Solution-processed Thin Films Research Articles

Effect of structure on semiconducting properties of a small molecule n-type organic semiconductor: Phenyl-C61-butyric acid methyl ester

The fullerene-based derivative phenyl-C61-butyric acid methyl ester (PCBM) has attracted attention as an n-type transistor channel and an organic photovoltaic material due to its solution processability, stability, and high electron mobility. However, disorder in solution-processed PCBM thin films makes understanding of charge carrier transport mechanisms difficult. We have fabricated PCBM-based field effect transistors and improved device performance by reducing electron trapping at the dielectric–semiconductor interface and improving charge carrier injection. Single-wall carbon nanotubes were successfully integrated into conventional gold electrodes to improve injection efficiency. Meyer–Neldel behavior has been investigated in a study of charge carrier transport in PCBM thin films. Crystallization of PCBM was observed during the measurement. We find that charge carriers hop between molecules in mostly amorphous regions from 145 to 240 K. The transport is facilitated by the formation of more crystallized regions when samples are heated as high as 240 K.

Improvement in Switching Characteristics and Bias Stability of Solution-Processed Zinc-Tin Oxide Thin Film Transistors via Simple Low-Pressure Thermal Annealing Treatment.

In this study, we used a low-pressure thermal annealing (LPTA) treatment to improve the switching characteristics and bias stability of zinc-tin oxide (ZTO) thin film transistors (TFTs). For this, we first fabricated the TFT and then applied the LPTA treatment at temperatures of 80 °C and 140 °C. The LPTA treatment reduced the number of defects in the bulk and interface of the ZTO TFTs. In addition, the changes in the water contact angle on the ZTO TFT surface indicated that the LPTA treatment reduced the surface defects. Hydrophobicity suppressed the off-current and instability under negative bias stress because of the limited absorption of moisture on the oxide surface. Moreover, the ratio of metal-oxygen bonds increased, while the ratio of oxygen-hydrogen bonds decreased. The reduced action of hydrogen as a shallow donor induced improvements in the on/off ratio (from 5.5 × 103 to 1.1 × 107) and subthreshold swing (8.63 to V·dec-1 and 0.73 V·dec-1), producing ZTO TFTs with excellent switching characteristics. In addition, device-to-device uniformity was significantly improved because of the reduced defects in the LPTA-treated ZTO TFTs.

Low-voltage solution-processed P-type Mg-doped CuI thin film transistors with NAND logic function

Low-voltage electric-double-layer (EDL) p-channel Mg-doped CuI thin-film-transistors (TFTs) have been fabricated on glass substrates at low temperatures. Electrical properties of the solution-processed CuI TFTs with different Mg doping concentrations were investigated. It is observed that compared to undoped CuI TFTs and Mg0.1Cu0.9Ix TFTs, Mg0.05Cu0.95Ix TFTs exhibit an excellent current on/off ratio of 1.1 × 105, a steep subthreshold swing of 21.78 mV/dec, a higher saturation field-effect mobility of 0.95 cm2 V−1 s−1, and the threshold voltage of 1.81 V. The high specific capacitance of 4.7 μF/cm2 is obtained in solution-processed chitosan dielectrics; when it was used as the gate dielectric instead of traditional SiO2, the operating voltage of TFTs can be reduced to 2.5 V. It is noteworthy that the NAND logic function has been realized on the dual in-plane-gate structure of such Mg0.05Cu0.95Ix-based TFTs. Finally, the effects of laser (λ = 638 nm) and negative bias stress (NBS) were observed on Mg0.05Cu0.95Ix TFTs. The transfer curves of the TFT drifted positively as the power of the laser progressively increased; the OFF-state current gradually increased as the NBS time became longer. This paper provides an effective way to improve the performance of p-channel CuI TFTs and indicates that Mg0.05Cu0.95Ix as a promising p-type material for next-generation high-performance low-power-consumption logic circuit applications.

Solution-processed bismuth sulfide incorporated with zinc for high-gain and low-noise photodetection

Bismuth sulfide possesses an extremely high absorption coefficient, a relatively small bandgap, and high charge carrier mobility, which are favorable for photovoltaics and photodetection. However, the device performance of binary Bi2S3 is still limited by the poor charge transport and complicated trap features caused by the stoichiometric imbalance, as both sulfur vacancy and bismuth vacancy could result in tremendous trap states. In this work, we incorporate a small amount of extrinsic elements in the solution-processed Bi2S3 thin films and systematically investigate the influence of extrinsic doping on the charge transport properties of Bi2S3 thin films via time-resolved microwave conductivity and field-effect transistors. We also fabricate photodetectors based on these Zn2+ incorporated Bi2S3 thin films and achieve state-of-the-art device performance, including relatively high on/off ratio, high responsivity, and extremely low dark current and noise, which is promising for next-generation solution-processed photodetection.

Solution-Processed Multiferroic Thin-Films with Large Magnetoelectric Coupling at Room-Temperature.

Experimental realization of thin films with a significant room-temperature magnetoelectric coupling coefficient, αME, in the absence of an external DC magnetic field, has been thus far elusive. Here, a large coupling coefficient of 750 ± 30 mV Oe-1 cm-1 is reported for multiferroic polymer nanocomposites (MPCs) thin-films in the absence of an external DC magnetic field. The MPCs are based on PMMA-grafted cobalt-ferrite nanoparticles uniformly dispersed in the piezoelectric polymer poly(vinylidene fluoride-co-trifluoroethylene, P(VDF-TrFE). It is shown that nanoparticle agglomeration plays a detrimental role and significantly reduces αME. Surface functionalization of the nanoparticles by grafting a layer of poly(methyl methacrylate) (PMMA) via atom transfer radical polymerization (ATRP) renders the nanoparticle miscible with P(VDF-TRFE) matrix, thus enabling their uniform dispersion in the matrix even in submicrometer thin films. Uniform dispersion yields maximized interfacial interactions between the ferromagnetic nanoparticles and the piezoelectric polymer matrix leading to the experimental demonstration of large αME values in solution-processed thin films, which can be exploited in flexible and printable multiferroic electronic devices for sensing and memory applications.

Modification of Two-Dimensional Tin-Based Perovskites by Pentanoic Acid for Improved Performance of Field-Effect Transistors.

Understanding and controlling the nucleation and crystallization in solution-processed perovskite thin films are critical to achieving high in-plane charge carrier transport in field-effect transistors (FETs). This work demonstrates a simple and effective additive engineering strategy using pentanoic acid (PA). Here, PA is introduced to both modulate the crystallization process and improve the charge carrier transport in 2D 2-thiopheneethylammonium tin iodide ((TEA)2 SnI4 ) perovskite FETs. It is revealed that the carboxylic group of PA is strongly coordinated to the spacer cation TEAI and [SnI6 ]4- framework in the perovskite precursor solution, inducing heterogeneous nucleation and lowering undesired oxidation of Sn2+ during the film formation. These factors contribute to a reduced defect density and improved film morphology, including lower surface roughness and larger grain size, resulting in overall enhanced transistor performance. The reduced defect density and decreased ion migration lead to a higher p-channel charge carrier mobility of 0.7 cm2 V-1 s-1 , which is more than a threefold increase compared with the control device. Temperature-dependent charge transport studies demonstrate a mobility of 2.3 cm2 V-1 s-1 at 100 K due to the diminished ion mobility at low temperatures. This result illustrates that the additive strategy bears great potential to realize high-performance Sn-based perovskite FETs.

Efficient Red Light Emitting Diodes Based on a Zero‐Dimensional Organic Antimony Halide Hybrid (Adv. Mater. 9/2023)

Organic Metal Halide Hybrids Efficient electroluminescent devices can now be fabricated using solution-processed thin films based on 0D organic metal halide hybrids (OMHHs). In article number 2209417, Biwu Ma and co-workers develop a highly luminescent 0D OMHH containing organic semiconducting cations, which successfully addresses the issues of low conductivity and poor energy alignment of existing 0D OMHHs for electrically driven light-emitting diodes (LEDs).

Fully solution-processed carbon nanotubes thin film transistors and PMOS inverters on glass substrate

We report fully solution-processed thin film transistors and PMOS inverters fabricated on glass substrates using single-walled carbon nanotubes (SWCNTs) as active semiconducting material. All the electrodes (gate, source, and drain) were inkjet-printed using silver (Ag) as conductive ink. Spin coated poly-4-vinylphenol dielectric was optimized in terms of thickness and heating conditions for solution-processed SWCNTs thin film transistors to achieve a mobility equal to 0.81 cm2 V−1s−1. We will show that, hole traps at the dielectric-semiconductor interface are responsible for the hysteresis in the transfer curve, and controlled by the different sweep rate of the gate field. Drain-current transients under different bias conditions were studied and the increase in current occurs due to slow polarizations of residual dipolar groups in the dielectric. The adopted technology has been exploited to fabricate a PMOS inverter and studied for high gain and noise margin values at the supply voltage, V DD = −40 V.

Preparation of solution-processed thin films of As-S-Se system from As40S60 solution modified by amorphous selenium

This work presents the possibility of As-S-Se chalcogenide glass thin film preparation from a solution of commercially available As40S60 glass by modification of the solution composition with elemental selenium. We studied the dissolution of elemental selenium in n-butylamine and ethylenediamine based chalcogenide glass solutions.Samples of four compositions ranging from 0% selenium content (pure As40S60) to 30% selenium content (As28S42Se30) were prepared by spin-coating in specular optical quality with low surface roughness (below 1 nm). Structure, refractive index, optical band gap, organic residua content, and chemical resistance were studied in dependence on the annealing temperature. The structure was studied using Raman spectroscopy, and the data suggest incorporation of selenium into the glass structure already in the solution, which resulted in an increased refractive index and reduced optical band gap of deposited thin films. Due to chalcogen over-stoichiometry, modified thin films have lower organic residua content.

Diethanolamine Modified Perovskite-Substrate Interface for Realizing Efficient ESL-Free PSCs.

Simplifying device layout, particularly avoiding the complex fabrication steps and multiple high-temperature treatment requirements for electron-selective layers (ESLs) have made ESL-free perovskite solar cells (PSCs) attractive. However, the poor perovskite/substrate interface and inadequate quality of solution-processed perovskite thin films induce inefficient interfacial-charge extraction, limiting the power conversion efficiency (PCEs) of ESL-free PSCs. A highly compact and homogenous perovskite thin film with large grains was formed here by inserting an interfacial monolayer of diethanolamine (DEA) molecules between the perovskite and ITO substrate. In addition, the DEA created a favorable dipole layer at the interface of perovskite and ITO substrate by molecular adsorption, which suppressed charge recombination. Comparatively, PSCs based on DEA-treated ITO substrates delivered PCEs of up to 20.77%, one of the highest among ESL-free PSCs. Additionally, this technique successfully elongates the lifespan of ESL-free PSCs as 80% of the initial PCE was maintained after 550 h under AM 1.5 G irradiation at ambient temperature.

Delineating magnetization dynamics in solution-processed doped yttrium iron garnet thin films

In this work, thin films of ruthenium-doped and cerium-doped yttrium iron garnet were deposited on silicon using solgel chemistry. Doped YIG could be produced in phase pure form up to a precursor stoichiometry of Y3Ru0.1Fe4.9O12 and Ce0.7Y2.3Fe5O12. Both dopants significantly increase the coercivity and anisotropy field of the materials either due to domain wall pinning or increased spin–orbit coupling from the dopant. To delineate these two effects, the dynamic magnetic properties were studied using strip line ferromagnetic resonance (FMR). The FMR linewidth was separated into intrinsic loss and inhomogeneous line broadening. Inhomogeneous line broadening was found to dominate the magnetic losses in all the films likely due to magnon scattering off grain boundaries, but the Gilbert damping remained fairly low. By comparing the two dopants, it was found that Gilbert damping increased more in Ce:YIG films than in Ru:YIG films. This finding was corroborated by changes in the anisotropy field of the films, indicating a larger contribution from spin–orbit coupling from cerium than from ruthenium. Surprisingly, while magnetic loss globally increased with higher substitution, adding a small amount of dopant actually reduced the inhomogeneous line broadening in both sets of films. This was corroborated by crystallite size. The damping in Ru:YIG also decreased with a small amount of the dopant, which has been predicted by Kittel for doped garnets. Thus, it follows that there is an ideal doping regime where solgel YIG can be doped at low levels without increasing magnetic loss.

Highly sensitive UV photodetector based on solution-processed bismuth oxyiodide epitaxial thin films

The as-fabricated photodetector based on high quality bismuth oxyiodide epitaxial thin film exhibited promising optoelectrical performance under UV light illumination and a tunable photoresponse mechanism depending on the film thickness.

Effect of channel thickness on radiation hardness of solution-processed oxide thin film transistors

The electrical properties of a-ZITO TFTs with different channel thicknesses were characterized under proton irradiation with electrical stress. The device measurements showed stronger radiation-tolerance of oxide TFTs with smaller channel thickness.

In situphotogenerated hydroxyl radicals in the reaction atmosphere for the accelerated crystallization of solution-processed functional metal oxide thin films

We propose a disruptive method to accelerate the crystallization at low temperatures of functional metal oxide films whereby hydroxyl radicals (•OH) are photogeneratedin situfrom the atmosphere where solution-deposited layers are UV-irradiated.

From synthesis to device fabrication: elucidating the structural and electronic properties of C7-BTBT-C7

Synthesis, polymorph investigation, crystallographic study, and fabrication of OFETs in solution-processed thin films of C7-BTBT-C7.

Achieving High-Performance Solution-Processed Thin-Film Transistors by Doping Strong Reducibility Element Into Indium-Zinc-Oxide

Achieving High-Performance Solution-Processed Thin-Film Transistors by Doping Strong Reducibility Element Into Indium-Zinc-Oxide

Effect on electrical properties of CuI thin film prepared by a spin coating technique

Copper Iodide (CuI) is a p-type semiconductor that is an inorganic semiconductor with significant applications in the thin film. It has potential application in solar cells as a hole transport layer, done by spin coating technique with annealing. The Hall-measurement system investigated the different annealing temperatures of solution-processed CuI thin films. The CuI thin films were p-type semiconductors with resistivities of 0.5–7.4 Ω cm, a carrier concentration of ∼ 1019 cm−3, and mobility of < 24 cm2 V−1 s−1, respectively. It was found that by increasing the annealing temperature above 220 °C, the resistivity of CuI thin films also decreased.

Low-temperature crystallization of indium oxide thin films with a photoactivable additive

In this study, we report a simple route to the low-temperature crystallization of solution-processed indium oxide thin films by introducing ammonium nitrate in the sol–gel metal oxide precursor solution as photoactivable additive and applying deep ultraviolet (DUV) irradiation onto the as-spun oxide films in an inert atmosphere. Thermal and structural analyses revealed that the initial temperatures for condensation and crystallization were reduced down to 130 and 200 °C, respectively, by the in situ generation of reactive chemical species enabled by DUV-assisted nitrate photolysis. Furthermore, transmission electron microscopy confirmed that the degree of indium oxide film crystallinity was gradually enhanced as the amount of nitrate in the precursor solution was increased. Finally, electrical characterizations showed that carrier mobility, threshold voltage, subthreshold swing, and threshold voltage shift under the positive bias stress of sol–gel indium oxide thin-film transistors were improved from 0.21 to 5.03 cm2/V s, from 4.18 to 1.64 V, from 1.33 to 0.72 V/dec, and from 6.44 to 4.04 V, respectively, by combining ammonium nitrate and DUV photoactivation.

Photocurrent generation and charge transport mechanism study in solution-processed CZTS thin films

Clean, benign and economical energy harvesting is envisioned to mitigate the global climate change – originated from the burning of fossil fuels – addressing both the energy crises and environmental issues. In this work, charge transport mechanism and the dynamics of photocurrent generation in thin films of CZTS nanocrystals is studied. A liquid phase processing route – owing to low temperature – has been adopted using a molecular based precursor solution for the in-situ development of CZTS crystals during film deposition. Results shows that charge carriers follow band conduction and nearest-neighbor hopping (NNH) mechanisms at elevated temperatures while Mott variable-range hopping (VRH) is the dominating phenomenon at low temperatures which are analogues to expensive vacuum-deposited kieserite thin films behavior.

Solution-processed CZTS thin films and its simulation study for solar cell applications with ZnTe as the buffer layer.

Using zinc tellurium (ZnTe) as the buffer layer in the Cu2ZnSnS4 (CZTS)-based solar cells showed an improvement in overall efficiency. ZnTe is investigated as an alternative to replace the conventional toxic Cd-contained buffer layers. It may also reduce the overall cost of these cells as both layers (ZnTe and CZTS) have eco-friendly and earth-abundant constituents. The sol-gel spin coating method is used for the deposition of CZTS thin films on the corning glass substrates. The X-ray diffraction studies showed the peaks corresponding to (112), (200), (220), and (312) planes which confirmed the formation of the essential kesterite phase. The optical band gap of the deposited films was found at around 1.45eV by the UV-visible-NIR spectrophotometer. The optimum thickness of the absorber layer (CZTS) and buffer layer (ZnTe) was investigated based on the performance of the ZnO:Al/ZnO/ZnTe/CZTS/Mo cell structure by using the AMPS-1D simulation tool. In contrast, the tool was molded by the experimentally investigated data for the constituent materials of the cell structure. The solar cells' efficiency was increased by 23.47% at 2500nm and 50nm thickness of the CZTS and ZnTe layers, respectively. In addition, it was analyzed and found that the current density value showed an improvement with operating temperature as it is one of the requirements in the high solar radiation areas where the temperature even rises more than 50°C in the summer.