Spin-coated Films Research Articles

Spin-coated CZTS films prepared by two different precursor mixing regimes, at room temperature and at 150 °C

In this paper, we examine the impact of the precursor's mixing temperature and mixing protocol on the crystal structure and morphological and optical properties of Cu2ZnSnS4 (CZTS) thin films. Four samples of CZTS thin films were synthesized with the sol-gel spin coating technique by previously mixing precursors at (a) 150 °C and (b) room temperature (RT), either (i) all at once or (ii) through sequential adding the individual chemicals 30 min apart. SEM-EDX, XRD, Raman and Visible spectroscopy analysis showed that sample 150°C-ST (chemicals mixed at the same time at 150 °C) fulfilled all the theoretical stoichiometric criteria (poor in Cu, rich in Zn) for the high-quality CZTS absorbers. The larger grain size (850 nm) and crystallite size (73.96 nm), lower strain (0.49×10−3) and band gap Eg=1.44eV which is closest to the Shockley–Queisser limit for single junction solar cells (1.34 eV).

A polarization-sensitive, high on/off ratio and self-powered photodetector based on Nb2CT x and Nd2CT x @MoS2

MXene two-dimensional materials have been widely used in energy storage, catalysis, sensing and other fields, Nb2C as a typical two-dimensional MXene material, its exploration in the field of optoelectronics is still in its infancy, especially Nb2C-based photodetectors are still to be developed. This paper demonstrates that two-dimensional films based on few-layer Nb2C have a photoelectric response in the wavelength range from visible to near-infrared. We have found that the light response performance can be easily adjusted by controlling the thickness of the spin-coated film, and that Nb2C photodetectors show great advantages in terms of wide bandwidth, polarization response, high switching ratio, etc. By adjusting the material concentration and sample thickness, the photocurrent can reach up to 330 nA, the switching ratio can reach 410, and the responsivity can reach 8.3 × 10−4 A W−1. In the polarization characteristic test, an extinction ratio of 7.6 can be obtained. By adjusting the content of that doped MoS2 quantum dot, the dark current can reach 7.6 × 10−13 A, and the switching ratio can reach 3 × 105, which can be increased by 700 times. The above results show that the few-layer Nb2C nanosheets can be used as optoelectronic detectors in the visible to near-infrared bands, which further broadens the application prospects of two-dimensional MXene.

Synergistic Zinc(II) and Formate Doping of Perovskites: Thermal Phase Stabilization of α-FAPbI3 and Enhanced Photoluminescence Lifetime of FA0.8MA0.2PbI3 up to 3.7 µs.

Adding zinc (II) cations and formate anions improves the thermal phase stability of α-FAPbI3 materials, and the spin-coated thin films of such doped FAPbI3 (produced using MACl) show an increased emission lifetime of up to 3.7 μs on quartz (for FA0.8MA0.2PbI3). This work investigates the effects of zinc and formate on the phase stability and time-resolved photoluminescence of FAPbI3 perovskites for solar cell applications. Perovskite samples with varying concentrations of zinc and formate were made by incorporating different amounts of zinc formate and zinc iodide and were characterized with XRD. Doping levels of 1.7% Zn(II) and 1.0% formate (relative to Pb) seem optimal. The thermal phase stability of the doped perovskite powders (FAPbI3) and thin films (FA0.8MA0.2PbI3) was assessed. XRD of the thin films after 6 months shows only the alpha-phase. The time-resolved photoluminescence spectroscopy of the doped spin-coated perovskite samples (FA0.8MA0.2PbI3 produced using MACl) is reported. The results show that synergy between an anionic and a cationic dopant can take place, making the perovskite thermally more phase-stable (not converting to the yellow delta-phase) with a longer charge carrier lifetime. In order to produce good thin films by spin coating, the use of MACl was essential.

Cleanroom-Free Direct Laser Micropatterning of Polymers for Organic Electrochemical Transistors in Logic Circuits and Glucose Biosensors.

Organic electrochemical transistors (OECTs) are promising devices for bioelectronics, such as biosensors. However, current cleanroom-based microfabrication of OECTs hinders fast prototyping and widespread adoption of this technology for low-volume, low-cost applications. To address this limitation, a versatile and scalable approach for ultrafast laser microfabrication of OECTs is herein reported, where a femtosecond laser to pattern insulating polymers (such as parylene C or polyimide) is first used, exposing the underlying metal electrodes serving as transistor terminals (source, drain, or gate). After the first patterning step, conducting polymers, such as poly(3,4-ethylenedioxythiophene):poly(styrene sulfonate) (PEDOT:PSS), or semiconducting polymers, are spin-coated on the device surface. Another femtosecond laser patterning step subsequently defines the active polymer area contributing to the OECT performance by disconnecting the channel and gate from the surrounding spin-coated film. The effective OECT width can be defined with high resolution (down to 2µm) in less than a second of exposure. Micropatterning the OECT channel area significantly improved the transistor switching performance in the case of PEDOT:PSS-based transistors, speeding up the devices by two orders of magnitude. The utility of this OECT manufacturing approach is demonstrated by fabricating complementary logic (inverters) and glucose biosensors, thereby showing its potential to accelerate OECT research.

Fabrication of palladium-enriched metallic structures by direct focused He+ and Ne+ beam nanowriting from organometallic thin films: a comparison with Ga+ and e- beams.

A direct nanowriting procedure using helium- and neon-focused ion beams and spin-coated organometallic thin films is introduced and applied to the fabrication of Pd-enriched metallic structures in a single lithography step. This process presents significant advantages over multi-step resist-based lithography and focused beam-induced deposition using gaseous precursors, such as its simplicity and speed, respectively. The optimized process leads to Pd-rich structures with low electrical resistivity values of 141 and 152 μΩ cm under Ne+ or He+ fluences of 1000 and 5000 μC cm-2, respectively. These resistivity values correlate well with compositional and microstructural studies, indicating a high Pd metallic content in a dense structure with a few-nm grain size. The obtained results are compared to similar structures fabricated by direct electron and gallium beam nanowriting, demonstrating the full potential of nanopatterned Pd-based organometallic thin films under the most common focused charged beams. The practical applications of combining spin-coated organometallic thin films with focused beam nanowriting in micro- and nano-lithography modern procedures are also discussed in this contribution.

A novel concept and design for highly efficient photoelectrocatalytic materials with high performance, stability, and charge transport properties: development of an innovative next-generation green technology.

In semiconductors, generating charges via catalysis is a highly challenging task and characteristic of heterojunction photoanodes. A dithiophene-4,8-dione spin-coated film layer has a positive effect on the holes (positive charge carriers) for a long time in BHJ films in the solid state of materials. The photoexcited holes created in the BHJ film can persist for long periods of time, which is beneficial for catalytic reactions. In this study, a photoanode is electrically coupled to a hydrogen gas-evolving platinum cathode. When the photoanode is electrically coupled to a H2 gas evolving Pt cathode, curiously long-lived hole polaron states are observed on the timescale of seconds under operational conditions. These long-lived holes play a crucial role in enhancing the hydrogen peroxide oxidation performance of the film overlayer spin-coated onto the photoanode. The spin-coated film overlayer on the photoanode achieves the best oxidation performance for hydrogen peroxide of approximately 6.5 mA cm-2 at 1.23 VRHE without the need of a catalyst. This demonstrates the effectiveness of the overlayer in improving the catalytic performance of the photoanode with a better efficiency of 17.5% when using 851 nm excitation. This indicates that a relatively high percentage of incident photons at that specific wavelength is converted into photocurrent by the photoanode. This approach can lead to more efficient oxidation catalysis as demonstrated in the case of hydrogen peroxide oxidation.

Improving photoluminescence properties and reducing recombination of CsPbBr3 perovskite through lithium doping.

This study investigates the impact of lithium doping on the structural and photophysical properties of spin-coated CsPbBr3 perovskite thin films. The deposited films display a pristine structure, preferentially growing along the (220) direction, and exhibit high-quality green photoluminescence at around 530 nm. The doping leads to an improvement in the optical properties of the films, as evidenced by a stronger photoluminescence (PL) intensity compared to undoped CsPbBr3, particularly at temperatures below 200 K. The increase in PL intensity suggests a decrease in defects and surface passivation. Additionally, the decrease in the power-law exponent β from 1.6 to 1.0 indicates a reduction in non-radiative recombination, likely due to trap states filling with free electrons induced by the doping. Overall, doping with lithium reduces non-radiative recombination, fills trap states, and reduces band tail/activation energy, leading to improved optoelectronic properties of the films. This investigation provides insights into the photophysical properties of the Li-CsPbBr3 absorber layer and the recombination mechanism, and helps to unravel new methods for the development of high-stability, high-performance perovskite thin-film solar cells and optoelectronic devices.

PASCAL: the perovskite automated spin coat assembly line accelerates composition screening in triple-halide perovskite alloys

PASCAL enables systematic exploration and data-driven analysis within the halide perovskite composition space, showcasing its efficacy as an automated platform for solution-processed optoelectronic thin film research.

Real time NIR detection of biogenic amine using an Yb4L4 tetrahedron

Fluorescent sensors of biogenic amines (BAs) due to their excitation or emission in the UV–Vis region, which limits its application in the field of bioanalysis. Herein, an Yb(III) tetrahedral Yb4L34 with ILCT characteristic was constructed from a tris-β-diketone ligand, its spin-coated film shows high sensitivity and fast reversible responses to some BAs with the ppm level detection limit and millisecond response time in NIR region. Compared with Yb4L24, the response time of Yb4L34 was effectively reduced by enlarge the cavity volume and rhombus opening lying on the edges of cage, this indicates that the porosity of film was further enhanced and the interaction time (between Yb4L34 and BAs) was decreased. Moreover, the response time of Yb4L34 was faster than that of most fluorescent amine sensors. In addition, the emission of Yb4L34 in NIR region shows significantly quenching after exposure to the vapor of spoiled fish in 89 ms, which implies that Yb4L34 could be used to real time monitor freshness of food.

Effect of Film Morphology on Electrical Conductivity of PEDOT:PSS.

Commercially available formulations of the popular conductive polymer, poly(3,4-ethylenedioxythiophene):polystyrene sulfonate (PEDOT:PSS) are aqueous dispersions that require the addition of secondary dopants such as dimethyl sulphoxide (DMSO) or ethylene glycol (EG) for fabricated films to have the desired levels of conductivity. CleviosTM F HC Solar, a formulation of PEDOT:PSS produced by Heraeus, GmbH, achieves over 500 S/cm without these secondary dopants. This work studies whether secondary dopants such as DMSO have any additional effect on this type of PEDOT:PSS. The temperature dependencies of the conductivity of F HC Solar spin-coated thin films measured using a four-probe method seem to exhibit different charge transport properties compared with secondary doped PH1000. Observations made using atomic force microscopy (AFM) show that different concentrations of DMSO affect the orientation of the PEDOT domains in the thin film. These morphological changes cause room temperature conductivity to reduce from 640 S/cm in pristine films to as low as 555 S/cm after adding 7 wt% of DMSO along the film. Such tuning may prove useful in future applications of PEDOT:PSS, such as nanoprobes, transistors and hybrid solar cells.

Characterization of Lactoperoxidase (LPO) Enzyme Thin Films for Volatile Organic Compound (VOC) Sensing

Spin-coated thin films of lactoperoxidase enzyme (LPO) were used on conjunction with the bio-composite (chitosan–gelatin), glutaraldehyde and cysteine as first-layers to characterize the interactions on the sensing characteristics. The prospect of tuning these three under-layers is to investigate the change of active vapor binding sites of LPO film after inter-layer interactions. Initially, spin-coated thin film properties of three under-layers and LPO are investigated by reporting deposited mass and layer thickness using the quartz crystal microbalance (QCM) frequency change. LPO spin-coated films with different under-layers are exposed to formic acid, acetic acid, chloroform, acetone and ethyl acetate vapors. The response characteristics of LPO films are investigated via QCM using time dependence frequency recording. LPO films are sensitive to those five vapors and the chemical and the physical properties of the analytes affect the sensitivity and the response rate. The results showed that the structural changes in the thin film affect the number of active binding sites of sensitive layer and thus the sensor response can be enhanced.

Intermolecular interaction-controlled novel azo dyes for use in the high-performance color conversion layers of microdisplays

We synthesized four novel red azo dyes for use in a low-temperature-cured white organic light-emitting diode color conversion layer. The various substituents were introduced into the synthesized dyes to induce steric strain within the base compound for enhancing their solubility. All synthesized dyes exhibited excellent maximum absorption peaks at 521 nm, and AR4, in particular, displayed the highest molar absorptivity of 42 500. Via optimal mixing, the synthesized dyes were used to form red color resists for use in microdisplay color conversion layers. As a white backlight was applied to the optimized spin-coated films, the AR3 and AR4 films, with large dihedral angles between their substituents and diazonium planes, exhibited excellent color coordinates and transmittances, as intermolecular aggregation was inhibited. The color resists fabricated using the AR3 and AR4 dyes also displayed clear micropatterning results, confirming their high compatibility with low-temperature curing binders for use in future display production.

Plasticizer-Induced Enhancement of Mesoscale Dissymmetry in Thin Films of Chiral Polymers with Variable Chain Length.

Conjugated polymers with chiral side chains are of interest in areas including chiral photonics, optoelectronics, and chemical and biological sensing. However, the low dissymmetry factors of most neat polymer thin films have limited their practical application. Here, a robust method to increase the absorption dissymmetry factor in a poly-fluorene-thiophene (PF8TS series) system is demonstrated by varying molecular weight and introducing an achiral plasticizer, polyethylene mono alcohol (PEM-OH). Extending chain length within the optimal range and adding this long-chain alcohol significantly enhance the chiroptical properties of spin-coated and annealed thin films. Mueller matrix spectroscopic ellipsometry (MMSE) analysis shows good agreement with the steady-state transmission measurements confirming a strong chiral response (circular dichroism (CD)and circular birefringence (CB)), ruling out linear dichroism, birefringence, and specific reflection effects. Solid-state NMR studies of annealed hybrid chiral polymer systems show enhancement of signals associated with aromatic π-stacked backbone and the ordered side-chain conformations. Further studies using Raman spectroscopy, X-ray diffraction (XRD), differential scanning calorimetry (DSC), atomic force microscopy (AFM), and polarized optical microscopy (POM) indicate that PEM-OH facilitates mesoscopic crystal domain ordering upon annealing. This provides new insights into routes for tuning optical activity in conjugated polymers.

Mechanistic exploration of charge transport and photosensitivity of metal/polymer/semiconductor (MPS) junction for sensitive light detection applications

Herein, PVA: PVP@Ni(OAc)2 nanocomposite spin-coated thin films have been fabricated as a barrier modifier interlayer in a metal/polymer/semiconductor configuration for light detection applications. The nanostructure, as well as the surface roughness profile of the deposited thin films, have been inspected using a high-resolution transmission electron microscope (HR-TEM) and field emission scan electron microscope (FE-SEM). The obtained results showed nanoplatelet architecture films with smooth surfaces of average roughness of ~ 7.08 nm. The optical absorption, reflection, and transmission spectra have been analyzed and the value of the fabricated film’s energy gap has been confirmed with several analytical approaches. Furthermore, the DC electrical properties of Ag/Si (n-type and p-type), as well as Ag/polymer nanocomposite/Si (n-type and p-type), have been investigated under dark conditions. The microelectronic properties have been estimated using thermionic emission, Norde’s, and Cheung-Cheung’s models. Besides, the mechanistic details of charge transport have been explored under forward and reverse bias conditions. The photoresponsive features of the designed Ag/ PVA/PVP@Ni(OAc)2 /p-Si junction have been evaluated under different illumination intensities. The current device achieved superior photodetection capability with high responsivity, detectivity, and fast switching behavior.

Structural and optical characterization of beta-gallium oxide

Demands for cheaper solar cells have led researchers to less complex, low-temperature, vacuum-free thin-film deposition processes, like spray pyrolysis and sol–gel spin coating. Previous studies of β-Ga2O3 thin-film deposition have used aqueous solutions of gallium nitrate which have strong tendencies to form hydroxide precipitates. This leads to the blockage of spray gun nozzles. To avoid precipitation, tetrahydroxogallate (III) ammonium was used as a novelty precursor in this study for the synthesis of β-Ga2O3. In the spray pyrolysis technique, the precursor was deposited on sapphire substrates at 200 ℃, with a carrier gas pressure of 200 kPa. The same precursor, with added monoethanolamine to enhance viscosity, was used in the spin coating method. A polycrystalline β-Ga2O3 structure was obtained by post-annealing films at 750 ℃ in ambient air. The spin-coated films with thicknesses ranging from 165 to 354 nm exhibited an average crystallite size of 17.78 nm and an optical band gap range between 4.80 eV and 4.95 eV. Films produced by spray pyrolysis had thicknesses ranging between 158 and 255 nm, an average crystallite size of 17.55 nm, and a band gap ranging between 4.69 eV and 4.93 eV. From Raman spectroscopy, the molecular vibrational modes Ag and Bg were detected, featuring three blue shifts and two red shifts. Films showed a UV-blue region originating from oxygen and gallium vacancies in the lattice, an important characteristic for good photodetectors and vital for solar cell passivation. When utilizing β-Ga2O3 as dielectric coating, the refractive index between air and solar cells is reduced, enhancing solar energy absorption. Similar results were obtained for both synthesis techniques confirming the reliability of the methods.

Perovskite BaSnO3 nanoparticles for solar-driven bi-functional photocatalytic activity: PEC water splitting and Wastewater treatment

The highly crystalline n-type BaSnO3 nanoparticles with size ∼30 nm, a larger surface area of ∼15.11 m2·g−1, and a wide optical band gap of 3.24 eV have been synthesized using a co-precipitation route for applications in photoelectrochemical water splitting and organic dye degradation. The spin-coated films of BSO nanoparticles photoanodes exhibited a photocurrent density of 20 μA·cm−2 at a forward bias potential of 0.6 V, a donor carrier density of 2.56 × 1018 cm−3 with a flat band potential of −0.82 V, and four-fold increment in the photocurrent density at a small bias voltage of 0.3 V, under AM 1.5 illumination (100 mW·cm−2). Pseudo-first-order kinetic study showed 96.49 and 95.38 % degradation performance of the Methylene Blue and Crystal Violet dyes at rate constant of 0.0128 and 0.0127 min−1, respectively, under constant irradiation for 240 min in the presence of BSO NPs, which is the highest degradation efficiency reported so far for BSO photocatalyst. The scavenger study revealed the significant role of h+ and ·OH− radicals in the degradation process. Liquid chromatography-mass spectroscopy provides intermediates obtained during the photocatalytic degradation of dyes. The present study focuses on the bifunctional photocatalytic performance of the BSO NPs as a potential candidate for PEC water splitting and wastewater treatment.

Structural and spectroscopic features of naphthol green B integrated for improved light harvesting capability of organic/inorganic hybrid solar cells

Regarding the intensified interest in photovoltaic devices for a wide range of applications, here, we exploited a promising naphthol green organic dye for designing efficient organic/inorganic heterojunction for solar cell applications. The crystal and molecular structures of the spin-coated NGB thin films were inspected using XRD and FTIR techniques, respectively. A nanostructured polycrystalline film was obtained with a crystallite size of ∼76.2 nm with a stable molecular configuration. The optical properties of the films were analyzed using spectrophotometrically measured transmission and reflection. The prepared films showed high absorption over the UV–Vis–NIR regimes with a relatively small energy gap of ∼1.42 eV and a low refractive index of ∼1.48 which increased its suitability for photosensing applicability. The photovoltaic performance of the fabricated Ag/NGB/p-Si/Al heterojunction was evaluated in detail yielding promising photovoltaic characteristics with Voc ∼0.77 V, Jsc ∼18.64 mA/cm2, and PCE ∼6.49 %.

Polyfluorinated Naphthalene-bis-hydrazimide for Solution-Grown n-Type Semiconducting Films.

Naphthalene tetracarboxylic diimides (NDIs), possessing low-lying and tunable LUMO levels, are of wide interest for their aptitude to provide cost-effective, flexible, and environmentally stable n-type organic semiconductors through simple solution processing. NDI-based aromatic hydrazidimides are herein studied in relation to their chemical and environmental stability and as spin-coated stable thin films. In the case of the pentafluorinated residue, these were found to be crystalline, highly oriented, and molecularly flat (roughness = 0.3 nm), based on optical and atomic force microscopy, X-ray diffraction in specular and grazing incidence geometry, and X-ray reflectivity measurements. A new polymorph, previously undetected during the isolation of bulk powders or in their controlled thermal treatments, is found in the thin film and was metrically and structurally characterized from 2D GIWAXS patterns (monoclinic, P2/c, a = 17.50; b = 4.56; c = 14.24 Å; β = 84.8°). This new thin-film phase, TF-F5, is formed no matter whether silicon, glass, or polymethylmethacrylate substrates are used, thus opening the way to the preparation of solution-grown flexible semiconducting films. The TF-F5 films exhibit a systematic and rigorous molecular alignment with both orientation and packing favorable to electron mobility (μ = 0.02 cm2 V-1 s-1). Structural and morphological differences are deemed responsible for the absence of measurable conductivity in thin films of polyfluorinated analogues bearing -CF3 residues on the hydrazidimide aromatic rings.

Thermal Annealing Impact on Optical Properties of Spin-coated P3HT: CdS Thin Film

Polymers are flexible materials that can be easily processed and are formed into a thin film by several methods such as spin-coating, dip-coating, film-casting, and printing. The spin coating method has been extensively utilized in fabricating solution-prepared organic/inorganic electronic devices, this technique is positively efficient in generating thin film apart from being a flexible method to execute. In this study, poly(3-hexylthiophene) (P3HT) material is selected as polymer and cadmium sulphide (CdS) as nanoparticles to produce a hybrid nanocomposite thin film through the process spin-coating method. The P3HT and cadmium ion solution were used to fabricate a thin film onto a quartz glass substrate at a spin speed of 500 rpm for 10 seconds. This spin-coated thin film was heated at different temperatures such as 40°C, 80°C, 120°C, and 160°C for optical properties using a UV-Vis spectrophotometer. The UV-Vis absorption spectra of P3HT: CdS indicated absorption peaks in the UV region, which were ascribed to the band gap of the P3HT: CdS thin film. Our results showed that the optical properties of the P3HT: CdS be contingent on the annealing temperature. The film at room temperature yielded a band gap value of 1.98 eV, at 40°C it resulted in 1.99 eV. The band gap value was increased when annealed at 80°C with 2.02 eV. Annealing temperatures were then raised to 120°C and 160°C, leading to band gap values of 3.11 eV and 2.80 eV respectively.

Optimized structural, optical, and electrical properties of spin-coated Pt(II) octaethylporphyrin thin films for optoelectronic applications

Octaethylporphyrin (PtOEP) is an organic molecule that has unique optical properties, such as high fluorescence quantum yields, strong light absorption, etc. Here we investigate the structural, optical, and electrical characteristics of spin-coated PtOEP thin film. X-ray diffraction (XRD) patterns indicated an increase in the crystallite of the annealed film. Field emission-scanning electron microscope (FESEM) images clearly showed agglomeration and an increase in the nanoparticle size of the annealed film. The Raman spectra of the thin films revealed symmetrical peak positions and improved peak strength for the annealed film. UV-Vis-NIR and photoluminescence (PL) spectroscopy were used to examine optical characteristics. The findings demonstrated that energy gap and PL peak emission were significantly influenced by the grown crystallite size as well as a decrease in lattice defect concentration at the grain boundary during annealing. The optical constant and interband transition strength spectra (Jcv) were estimated and addressed. Based on the linear refractive index and optical gap, third-order nonlinear susceptibility χ(3), nonlinear refractive index n2, and two-photon absorption coefficient, βc of spin-coated PtOEP thin films were calculated and discussed. Finally, the dark current-voltage (J-V) curves were utilized to assess the diode parameters, specifically the zero-bias barrier height (ΦB) and the ideality factor (n), for the ITO/PtOEP/Al diode using thermionic emission theory. Additionally, an investigation was conducted to examine the conduction mechanism of the ITO/PtOEP/Al diode under both forward and reverse bias voltage conditions. On the basis of these findings, spin-coated PtOEP thin films were concluded to be helpful in producing cutting-edge optoelectronic devices.