. Furthermore, we demonstrate the device integration of these OSCs for charge-transfer complex channel, revealing ambipolar behavior during gate sweep. This innovative OSCs production method has the potential to advance the various field of science and electronics, traditionally hindered by the scarcity of adequately sized OSCs.

Highly-Polarized Solar-Blind Ultraviolet Organic Photodetectors.

Developing high-performance polarization-sensitive ultraviolet photodetectors is crucial for their application in military remote sensing, detection, bio-inspired navigation, and machine vision. However, the significant absorption in the visible light range severely limits the application of polarization-sensitive ultraviolet photodetectors, such as high-quality anti-interference imaging. Here, based on a wide-bandgap organic semiconductor single crystal (trans-1,2-bis(5-phenyldithieno[2,3-b:3',2'-d]thiophen-2-yl)ethene, BPTTE), high-performance polarization-sensitive solar-blind ultraviolet photodetectors with a dichroic ratio close to 4.26 are demonstrated. The strong anisotropy of 2D grown BPTTE single crystals in molecular vibration and optical absorption is characterized by various techniques. Under voltage modulation, stable and efficient detection of polarized light is demonstrated, attributed to the intrinsic anisotropy of transition dipole moment in the bc crystal plane, rather than other factors. Finally, high-contrast polarimetric imaging and anti-interference imaging are successfully demonstrated based on BPTTE single crystal photodetectors, highlighting the potential of organic semiconductors for polarization-sensitive solar-blind ultraviolet photodetectors.

Growth and characterization of organic p-nitroacetophenone single crystals for nonlinear optical applications

Growth and characterization of organic p-nitroacetophenone single crystals for nonlinear optical applications

Impact of doping on the Bridgman grown organic stilbene single crystal for third order NLO applications

Transparent 1, 3, 5-Triphenylbenzene doped Stilbene (TBS) single crystal was successfully grown by employing the Bridgman technique. SCXRD studies found crystallographic parameters, which reveal that the TBS single crystal has crystallized in a monoclinic crystal structure with the space group of P21/C. The identification of the functional groups in the TBS crystal was accomplished through the FTIR analysis. The UV–Vis spectral data shows that the TBS crystal exhibits minimal absorption across the visible spectrum, with a lower cutoff wavelength of 365 nm. The violet emission is observed at 380 and 405 nm in the fluorescence analysis. Additionally, the crystal's high quality was confirmed by a full width at half maximum value of 123 arcsec in the prominent rocking curve peak. Third-order nonlinear optical susceptibility χ(3) was determined to be 4.26 × 10−6 esu using the Z-scan technique. These are exciting findings that highlight the TBS crystal's suitability for various applications, including scintillation and optoelectronic device fabrication.

Tuning Electrode Work Function and Surface Energy for Solution Shearing High-Performance Organic Field-Effect Transistors.

A bottom-contact organic field-effect transistor (OFET) is easily adaptable to the standard lithography process because the contact electrodes are deposited before the organic semiconductor (OSC). However, the low surface energy of bare electrodes limits utilizing solution-processed single-crystal OSCs. Additionally, the bare electrode usually leads to a significant charge injection barrier, owing to its relatively low work function (WF). Here, we simultaneously improved the surface energy and WF of gold electrodes by conducting oxygen plasma treatment to achieve high-performance OFET based on solution-processed organic single crystals. We cultivated a thin layer of gold oxide on Au electrodes to increase the WF by ∼0.7 eV. The surface energy of Au electrodes was enhanced to the same as AlOx dielectric surface, enabling the seamless growth of large-area C8-BTBT (2,7-dioctyl[1]benzothieno[3,2-b][1]benzothiophene) organic single-crystal thin films via solution shearing. This technique facilitates the production of high-performance OFETs with the highest carrier mobility of 6.7 cm2 V-1 s-1 and sharp switching characterized by a subthreshold swing of 63.6 mV dec-1. The bottom-contact OFETs exhibited a lower contact resistance of 1.19 kΩ cm than its F4-TCNQ-doped top-contact control device. This method offers a straightforward and effective strategy for producing high-quality single-crystal OFETs, which are potentially suitable for commercial applications.

2D organic-inorganic lead perovskite: Advancing X-ray detection capability

Two-dimensional (2D) perovskite single crystals have risen to be prominent in the domain of optoelectronic materials due to their exceptional characteristics including notably low ion migration and defect density. A distinguishing feature is the strategic inclusion of larger organic amine spacer, alternately inserted between inorganic lead halide octahedral layers. This spacer effectively mitigates ion migration, even under higher bias voltages, which is particularly advantageous for X-ray detection. However, the simultaneous realization of multiple functions within this realm remains a formidable challenge. In this work, we have synthesized a high-quality organic spacer-incorporated single layered 2D perovskite single crystal of [CYP]PbBr4 (CYP = 1-cyclohexylpiperazine). Our findings reveal the impressive potential of [CYP]PbBr4 in the domain of X-ray detection, as evidenced by the ultrahigh X-ray sensitivity, long-term stability, and astonishingly low detection limit of 1.72 nGyairs-1. Notably, [CYP]PbBr4 also emits bright broadband yellow light with quantum yield of 30.3%, and the fabricated white LED achieves a high Color Rendering Index of 94.1, which surpasses that of commercially available white LED based on YAG: Ce3+ (< 80).