Metal Organic Framework Thin Films Research Articles

Influence of Humidity on Layer-by-Layer Growth and Structure in Coordination Networks.

Metal-organic frameworks (MOFs) are promising materials because of their high designability of pores and functionalities. Especially, MOF thin films and their properties have been investigated toward applications in nanodevices. Typically, MOF thin films are fabricated by using a bottom-up method such as layer-by-layer (LbL) growth in air. Because the water molecules can coordinate and be replaced with organic linkers during synthesis, humidity conditions will be expected to influence the LbL growth processes. In this study, we fabricated MOF thin films composed of Zn2+, tetrakis-(4-carboxyphenyl)-porphyrin (TCPP), and 4,4'-bipyridyl (bpy) at 10 and 40% relative humidity (RH) conditions. Then, we investigated the humidity effects on chemical compositions of TCPP and bpy, periodic structure, orientation, and surface morphology. At high RH, coordination replacement of water with the organic linkers becomes more competitive than that at low RH, resulting in a different TCPP/bpy composition ratio between the two RH conditions. Also, more frequent coordination replacements of water with the organic linkers at high RH led to the formation of phases other than that observed at low RH, loss of growth orientation, and rough surface. The findings clarified the importance of controlling the RH condition during LbL growth to obtain the desired coordination networks.

Layer-by-layer growth of Cu3(HHTP)2 films on Cu(OH)2 nanowire arrays for high performance ascorbic acid sensing

Growing three-dimensional (3D) metal organic frameworks (MOFs) via heterogeneous epitaxial growth on metal hydroxide arrays are effective for constructing electrochemical sensor. However, the growth of MOFs is difficult to control, resulting in thick and irregular morphologies and even damage the metal hydroxide template. In this work, Cu3(HHTP)2 (HHTP = 2, 3, 6, 7, 10, 11-hexahydroxytriphenylene) films with controllable thickness and morphology were successfully prepared on Cu(OH)2 nanowire arrays (NWAs) through layer-by-layer (LBL) growth method. We have discovered that the LBL cycle and the reaction solvent composition are crucial for growing homogenous MOF thin films. The Cu3(HHTP)2 based ascorbic acid (AA) sensor, fabricated in ethanol within 10 LBL cycles, generated an ultrahigh sensitivity of 821.64 μA mM−1 cm−2 in the range of 6–981.41 μM, a low detection limit of 60 nM as well as the great selectivity, stability and reproducibility. Moreover, the relative deviation for AA detection in two fruit juices were 3.22 % and 3.71 %, and the test result for human sweat fall within the normal AA concentration range, verifying the feasibility of as-prepared sensor for practical application.

Development of Anti-TNT@Cu-BTC MOF thin film using drop caste method for trinitrotoluene (TNT) sensing

Antibody functionalised Cu-BTC MOF thin film was prepared using drop-casting method on indium tin oxide (ITO) coated glass substrate for trinitrotoluene (TNT) sensing under certain experimental conditions. Initially, APTES functionalization on ITO substrate using EDC-NHS chemistry was carried out, after which biofunctionalization of Anti-TNT on Cu-BTC MOF (1,3,5-tricarboxylic acid as an organic linker and copper ions as metal) thin film was carried out. Each step of sensor fabrication was characterised by the X-ray diffraction, microscopic and spectroscopic techniques. The interaction of one layer with another is confirmed with the help of FTIR and EDX. ITO substrate modification increases resistance at each stage from 1.29 to 3.3 KΩ. This modified substrate used as a working electrode during the sensing experiment. Afterward, response cum detection of 2,4,6-trinitrotoluene (TNT) in the 0.1 ppm to 0.6 ppm range has been noted by impedance method using three electrode systems of an electrochemical workstation. Host-guest interaction cum mechanism between TNT antibody functionalised APTES@Cu-BTC and TNT analyte has been observed which origins change in their resistance/impedance. The variation in resistance is directly proportional to the concentrations, exhibiting a strong linear relationship with 0.9702 value for R2. We find out that the presence of TNT antibody increases the specificity of TNT sensing and minimizes cross-reactivity with unknown/other interfering compounds. The concentration–response graph shows a 0.04 ppm limit of detection at room temperature.

Layer by Layer Spraying Fabrication of Aggregation-Induced Emission Metal-Organic Frameworks Thin Film.

The development of new metal-organic frameworks (MOFs) thin films is important for expanding their functions and applications. Herein, we first report a new kind of MOF thin film by using aggregation-induced emission (AIE) dicarboxyl ligand through a liquid-phase epitaxial (LPE) layer-by-layer (LBL) spraying method (named AIE surface-coordinated metal-organic frameworks thin film, AIE-SURMOF). The obtained AIE-SURMOF Zn4O(TPE)3 (ZnTPE) has highly growth orientation and homogeneous thin film, showing strong fluorescent property. Furthermore, by loading chiral guest in the MOF pore, the formed chiral encapsulated AIE-SURMOF can clearly indicate obvious circularly polarized luminescence performance with glum of 0.01. This study provides new MOF thin film and new strategy for expanding function and application of MOF materials.

Ultrastarke Elektron‐Phonon‐Kopplung in Uran‐organischen Gerüstverbindungen führt zu einer inversen Temperaturabhängigkeit der Lumineszenz

AbstractElektron‐Phonon‐Wechselwirkungen, die in kondensierter Materie von entscheidender Bedeutung sind, werden in metallorganischen Gerüstverbindungen (MOFs) selten beobachtet. In Lanthanoid‐ oder Actinoid‐basierten Verbindungen gelingt der Nachweis dieser Wechselwirkungen typischerweise über die Analyse der Lumineszenz. Frühere Studien zu Ln‐ und Ac‐basierten MOFs bei hohen Temperaturen ergaben zusätzliche Lumineszenzsignale, die jedoch zu schwach für eine gründliche Analyse waren. Im Rahmen unserer Untersuchungen haben wir mithilfe eines Schicht‐für‐Schicht‐Verfahrens eine hochgeordnete, kristalline uranbasierte MOF‐Dünnschicht (KIT‐U‐1) hergestellt. Unter UV‐Licht zeigte diese Schicht zwei ausgeprägte „heiße Banden“, die auf eine starke Elektron‐Phonon‐Wechselwirkung hinweisen. Während bei 77 K keine Emissionsbanden sichtbar waren, erschien bei 300 K eine Emissionsbande mit der halben Intensität der Hauptbande. Überraschenderweise tauchte oberhalb von 320 K eine zweite, sogenannte heiße Bande auf, die von früheren Ergebnissen aus Seltenerd‐Verbindungen abweicht. Wir haben eine detaillierte ab initio‐Analyse mithilfe der zeitabhängigen Dichtefunktionaltheorie durchgeführt, um dieses ungewöhnliche Verhalten zu verstehen und die für die starke Elektron‐Phonon‐Kopplung verantwortliche Gitterschwingung zu identifizieren. Die heißen Emissionsbanden der KIT‐U‐1‐Schicht wurden dann dazu genutzt, ein hochempfindliches optisches Einkomponenten‐Thermometer zu entwickeln. Diese Ergebnisse belegen das Potenzial hochwertiger MOF‐Dünnschichten bei der Nutzung der einzigartigen Lumineszenz von Lanthanoiden und Actinoiden für neuartige Anwendungen.

Ultrastrong Electron-Phonon Coupling in Uranium-Organic Frameworks Leading to Inverse Luminescence Temperature Dependence.

Electron-phonon interactions, crucial in condensed matter, are rarely seen in Metal-Organic Frameworks (MOFs). Detecting these interactions typically involves analyzing luminescence in lanthanide- or actinide-based compounds. Prior studies on Ln- and Ac-based MOFs at high temperatures revealed additional peaks, but these were too faint for thorough analysis. In our research, we fabricated a high-quality, crystalline uranium-based MOF (KIT-U-1) thin film using a layer-by-layer method. Under UV light, this film showed two distinct "hot bands," indicating a strong electron-phonon interaction. At 77 K, these bands were absent, but at 300 K, a new emission band appeared with half the intensity of the main luminescence. Surprisingly, a second hot band emerged above 320 K, deviating from previous findings in rare-earth compounds. We conducted a detailed ab-initio analysis employing time-dependent density functional theory to understand this unusual behaviour and to identify the lattice vibration responsible for the strong electron-phonon coupling. The KIT-U-1 film's hot-band emission was then utilized to create a highly sensitive, single-compound optical thermometer. This underscores the potential of high-quality MOF thin films in exploiting the unique luminescence of lanthanides and actinides for advanced applications.

Control of ZIF-62 and ag ZIF-62 Film Thickness within Asymmetric Tubular Supports through Pressure and Dose Time Variation of Atomic Layer Deposition.

Thin-films of metal-organic frameworks (MOFs) have widespread potential applications, especially with the emergence of glass-forming MOFs, which remove the inherent issue of grain boundaries and allow coherent amorphous films to be produced. Herein, it is established that atomic layer deposition (ALD) of zinc oxide lends excellent control over the thickness and localization of resultant polycrystalline and glass zeolitic imidazole framework-62 (ZIF-62) thin-films within tubular α-alumina supports. Through the reduction of the chamber pressure and dose times during zinc oxide deposition, the resultant ZIF-62 films are reduced from 38µm to 16µm, while the presence of sporadic ZIF-62 (previously forming as far as 280µm into the support) is prevented. Furthermore, the glass transformation shows a secondary reduction in film thickness from 16 to 2µm.

Synthesis of novel Cu/Fe based benzene Dicarboxylate (BDC) metal organic frameworks and investigations into their optical and electrochemical properties

In the recent past Metal-organic frameworks (MOFs) based thin films have demonstrated superior performance in various technological applications such as optical and optoelectronic devices, electrochemical energy storage, catalysis, and sensing. Herein we report tuning the optical performance of stable complexes using Cu and Fe metal ions with carboxylate benzene dicarboxylic (BDC), leading toward the formation of novel MOF structures. The formation of Cu-BDC and Fe-BDC were confirmed by XRD and SEM studies. The thermal stability of two MOFs was investigated, indicating that, the Cu-BDC is more stable than Fe-BDC. Further, the optical properties were investigated in the wavelength range 325–1100 nm, and the Fe-BDC exhibited greater optical transmission properties than Cu-BDC by 33 %, as investigated by Wemple-DiDomenico and Tauc models. The dispersion parameters related to optical studies for Cu-BDC were better in comparison to Fe-BDC, which could be attributed to the increase in Cu valence electrons due to an increase in the number of cations. The electrochemical behavior in terms of CV measurements shows the presence of pseudo capacitance in both Fe-BDC and Cu-BDC MOFs. The improved CV performance of Cu-BDC MOF suggests that it could be used as a storage material. This work successfully demonstrates the tailoring of optical properties related to MOF thin films through the formation of stable complexes using BDC as a potential material for the fabrication of OLED's and Solar cells. The improved CV performance suggests that these MOF based materials could be used as anodes in fabrication of batteries or supercapacitors.

Stress-driven recrystallization of pentacene films via diffusion-induced ingress of MOF nanocrystals into the grain boundaries

Metal-organic frameworks (MOFs) have been identified as versatile candidates for producing functional materials for various applications. However, the growth of MOF thin film becomes challenging due to non-availability of a proper solvent that restricts the use of the materials in electronic sensor fabrication. The receptor molecules in sensors are often used to functionalize the semiconducting channel. However, integrating such molecules degrade the crystallinity of channel materials, leading to poor sensor performance. In this work, we report the growth of a MOF (CPO-27-Ni) thin film and the recrystallization of semiconducting pentacene thin films due to diffusion of the crystallites into the grain boundaries. MOF films were successfully spin coated at various revolutions per minute (rpm) on pentacene surfaces. The growth of MOF films was studied using statistical analysis of rough surfaces by utilizing scaling theory to capture the evolution of surface morphologies. The x-ray reflectivity study unveiled the diffusion-induced ingress of the MOF through the grain boundaries of pentacene films that imparts compressive stress within the grains leading to subsequent rearrangement of pentacene molecules in the thin-film phase and recrystallizes the bulk crystallographic phase, which in a way will enhance the device performance.

Metal–organic framework thin films: review of their room-temperature synthesis and applications

This review presents diverse growth methods employed in the fabrication of room temperature-synthesized MOF films, emphasizing their significant applications across various fields.

Vapor-phase methods for synthesizing metal-organic framework thin films

<p>Due to their unique structures and exceptional physical and chemical properties, metal-organic framework (MOF) materials have garnered extensive attention in various fields, including catalysis, separations, sensing, and optics. Compared with powders or bulk MOF materials, MOF thin films exhibit large vertical and horizontal dimensions, higher specific surface areas, and abundant active sites and undergo facile combination with other functional centers for adsorption/separation, catalysis, and photoelectronic device applications. Among the methods used in preparing MOF thin films, the vapor phase approach enables more effective growth of MOF films with controllable thicknesses, uniformity, and compatibility; thus, it has attracted significant interest. This extensive review presents four vapor-phase approaches for preparing MOF thin films: the steam-assisted conversion method, vapor-phase transformations of metal oxide templates, vapor-phase linker exchange, and the atomic layer deposition/molecular layer deposition method. We summarize the advantages and disadvantages of these different vapor-phase-based methods for thin-film preparation, aiming to promote their use in precise and controllable surface syntheses.</p>

Polymorphism and orientation control of copper-dicarboxylate metal-organic framework thin films through vapour- and liquid-phase growth.

Precise control over the crystalline phase and crystallographic orientation within thin films of metal-organic frameworks (MOFs) is highly desirable. Here, we report a comparison of the liquid- and vapour-phase film deposition of two copper-dicarboxylate MOFs starting from an oriented metal hydroxide precursor. X-ray diffraction revealed that the vapour- or liquid-phase reaction of the linker with this precursor results in different crystalline phases, morphologies, and orientations. Pole figure analysis showed that solution-based growth of the MOFs follows the axial texture of the metal hydroxide precursor, resulting in heteroepitaxy. In contrast, the vapour-phase method results in non-epitaxial growth with uniplanar texture only.

Fabrication of Two-Dimensional Homo-Bimetallic Porphyrin Framework Thin Films for Optimizing Nonlinear Optical Limiting.

Developing efficient metal-organic framework (MOF) optical devices with tunable third-order nonlinear optical (NLO) properties is an important challenge for scientific research and practical application. Herein, 2D monometallic and hetero/homo-bimetallic porphyrin MOF thin films (ZnTCPP(M) M = H2, Fe, Zn) were fabricated using the liquid-phase epitaxial (LPE) layer-by-layer (LBL) method to investigate the metal substitution dependent third-order NLO behavior. The prepared homo-bimetallic ZnTCPP(Zn) thin film exhibited enhanced third-order NLO performance with a higher third-order nonlinear susceptibility of ∼4.21 × 10-7 esu compared to monometallic and hetero-bimetallic counterparts. Additionally, theoretical calculations were performed to complement the experimental findings and revealed that the enhanced NLO effect of the ZnTCPP(Zn) thin film is mainly attributed to the enhanced local excitation. These findings not only provide a comprehensive understanding of the relationship between metal types and the NLO behavior of porphyrin MOF thin films but also offer valuable insights into the design and optimization of NLO devices.

MOF thin film memristor prototype of 10×10 memory cells for automated electronic data recording

Metal–organic frameworks (MOFs) have recently emerged as a new class of functional materials for opto- and micro-electronic applications. Herein, the transition from laboratory samples of devices to their prototypes remains a challenge. Here we report a prototype of memristive device based on MOF (HKUST-1). The MOF thin film with a thickness of 130 nm and a size of 1 × 1 in. has been fabricated Layer-by-layer technique on a conductive substrate followed by the deposition of top Ag contacts. A fully automated process of applying voltage to write the binary data (at 0.8 ± 0.1 V), read it (by 0.4 V) and then erase (by inverted polarity with 0.4 ± 0.1 V) made it potentially possible to process arbitrary words for at least 10 cycles. The provided prototype, consisting of 10 × 10 memory cells, opens up prospects for real-life application of MOF-based logic elements, as well as reveals the challenges for their fabrication and exploitation.

Comprehensive Qualitative and Quantitative Colorimetric Sensing of Volatile Organic Compounds Using Monolayered Metal-Organic Framework Films.

Cross-responsive chemical sensors are in high demand owing to their ability to distinguish a broad range of analytes. In this study, a vapochromic sensor array based on metal-organic frameworks (MOFs), which exhibits distinct patterns when exposed to volatile organic compounds (VOCs) and humidity, is developed. Conventional sensor arrays consist of various receptors that produce different responses. The vapochromic MOF-based sensor comprises dicopper paddlewheel clusters and dimethylamine azobenzene as binary colorimetric sensing moieties. Upon exposure to VOCs, the constructed sensor encompasses a broad spectrum of colors, ranging from green to red. Furthermore, the color of the MOF is influenced by the solvent used during the pretreatment. Consequently, monolayered MOF thin films can be adapted to multicomponent array systems by immersing the MOF in different solvents. This system provides both qualitative and quantitative sensing, generating unique color patterns corresponding to specific VOC types. Notably, the sensor successfully discriminates each of 14 common VOCs and water and accurately categorizes unknown samples. Moreover, the system undergoes reversible color changes in response to humidity, obviating the need for high-temperature regeneration steps. This novel approach offers insights into the versatile applications of MOFs by creating a colorimetric sensor array capable of detecting various analytes.

Electrochromism in Isoreticular Metal-Organic Framework Thin Films with Record High Coloration Efficiency.

The power of isoreticular chemistry has been widely exploited to engineer metal-organic frameworks (MOFs) with fascinating molecular sieving and storage properties but is underexplored for designing MOFs with tunable optoelectronic properties. Herein, three dipyrazole-terminated XDIs (X = PM (pyromellitic), N (naphthalene), or P (perylene); DI = diimide) with different lengths and electronic properties are prepared and employed as linkers for the construction of an isoreticular series of Zn-XDI MOFs with distinct electrochromism. The MOFs are grown on fluorine-doped tin oxide (FTO) as high-quality crystalline thin films and characterized by X-ray diffraction (XRD) and scanning electron microscopy (SEM). Due to the constituting electronically isolated XDI linkers, each member of the isoreticular thin film series exhibits two reversible one-electron redox events, each at a distinct electrochemical potential. The orientation of the MOFs as thin films as well as their isoreticular nature results in identical cation-coupled electron hopping transport rates in all three materials, as demonstrated by comparable apparent electron diffusion coefficients, Deapp. Upon electrochemical reduction to either the [XDI]•- or [XDI]2- state, each MOF undergoes characteristic changes in its optical properties as a function of linker length and redox state of the linker. Operando spectroelectrochemistry measurements reveal that Zn-PDI@FTO (PDI = perylene diimide) thin films exhibit a record high coloration efficiency of 941 cm2 C-1 at 746 nm, which is attributed to the maximized Faradaic transformations at each electronically isolated PDI unit. The electrochromic response of the thin film is retained to more than 99% over 100 reduction-oxidation cycles, demonstrating the applicability of the presented materials.

Nanographene‐Based Metal‐Organic Framework Thin Films: Optimized Packing and Efficient Electron‐Hole Separation Yielding Efficient Photodetector

AbstractOrganic semiconductors, specifically polycyclic aromatic chromophores like pentacene, coronene, and nanographenes (hexa‐peri‐hexabenzocoronene, HBC), are often utilized in optoelectronic applications due to their intriguing single‐molecule properties. However, the integration of these aromatic compounds into optoelectronic devices frequently encounters significant obstacles, primarily due to the unpredictable and challenging control over the structure and morphology of their condensed phase. Rather than resorting to chemical modifications or advanced thin‐film manufacturing methods such as chemical vapor deposition, the so‐called metal‐organic framework (MOF) approach is employed to create a highly photoresponsive, nanographene‐based thin film employing a layer‐by‐layer, liquid‐phase epitaxy method. It is demonstrated that the novel Cu‐HBC MOF thin film exhibits excellent photoresponsive behavior under ultraviolet illumination, including a fast response time (˂ 0.02 s) and high current switching ratio (≈104), which significantly outperforms an isostructural MOF Zn‐HBC. Furthermore, it is demonstrated that the metal nodes inside the MOF can be used to enhance the photoresponse by efficient exciton splitting.

Ag Nanoparticles-Induced Metallic Conductivity in Thin Films of 2D Metal-Organic Framework Cu3(HHTP)2.

Two-dimensional (2D) metal-organic frameworks (MOFs) are usually associated with higher electrical conductivity and charge carrier mobility when compared with 3D MOFs. However, attaining metallic conduction in such systems through synthetic or postsynthetic modifications is extremely challenging. Herein, we present the fabrication of thin films of a 2D MOF, Cu3(HHTP)2 (HHTP = 2,3,6,7,10,11-hexahydroxytriphenylene), decorated with silver nanoparticles (AgNPs) exhibiting significant conductivity enhancement at room temperature. Variable-temperature electrical transport measurements across the low-temperature (200 K) to high-temperature (373 K) regime evidenced metallic conduction. Interestingly, thin films of a 3D MOF, CuTCNQ (TCNQ = 7,7,8,8-tetracyanoquinodimethane), upon decoration with AgNPs, disclosed a converse trend. The origin of such distinctive observations on AgNPs@Cu3(HHTP)2 and AgNPs@CuTCNQ systems was comprehended by using first-principles density functional theory (DFT) calculations and attributed to an interfacial electronic effect. Our work sheds new light on rationally designing synthetic modifications in thin films of MOFs to tune the electrical transport property.

Recent Advances in Lanthanide Metal–Organic Framework Thin Films Based on Eu, Tb, Gd: Preparation and Application as Luminescent Sensors and Light-Emitting Devices

Lanthanide Metal–Organic Frameworks (LnMOFs), in recent years, have developed into an interesting subclass of MOFs. While the number of published papers, in particular, were dedicated to their synthesis and functional properties, along with the application mechanisms of MOFs, only a few of them have been focused on LnMOFs thin films independently. LnMOFs have become interesting thanks to their outstanding properties, for example, excellent structural flexibility, tunable pore size, surface area, functionality, and good chemical stability. Significant progress over the past two decades in the preparation of MOF films has been achieved, especially towards the development of green, or at least greener, synthesis approaches. We begin with insight into various types of MOFs and summarize recent achievements in the production of LnMOF films, along with various film preparation approaches. Afterward, we briefly discuss the applications of luminescence features of lanthanide ions in films and their potential as white-light source materials. We also covered films based on Eu, Tb, and Gd with particular accents on different design approaches. Moreover, specifically, luminescent features applied for sensing temperature, a variety of ions, gases, and biomolecules are highlighted. The review ends with a comprehensive conclusion about the state-of-art-potential of LnMOFs together with an outlook on the future of LnMOF films in future technologies.

Morphology-dependent optical properties of a 3D CH3NH3PbBr3 based metal − organic framework

More recently, Metal–Organic Frameworks (MOFs) have displayed extensive promise in the fields of energy storage, solar cells, catalysis, super capacitors, and optoelectronic devices. This work investigates the nonlinear thermo-optical responses of CH3NH3PbBr3 (MAPbBr3) and mix MAPbBr3 with UiO-66-NH2 (MAPbBr3 + MOF) thin films using the Z-scan technique with different incident power of laser ranging from 10 mW to 50 mW. The results show that the third-order nonlinear optical coefficients of MAPbBr3 + MOF thin films were improved obviously than MAPbBr3 thin films. Furthermore, nonlinear optical properties of MAPbBr3 + MOF thin film is evaluated to be improved from 12.5 × 10-8 to 38.2 × 10-8 by decreasing the input power of laser from 50 mW to 10 mW. This treatment repeated for MAPbBr3 thin film, as well. Considering Kubelka-Munk equation, energy gap) Eg for the MAPbBr3 and MAPbBr3 + MOF thin films deposited on glass film is calculated to be 2.565 and 2.530 eV. Due to analyze the optical characterization of the synthesized samples, optical reflection, transmission and absorption were studied. Kramers-Kronig relations and the reflectance data were used for calculation of complex refractive index and dielectric constant. The transverse and the longitudinal optical phonon modes of MAPbBr3 and MAPbBr3 + MOF thin films locate at about 548 and 598 nm, and 590 and 640 nm, respectively. This research opens a new window for wide scale optoelectronic devices in Q-switching for the generation of pulsed lasers including MAPbBr3 with UiO-66-NH2 by detecting the remarkable nonlinear optical characteristics in lower incident power.