Spin-coated Films Research Articles

Enhancement of organic field-effect transistor performance via precision molecular alignment of a P4T2F-HD-based conjugated polymer

This study conducts a detailed exploration of how the orientation of molecules affects the efficiency of organic field-effect transistors (OFETs), with a particular focus on a new conjugated polymer, P4T2F-HD. The study examines the fabrication of both large-scale, anisotropically oriented thin films and non-oriented, isotropic thin films of P4T2F-HD through two separate approaches: the Unidirectional Film Transfer Method (UFTM) for oriented films and spin-coating for isotropic films. Results indicate that UFTM notably excels in directing the molecular alignment of P4T2F-HD across extensive areas, thereby creating anisotropic thin films, whereas spin-coating yields isotropic thin films lacking specific orientation. Further investigation into the properties of these films through various analytical techniques sheds light on the role of molecular orientation in influencing their electronic characteristics. OFETs fabricated with anisotropically oriented P4T2F-HD films exhibit markedly improved performance, characterized by higher charge carrier mobility and enhanced electrical stability, in comparison to their isotropic counterparts. The study evidences that the directional arrangement of macromolecules plays a pivotal role in OFETs functionality, with UFTM-derived films demonstrating a significant leap in field-effect mobility—showing an over 100-fold improvement over spin-coated films. This boost is linked to the effective charge transmission along the polymer chains, enabled by precise molecular alignment.

Efficient Redirection of Trapped Broad-Band Fluorescence from Substrates into Free Space Using c-Si Metasurfaces.

Fluorescent dye films on transparent substrates are essential for OLEDs, flexible displays, X-ray detection, and wireless optical communications. However, their efficiency is often hampered by fluorescence trapping due to total internal reflection (TIR) and waveguiding. This study tackles this longstanding challenge by reconceptualizing the integration of dye films with nanoantenna metasurfaces. Traditional methods involve directly spin-coating films onto c-Si metasurfaces on quartz substrates, resulting in edge luminescence and weak inner signals. We present a straightforward, adjustable approach by integrating dye films on the opposite side of quartz substrates, reaching a 2.5-fold photoluminescence enhancement and improving the uniformity of the emission compared to the conventional methods. These gains stem from redirecting a significant portion of leaked fluorescence light trapped inside the substrate into free space, surpassing TIR conditions through in-plane diffraction orders of the metasurfaces across the full RGB spectrum. Our findings facilitate the design of more efficient luminescent devices.

Investigation on TiO2 spin-coated thin films effect on the optoelectronic properties of stain-etched porous silicon for solar cell applications

This article aims to improve the opto-electronic properties of porous silicon (PS) to integrate it as an anti-reflecting coating in solar cell applications. The enhancement of its properties is achieved through the passivation of its surface by titanium dioxide (TiO2). Samples of porous silicon were elaborated using stain etching technique, then treated with the metal oxide using spin-coating technique. The film thickness was varied to study the thickness effect on the properties of the TiO2/PS structure. Morphological study has shown that most pores were covered with TiO2 structures, resulting in an overall change in the surface morphology. Fourier transform infrared spectroscopy (FTIR) and X-ray diffraction (XRD) analysis has confirmed the TiO2 deposition on PS surface. The passivation of PS with TiO2 had more interesting results, especially in the case of PS passivated with three layers of TiO2, which suggests a good coverage of the surface of PS, results confirmed by optical study and minority carrier lifetime measurement. Moreover, a simulation was also carried out using PC1D. The optoelectronic results of the synthesized TiO2/PS samples were applied on a built-in model of a commercialized silicon-based solar cell. The efficiency increased from 11% for an untreated silicon solar to 15.8% for the cell modeled with 3 layers of TiO2 deposited on PS.

Magnetron sputtered nickel oxide with suppressed interfacial defect states for efficient inverted perovskite solar cells

Widely used spin-coated nickle oxide (NiOx) based perovskite solar cells often suffer from severe interfacial reactions between the NiOx and adjacent perovskite layers due to surface defect states, which inherently impair device performance in a long-term view, even with surface molecule passivation. In this study, we developed high-quality magnetron-sputtered NiOx thin films through detailed process optimization, and compared systematically sputtered and spin-coated NiOx thin film surfaces from materials to devices. These sputtered NiOx films exhibit improved crystallinity, smoother surfaces, and significantly reduced Ni3+ or Ni vacancies compared to their spin-coated counterparts. Consequently, the interface between the perovskite and sputtered NiOx film shows a substantially reduced density of defect states. Perovskite solar cells (PSCs) fabricated with our optimally sputtered NiOx films achieved a high power conversion efficiency (PCE) of up to 19.93% and demonstrated enhanced stability, maintaining 86.2% efficiency during 500 h of maximum power point tracking under one standard sun illumination. Moreover, with the surface modification using (4-(2,7-dibromo-9,9-dimethylacridin-10(9H)-yl)butyl)phosphonic acid (DMAcPA), the device PCE was further promoted to 23.07%, which is the highest value reported for sputtered NiOx based PSCs so far.

Influence of Ag doping on structural, morphological, and optical characteristics of sol-gel spin-coated TiO2 thin films

Pure and Ag-doped Titanium dioxide (TiO2) thin films have been synthesized via the sol-gel spin coating method, and their structural, morphological, and optical properties have been investigated. X-ray diffraction analysis verifies that the polycrystalline anatase TiO2 phase is retained up to 2 % Ag doping. However, lattice expansion and grain refinement down to 25.345 nm are observed with increasing Ag content. Scanning electron microscopy (SEM) reveals the formation of large, isolated TiO2 aggregates separated by drying-induced cracks across the film surface. Optical studies show the undoped TiO2 films demonstrate excellent visible transparency (>75 % transmittance) that slightly decreases upon Ag doping, though it remains suitably high for device applications. Meanwhile, optical absorption and defect states improve with more Ag incorporation, narrowing the TiO2 bandgap from 3.83 eV (undoped) to 3.51 eV (2 % Ag-doping) due to the incorporation of Ag-induced electronic states just below the conduction band minimum. The capability to control optical and structural properties through Ag doping highlights the potential of these TiO2 films suitably tailored for photovoltaic devices or self-cleaning coatings.

Spin-coated films of calix[4]resorcinarenes as sensors for chlorinated solvent vapours

Spin-coated films of calix[4]resorcinarenes as sensors for chlorinated solvent vapours

Systematic anode engineering enabling universal efficiency improvements in organic solar cells

Anode modification and optimization is crucial towards improving performance of organic solar cells (OSCs). PEDOT:PSS is the most common choice as a hole transport layer (HTL) material, but suffers from issues including low conductivity. In this work, three alkyl amine derivatives - methylamine hydrochloride (MA), ethylamine hydrochloride (EA) and propylamine hydrochloride (PA) are doped into the commercially available Al 4083 PEDOT:PSS to form PEDOT:PSS-MA, PEDOT:PSS-EA and PEDOT:PSS-PA, as modified HTLs. All these modified HTLs exhibit improved chemical and electrical properties including work functions (WF), conductivities and charge carrier motilities. The alkyl amine doping shows compatibility in both Small Molecular Acceptors and All-Polymer OSCs. With PEDOT:PSS-MA demonstrates a highest PCE of 18.49 % compared to the 17.84 % of OSC devices prepared with pristine PEDOT:PSS with the PM6:L8-BO system, while PM6:PY-IT all-polymer OSCs improve PCE from 14.53 % to 15.22 %. AFM characterizations reveal that the introduction of the dopants have smoothened the surface morphology of spin-coated HTL films, which contributes towards more efficient charge extraction. In summary, this study not only presents a method of improving OSC efficiencies, but also provides insight and further possible directions towards anode optimization of OSCs.

Photoresponsive Dioxazaborocanes-Containing Oligomers.

The synthetic methodology for the preparation of photoresponsive dioxazaborocanes-containing oligomers is developed. It relies on the transformation of the (diisopropylamino)boryl group (-BH(NiPr2)) into a dioxazaborocane unit in the presence of β-aminodiols and involves a bis-borylated dithienylethene photochromic unit. The photophysical properties of the obtained oligomers are evaluated as well as their processability for the preparation of spin-coated films. The photomechanical behavior of the resulting films is assessed via displacement tracking profile.

Tailored thermoelectric performance of poly(phenylene butadiynylene)s/carbon nanotubes nanocomposites towards wearable thermoelectric generator application

In this study, two conjugated polymers (CPs) featuring poly(phenylene butadiynylene) (PPB) were meticulously synthesized and composited with single-walled carbon nanotubes (SWCNTs) to investigate their thermoelectric properties and fabricate wearable thermoelectric generators (TEGs). These CPs, designated as P1 and P2, were tailored with distinct side chain configurations by incorporating 2-butyloctyloxy and 6-(methyldioctylsilyl)hexyloxy groups, respectively. Notably, P2, characterized by longer side chains with branchpoints farther from the backbone, exhibited planar backbone structure and enhanced solubility, consequently engendering stronger π–π interaction with SWCNTs and facilitating the disperse of SWCNTs through polymer wrapping at bundle surface. Such characteristics therefore contributed to the superior thermoelectric performances of the P2/SWCNTs nanocomposite, yielding a higher power factor (PF) of 216.5 μW m−1 K−2 for the spin-coated film. Furthermore, the corresponding wearable TEGs, which were constructed through spray-coating with 14 legs, resulted in an output power of approximately 49.6 nW under a temperature difference of 25 K, exhibiting successful harvesting of waste heat. Further applications also demonstrated operational efficacy under diverse conditions. These findings not only underscored the significance of side chain engineering in tailoring the thermoelectric properties of CP/SWCNTs nanocomposites but also demonstrated the feasibility of fabricating high-performance wearable thermoelectric devices applicable in versatile contexts.

Reliable Fabrication of Mineral-Graded Scaffolds by Spin-Coating and Laser Machining for Use in Tendon-to-Bone Insertion Repair.

A reliable method for fabricating biomimetic scaffolds with a controllable mineral gradient to facilitate the surgical repair of tendon-to-bone injuries and the regeneration of the enthesis is reported. The gradient in mineral content is created by sequentially spin-coating with hydroxyapatite/poly(ε-caprolactone) suspensions containing hydroxyapatite nanoparticles in decreasing concentrations. To produce pores and facilitate cell infiltration, the spin-coated film is released and patterned with an array of funnel-shaped microchannels by laser machining. The unique design provided both mechanical (i.e., substrate stiffness) and biochemical (e.g., hydroxyapatite content) cues to spatially control the graded differentiation of mesenchymal stem cells. Immunocytochemical analysis of human mesenchymal stem cell-seeded scaffolds after 14 days of culture demonstrated the formation of a spatial phenotypic cell gradient from osteoblasts to mineralized chondrocytes based on the level of mineralization in the scaffold. By successfully recreating compositional and cellular features of the native tendon enthesis, the biomimetic scaffolds offer a promising avenue for improved tendon-to-bone repair.

Role of Annealing with Electric Field Toward Improvement of Ferroelectric and Electroactive Properties of PVDF Copolymer and Terpolymer Thin Films.

The present study elucidates the role of annealing with electric field on lamellar crystalline structure and molecular orientation of polymer chains in ferroelectric copolymer (P(VDF-TrFE)) and ferroelectric terpolymer (P(VDF-TrFE-CFE)) spin-coated thin films. The ferroelectric polymer thin films annealed under an electric field support the growth of nanostructure with an "edge-on" lamellar crystalline structure having in-plane molecular chain orientation. The poled P(VDF-TrFE) thin films have higher remnant polarization (Pr) ≈6.2µCcm-2 and saturation polarization (Ps) ≈8.2µCcm-2 at an applied electric field of 250 MV/m compared to unpoled thin films having Pr ≈4.7 and Ps ≈6.2µCcm-2. Also, poled P(VDF-TrFE) thin films show lower coercive field (Ec) ≈94 MV/m compared to an unpoled thin film having Ec ≈105 MV/m. Similarly, poled PVDF-TrFE-CFE thin film shows better ferroelectric properties having Pr ≈0.4 and Ps ≈5.7µCcm-2 at an applied electric field of 200 MVm-1 compared to unpoled thin films having Pr ≈0.4 and Ps ≈4.1µCcm-2. The storage energy efficiency of unpoled and poled P(VDF-TrFE-CFE) thin films is measured to be ≈75% and 80%. Annealing of ferroelectric P(VDF-TrFE) polymer thin films under an electric field demonstrates improved ferroelectric and electroactive properties.

Spin-coated BiFeO3 films on Si wafers: Low processing temperature but prominent piezoelectricity

The direct integration of crystalline oxide layers with industrial Si substrate, specifically compatible with CMOS technology, requires the development of relatively simple, low-temperature processing routes below 450 °C. Here, a novel nonstoichiometric approach is proposed to achieve fabrication of BiFeO3 films at 450 °C. Of particular importance is that, a saturation and remnant polarization of ∼80 μC/cm2 and ∼60 μC/cm2 and a strain as large as 1% are obtained. This strain stands as one of the most impressive values reported for thin films, comparable to the most superior strain obtained in ferroelectric films fabricated at temperatures exceeding 700 °C. The current work provides a new paradigm with significant simplicity and novel efficacy in reducing processing temperatures, as well offers a promising material for memory and piezo-driven actuating applications, especially meeting the increasing demand for precision position control systems at the nanometer scale.

Outstanding ferroelectric properties in the narrow bandgap cobalt-substituted BiFeO3 spin-coated films

Outstanding ferroelectric properties in the narrow bandgap cobalt-substituted BiFeO3 spin-coated films

Compatibility and performance study of electrohydrodynamic printing using zinc oxide inkjet ink

The demand for modern electronics and semiconductors has increased throughout the years, which has enabled the innovation and exploration of solution-processed deposition. Solution-based processes have gained a lot of interest due to the low-cost fabrication and the large fabrication areas without the need for high-vacuum equipment. In this study, we utilized the ZnO ink for inkjet printer ink to fabricate a thin film via Electrohydrodynamic printing. Three different ink solutions were prepared for experimentation. The EHD printing technique demonstrated the ink’s compatibility with and without the modifications. The outcomes of the EHD printed materials were comparable with the spin-coated thin films. The EHD-printed films demonstrated better results in comparison to spin-coated films. Ra and Rq of the EHD film measured at 3.651 nm and 4.973 nm, respectively. It improved the absorbance up to two-fold at 360 nm wavelength and electrical conductivity up to 40% compared to the spin-coated films. Furthermore, the optimization of the printing parameters can lead to the improved morphology and thickness of the EHD thin films.

Friction Force Mapping of Molecular Ordering and Mesoscopic Phase Transformations in Layered-Crystalline Organic Semiconductor Films.

It is critical to understand molecular ordering processes in small-molecule organic semiconductor (OSC) films in optimizing electronic device applications, although it is difficult to observe and investigate the ordering characteristics at a mesoscopic or device scale. Here, we report that friction force microscopy (FFM) allows visualizing the ordering transformation process from a thermodynamically metastable phase to a stable phase at a mesoscopic scale. We utilized 2-octyl-benzothieno[3,2-b]naphtho[2,3-b]thiophene (2-C8-BTNT) as a typical highly layered-crystalline OSC. We found that the friction force between an AFM tip and spin-coated OSC films significantly depends on whether local film states are in metastable monolayer phase or stable bilayer-type herringbone (b-LHB) phase that exhibits high carrier mobility. The formation of the stable b-LHB phase leads to lower friction than the metastable monolayer phase, clearly visualizing the molecular order. Force map (Fmap) analysis indicates that the lower friction in the b-LHB phase should be associated with the reduction of interfacial adhesion force. Notably, the observed results demonstrate that the spin-coated thin film changes from continuous film with the monolayer phase to rugged microcrystal grains with the b-LHB phase when left at ambient conditions. By contrast, an appropriate post-thermal annealing process facilitates the phase transformation without inducing such morphological changes. The technique provides a unique and effective tool for revealing the relationship between processing conditions and device performance in polycrystalline OSC films.

Thickness Determination and Control in Protein-Based Biomaterial Thin Films.

Controlling the thickness and uniformity of biomaterial films is crucial for their application in various fields including sensing and bioelectronics. In this work, we investigated film assemblies of an engineered repeat protein─specifically, the consensus tetratricopeptide repeat (CTPR) protein ─a system with unique robustness and tunability. We propose the use of microreflectance spectroscopy and apparent color inspection for the quick assessment of the thickness and uniformity of protein-based biomaterial films deposited on oxidized silicon substrates. Initially, we characterized the thickness of large, uniform, spin-coated protein films and compared the values obtained from microreflectance spectroscopy with those obtained from other typical methods, such as ellipsometry and atomic force microscopy. The excellent agreement between the results obtained from the different techniques validates the effectiveness of microreflectance as a fast, noninvasive, and affordable technique for determining the thickness of biomaterial films. Subsequently, we applied microreflectance spectroscopy to determine the thickness of drop-casted CTPR-based films prepared from small protein solution volumes, which present a smaller surface area and are less uniform compared to spin-coated samples. Additionally, we demonstrate the utility of apparent color inspection as a tool for assessing film uniformity. Finally, based on these results, we provide a calibration of film thickness as a function of the protein length and concentration for both spin-coated and drop-casted films, serving as a guide for the preparation of CTPR films with a specific thickness. Our results demonstrate the remarkable reproducibility of the CTPR film assembly, enabling the simple preparation of biomaterial films with precise thickness.

Two-step preparation of methylammonium lead triiodide perovskite film via electrospray deposition of methylammonium iodide solution for solar cell applications

Solution-processable perovskite solar cells (PSCs) have the potential to revolutionize solar cell technology by enabling low power generation costs via low-cost device fabrication. However, most existing research regarding PSCs relies on the spin-coating method, which is not conducive to large-area film deposition. Therefore, the development of an alternative deposition method for perovskite films has become increasingly important for commercialization, for which electrospray deposition is a promising technique. This study investigates the two-step preparation of methylammonium lead triiodide (MAPbI3) perovskite films via the electrospray deposition of a methylammonium iodide (MAI) solution on a spin-coated PbI2 film. The gradual conversion of PbI2 to MAPbI3 with increasing MAI deposition time was revealed, accompanied by an increase in the size of the perovskite crystals. In addition, PSCs were successfully fabricated by electrospraying MAI, achieving a considerable power conversion efficiency of 7.86 % at the optimal MAI deposition time.

Blade-Coating of High Crystallinity Cesium-Formamidinium Perovskite Formulations.

Up-scalable coating processes need to be developed to manufacture efficient and stable perovskite-based solar modules. In this work, we combine two Lewis base additives (N,N'-dimethylpropyleneurea and thiourea) to fabricate high-quality Cs0.15FA0.85PbI3 perovskite films by blade-coating on large areas. Selected-area electron diffraction patterns reveal a minimization of stacking faults in the α-FAPbI3 phase for this specific cesium-formamidinium composition in both spin-coated and blade-coated perovskite films, demonstrating its scaling potential. The underlying mechanism of the crystallization process and the specific role of thiourea are characterized by Fourier transform infrared spectroscopy and in situ optical absorption, showing clear interaction between thiourea and perovskite precursors and halved film-formation activation energy (from 114 to 49 kJ/mol), which contribute to the obtained specific morphology with the formation of large domain sizes on a short time scale. The blade-coated perovskite solar cells demonstrate a maximum efficiency of approximately 16.9% on an aperture area of 1 cm2.

Determining Structures of Layer-by-Layer Spin-Coated Zinc Dicarboxylate-Based Metal-Organic Thin Films.

Thin films of crystalline solids with substantial free volume built from organic chromophores and metal secondary building units (SBUs) are promising for engineering new optoelectronic properties through control of interchromophore coupling. Zn-based SBUs are especially relevant in this case because they avoid quenching the chromophore's luminescence. We find that layer-by-layer spin-coating using Zn acetate dihydrate and benzene-1,4-dicarboxylic acid (H2BDC) and biphenyl-4,4'-dicarboxylic acid (H2BPDC) linkers readily produces crystalline thin films. However, analysis of the grazing-incidence wide-angle X-ray scattering (GIWAXS) data reveals the structures of these films vary significantly with the linker, and with the metal-to-linker molar ratio used for fabrication. Under equimolar conditions, H2BPDC creates a type of structure like that proposed for SURMOF-2, whereas H2BDC generates a different metal-hydroxide-organic framework. Large excess of Zn2+ ions causes the growth of layered zinc hydroxides, irrespective of the linker used. Density functional theory (DFT) calculations provide structural models with minimum total energy that are consistent with the experimentally observed diffractograms. In the broader sense, this work illustrates the importance in this field of careful structure determination, e. g., by utilizing GIWAXS and DFT simulations to determine the structure of the obtained crystalline metal-organic thin films, such that properties can be rationally engineered and explained.

Formation and degradation mechanism of methylammonium lead iodide perovskite thin film fabricated by electrospray technique

Electrospray deposition technique has been reported previously for fabricating effective and stable perovskite thin film, leading to efficient perovskite solar cells. In this work, a comprehensive investigation of the formation mechanism of methylammonium lead iodide perovskite (CH3NH3PbI3) film by electrospray technique is demonstrated and compared to the formation mechanism through the conventional spin coating technique. In the electrospray process, charged MAI nanoparticles are gradually introduced onto the PbI2 film, intercalating within the PbI2 structure to produce the perovskite film. In contrast, the spin-coating method involves supplying the MAI solution in bulk, leading to perovskite crystal formation through the dissolution of the PbI2 layer by the MAI solution, followed by recrystallization into perovskite oriented in the [110] direction, 30° inclined to the substrate. The impact of charge and the electric field on the formation of perovskite film using the electrospray is explored.Furthermore, the intrinsic stability of perovskite films is monitored in real-time in a highly humid environment (≥80 % relative humidity (RH)) using in-situ Grazing Incidence Wide Angle X-ray Scattering (GIWAXS), and a degradation mechanism is proposed to enhance the durability of the perovskite-based devices. The study further delves into the comparison of the stability of electrosprayed and spin-coated perovskite film, and the impact of humidity level and the presence of a hole-transporting layer on the stability of the perovskite layer. Overall, this work provides a detailed understanding of the formation and humidity-induced degradation mechanism of electrosprayed perovskite films, offering insights that can extend to various applications of perovskite materials.