Ultrastable 3D Heterogeneous Integration via N-Heterocyclic Carbene Self-Assembled Nanolayers.

The commercialization of 3D heterogeneous integration through hybrid bonding has accelerated, and accordingly, Cu-polymer bonding has gained significant attention as a means of overcoming the limitations of conventional Cu-SiO2 hybrid bonding, offering high compatibility with other fabrication processes. Polymers offer robust bonding strength and a low dielectric constant, enabling high-speed signal transmission with high reliability, but suffer from low thermomechanical stability. Thermomechanical stability of polymers was not achieved previously because of thermal degradation and unstable anchoring. To overcome these limitations, wafer-scale Cu-polymer bonding via N-heterocyclic carbene (NHC) nanolayers was presented for 3D heterogeneous integration, affording ultrastable packing density, crystallinity, and thermal properties. NHC nanolayers were deposited on copper electrodes via electrochemical deposition, and wafer-scale 3D heterogeneous integration was achieved by adhesive bonding at 170 °C for 1 min. Ultrastable conductivity and thermomechanical properties were observed by the spatial mapping of conductivity, work function, and force-distance curves. With regard to the characterization of NHC nanolayers, low-temperature bonding, robust corrosion inhibition, enhanced electrical conductivity, back-end-of-line process compatibility, and fabrication process reduction, NHC Cu/polymer bonding provides versatile advances in 3D heterogeneous integration, indicating that NHC Cu/polymer bonding can be utilized as a platform for future 3D vertical chip architectures.

Free-standing two-dimensional ferro-ionic memristor.

Two-dimensional (2D) ferroelectric materials have emerged as significant platforms for multi-functional three-dimensional (3D) integrated electronic devices. Among 2D ferroelectric materials, ferro-ionic CuInP2S6 has the potential to achieve the versatile advances in neuromorphic computing systems due to its phase tunability and ferro-ionic characteristics. As CuInP2S6 exhibits a ferroelectric phase with insulating properties at room temperature, the external temperature and electrical field should be required to activate the ferro-ionic conduction. Nevertheless, such external conditions inevitably facilitate stochastic ionic conduction, which completely limits the practical applications of 2D ferro-ionic materials. Herein, free-standing 2D ferroelectric heterostructure is mechanically manipulated for nano-confined conductive filaments growth in free-standing 2D ferro-ionic memristor. The ultra-high mechanical bending is selectively facilitated at the free-standing area to spatially activate the ferro-ionic conduction, which allows the deterministic local positioning of Cu+ ion transport. According to the local flexoelectric engineering, 5.76×102-fold increased maximum current is observed within vertical shear strain 720 nN, which is theoretically supported by the 3D flexoelectric simulation. In conclusion, we envision that our universal free-standing platform can provide the extendable geometric solution for ultra-efficient self-powered system and reliable neuromorphic device.

High-Throughput Roll-to-Roll Processed Large-Area Perovskite Solar Cells Using Rapid Radiation Annealing Technique.

The development of a stable roll-to-roll (R2R) process for flexible large-area perovskite solar cells (PSCs) and modules is a pressing challenge. In this study, we introduced a new R2R PSC manufacturing system that employs a two-step deposition method for coating perovskite and uses intensive pulsed light (IPL) for annealing. This system has successfully fabricated small-sized cells and the first-ever large-sized, R2R-processed flexible modules. A key focus of our work was to accelerate the conversion of PbI2 to perovskite. To this end, we utilized IPL annealing and incorporated additives into the PbI2 layer. With these modifications, the R2R-processed perovskite films achieved a power conversion efficiency (PCE) of 16.87%, representing the highest reported value for R2R two-step processed PSCs. However, these cells exhibited hysteresis in reverse and forward PCE measurements. To address this, we introduced a dual-annealing process consisting of IPL followed by a 2-min thermal heating step. This approach successfully reduced hysteresis, resulting in low-hysteresis, R2R-processed flexible PSCs. Moreover, we fabricated large-scale flexible modules (10 × 10 cm2) with a PCE of 11.25% using the dual-annealing system, marking a significant milestone in this field.

One-Shot Remote Integration of Macromolecular Synaptic Elements on a Chip for Ultrathin Flexible Neural Network System.

The field of biomimetic electronics that mimic synaptic functions has expanded significantly to overcome the limitations of the von Neumann bottleneck. However, the scaling down of the technology has led to an increasingly intricate manufacturing process. To address the issue, this work presents a one-shot integrable electropolymerization (OSIEP) method with remote controllability for the deposition of synaptic elements on a chip by exploiting bipolar electrochemistry. Condensing synthesis, deposition, and patterning into a single fabrication step is achieved by combining alternating-current voltage superimposed on direct-current voltage-bipolar electropolymerization and a specially designed dual source/drain bipolar electrodes. As a result, uniform 6 × 5 arrays of poly(3,4-ethylenedioxythiophene) channels are successfully fabricated on flexible ultrathin parylene substrates in one-shot process. The channels exhibited highly uniform characteristics and are directly used as electrochemical synaptic transistor with synaptic plasticity over 100 s. The synaptic transistors have demonstrated promising performance in an artificial neural network (NN) simulation, achieving a high recognition accuracy of 95.20%. Additionally, the array of synaptic transistor is easily reconfigured to a multi-gate synaptic circuit to implement the principles of operant conditioning. These results provide a compelling fabrication strategy for realizing cost-effective and disposable NN systems with high integration density.

Controlling Fluorination Density of Soluble Polyimide Gate Dielectrics and its Influence on Organic Crystal Growth and Device Operational Stability.

Fluorinated polyimides (PIs) are among the most promising candidates for gate dielectric materials in organic electronic devices because of their solution processability and outstanding chemical, mechanical, and thermal stabilities. Additionally, fluorine (F) substitution improves the electrical properties of PI thin films, such as enhanced dielectric properties and reduced surface trap densities. However, the relationship between the fluorination density of PIs and crystal growth modes of vacuum-deposited conjugated molecules on PI thin films, which is directly related to the lateral charge transport along the PI-organic semiconductor interface, has not been systematically studied. Herein, five different soluble PIs with different F densities were synthesized, and the correlation between fluorination and thin-film properties was systematically investigated. Not only were their dielectric properties modulated, but the growth modes of the organic molecules deposited on the PI thin films also changed with increasing surface F density. This phenomenon was observed by both surface and crystallographic analyses, which resulted in extremely high operational stability of field-effect transistors and the successful fabrication of organic complementary circuits. We believe that the correlation between PI backbone fluorination and its thin-film properties will provide practical insights into the material design based on controlled molecular directed surface assembly on fluorinated polymer dielectrics.

Low-Temperature Alignment of Conjugated Polymers by Plasticizer-Aided Physical Rubbing.

Rubbing-induced alignment of conjugated polymers is systematically investigated in terms of intra- and inter-molecular interaction. Various polymer films with a broad range of polymer chain rigidity are rubbed, and the degree of polymer chain alignment is quantitatively characterized. The rubbing technique effectively aligns crystalline domains in conjugated polymer films when the temperature approaches the critical rubbing temperature ( T r c $T_{\mathrm{r}}^{\mathrm{c}}$ ), at which the rearrangement and the slip of polymer chains are possible. A polymer with significant intra-/inter-molecular interactions exhibits higher T r c $T_{\mathrm{r}}^{\mathrm{c}}$ , though quantitative analysis reveals an intermediately aligned state at temperature Tr ' lower than T r c $T_{\mathrm{r}}^{\mathrm{c}}$ . This state originates from polymer chain aggregation in an amorphous domain. The intermediately aligned state can be controlled by plasticizer, which enables low-temperature alignment of high-mobility polymer film by reducing Tr ' to near 100 °C, increases the crystallinity, and improves the alignment effect at this state comparable to that of the completely aligned state obtained at extremely high temperatures.

Achieving ideal transistor characteristics in conjugated polymer semiconductors.

Organic thin-film transistors (OTFTs) with ideal behavior are highly desired, because nonideal devices may overestimate the intrinsic property and yield inferior performance in applications. In reality, most polymer OTFTs reported in the literature do not exhibit ideal characteristics. Supported by a structure-property relationship study of several low-disorder conjugated polymers, here, we present an empirical selection rule for polymer candidates for textbook-like OTFTs with high reliability factors (100% for ideal transistors). The successful candidates should have low energetic disorder along their backbones and form thin films with spatially uniform energetic landscapes. We demonstrate that these requirements are satisfied in the semicrystalline polymer PffBT4T-2DT, which exhibits a reliability factor (~100%) that is exceptionally high for polymer devices, rendering it an ideal candidate for OTFT applications. Our findings broaden the selection of polymer semiconductors with textbook-like OTFT characteristics and would shed light upon the molecular design criteria for next-generation polymer semiconductors.

Disordered Phase-Assisted Growth of Organic Semiconductor Crystals on Self-Assembled Monolayer Templates.

Achieving high mobility and bias stability is a challenging obstacle in the advancement of organic thin-film transistors (OTFTs). To this end, the fabrication of high-quality organic semiconductor (OSC) thin films is critical for OTFTs. Self-assembled monolayers (SAMs) have been used as growth templates for high-crystalline OSC thin films. Despite significant research progress in the growth of OSC on SAMs, a detailed understanding of the growth mechanism of the OSC thin films on a SAM template is lacking, which has limited its use. In this study, the effects of the structure (thickness and molecular packing) of SAM on the nucleation and growth behavior of the OSC thin films were investigated. We found that disordered SAM molecules assisted in the surface diffusion of the OSC molecules and resulted in a small nucleation density and large grain size of the OSC thin films. Moreover, a thick SAM with disordered SAM molecules on the top was found to be beneficial for the high mobility and bias stability of the OTFTs.

Fluorination-Induced Charge Trapping and Operational Instability in Conjugated-Polymer Field-Effect Transistors.

Fluorination of a conjugated polymer backbone is an effective strategy to control the microstructure and electronic structure of a conjugated polymer. Although fluorination has been widely reported to increase charge carrier mobility, its effect on the operational stability of electronic devices has not been extensively investigated. Here, the effect of fluorination of a conjugated polymer backbone on charge trapping and the operational stability of organic field-effect transistors is investigated. The results show that the device based on a fluorinated conjugated polymer exhibits relatively poor operational stability despite its greater charge carrier mobility compared with that in the device based on its nonfluorinated polymer counterpart. Experimental results reveal that the low stability originates from the greater degree of shallow trapping of charge carriers within the fluorinated polymer thin film and that the shallow trapping is closely related to the presence of minority charge carriers. A mechanism of charge trapping is proposed.

Novel Dithienopyrrole-Based Conjugated Copolymers: Importance of Backbone Planarity in Achieving High Electrical Conductivity and Thermoelectric Performance.

The development of conjugated polymers with structures that are suitable for efficient molecular doping and charge transport is a key challenge in the construction of high-performance conjugated polymer-based thermoelectric devices. In this study, three novel conjugated polymers based on dithienopyrrole (DTP) are synthesized and their thermoelectric properties are compared. When doped with p-dopant, a donor-acceptor type copolymer, DPP-MeDTP, exhibits higher electrical conductivity and thermoelectric power factor compared to the other donor-donor type copolymers. The high electrical conductivity of DPP-MeDTP compared to the other polymers originates from the high degree of backbone planarity and molecular order, which contributes to its high charge carrier mobility. In addition, the highly crystalline structure of DPP-MeDTP is well maintained upon doping, while the crystalline order of the other polymers decreases significantly upon doping. The findings of this work not only provide insights into the design of DTP-based conjugated polymers for thermoelectric use but also demonstrate the significance of a high degree of molecular order and structural robustness upon doping to achieve high thermoelectric performance.

Effect of Providing Environmental Enrichment into Aviary House on the Welfare of Laying Hens.

This study aimed to determine the effects of providing environmental enrichment materials­pumice stone and alfalfa hay­to laying hens in the aviary system. A total of 2196 40-week-old Hy-Line Brown laying hens were randomly allotted to three treatment groups: (1) no enrichment (control; CON), (2) enrichment with pumice stone (PS), and (3) enrichment with alfalfa hay (HAY). Each treatment comprised four replicates of 183 hens each, and four of the same materials were provided per replicate. The experiment lasted for 26 weeks. Feed and water were provided ad libitum. As a result, the PS and HAY groups demonstrated increased egg production (p < 0.001). The HAY group showed a reduced rate of mislaid eggs (p < 0.01) and produced low egg weight and pale-yellow yolk (p < 0.05). Both enrichment materials decreased blood creatinine (CRE) or lactate dehydrogenase (LDH) in the blood and resulted in a significantly lower corticosterone (CORT) level (p < 0.05). However, the feather condition scores for the laying hens were similar across all treatments (p > 0.05). In summary, although pumice stone and alfalfa hay are effective in alleviating stress and improving the production of laying hens, additional environmental improvement studies are needed to contribute to reducing pecking behaviors in poultry farming.

Solution-Processable Semiconducting Conjugated Planar Network.

After the emergence of graphene in the material science field, top-down and bottom-up studies to develop semiconducting organic materials with layered structures became highly active. However, most of them have suffered from poor processability, which hampers device fabrication and frustrates practical applications. Here, we suggest an unconventional approach to fabricating semiconducting devices, which avoids the processability issue. We designed a soluble amorphous network using a solution process to form a thin film on a substrate. We then employed heat treatment to develop a flattened organic structure in the thin film, as an active layer for organic thin-film transistors (TFTs). The fabricated TFTs showed good performance in both horizontal and vertical charge transport, suggesting a versatile and useful approach for the development of organic semiconductors.

Direct Laser Interference Ink Printing Using Copper Metal-Organic Decomposition Ink for Nanofabrication.

In this study, we developed an effective and rapid process for nanoscale ink printing, direct laser interference ink printing (DLIIP), which involves the photothermal reaction of a copper-based metal-organic decomposition ink. A periodically lined copper pattern with a width of 500 nm was printed on a 240 µm-wide line at a fabrication speed of 17 mm/s under an ambient environment and without any pre- or post-processing steps. This pattern had a resistivity of 3.5 µΩ∙cm, and it was found to exhibit a low oxidation state that was twice as high as that of bulk copper. These results demonstrate the feasibility of DLIIP for nanoscale copper printing with fine electrical characteristics.

Effects of Animal Welfare-Certified Rearing Systems on the Blood Parameters and Meat Quality Characteristics of Broilers at the Farm Level in Korea.

Compared to the conventional farms (CF) rearing of broilers, the rearing management of animal welfare-certified farms (AF) must provide low stocking density, perch, air regulation, and feeding plant-based protein. This study aimed to compare the effects of rearing management in CF and AF on blood parameters, meat quality, and bioactive compound content in Ross 308 broiler chickens at the farm level before transportation to slaughterhouses. Blood and meat samples were obtained at 28-35-day-old chickens from three CF and three AF. In blood samples, low-density lipoprotein cholesterol (p<0.05), triglyceride (p<0.001), glucose (p<0.01), total protein (p<0.001), albumin (p<0.01), and white blood cell (p<0.001) levels as well as the heterophil/ lymphocyte ratio [stress index (SI), p<0.001] were lower in broilers from AF than in CF. In meat samples, shear force (p<0.001, p<0.05), and carnosine contents (p<0.001, p<0.05) in both breast and thigh meat from AF were higher than those in meat from CF. The contents of linoleic acid (p<0.001), α-linolenic acid (p<0.001), and eicosapentaenoic acid (p<0.05) were higher in the samples from AF than those from CF. This study reveals that such differences are influenced by the different rearing factors in nutrition, housing, and management practices between CF and AF. Supplementation of plant-based protein and enough space to move due to lower stocking density accounts for the large differences between them. These results can be used as preliminary data showing that the AF system reduces the SI and enhances carnosine and polyunsaturated fatty acids levels in chicken meat at the farm level before transportation.

Studies on the concentrations of particulate matter and ammonia gas from three laying hen rearing systems during the summer season.

This study aimed to measure the concentrations of particulate matter (PM10, PM2.5) and ammonia gas (NH3) from different types of laying hen houses during summer. The treatment groups included conventional cage, floor pens, and aviary system, with tunnel ventilation system applied to all poultry houses. The PM10 concentration was highest in the aviary system from 10:00 h to 18:30 h, whereas in the cage, it remained high after 18:30 h until 7:30 h the next day. The cage showed high levels of PM2.5 from 18:30 h to 7:30 h the next day. The correlation between the three breeding systems showed an R2 < 0.2. The mean daily concentrations of PM10, PM2.5, and NH3 were highest in the cage, among all the poultry houses. On comparing the two welfare breeding systems (floor pens and aviary system), particulate matter concentrations were higher in the floor pens, while the aviary system had higher level of NH3. However, no significant differences were observed between the concentrations of PM10, PM2.5, and NH3 between the three laying hen houses in summer. This study provides basic data for improving the rearing environment in the three different types of poultry housing systems.

Metal-Organic Framework as a Functional Analyte Channel of Organic-Transistor-Based Air Pollution Sensors.

Air pollution sensors based on organic transistors have attracted much interest recently; however, the devices suffer from low responsivity and slow response and recovery rates for gas analytes. These shortcomings are attributed to the low charge-carrier mobility of organic semiconductors and to a structural limitation resulting from the use of a thick and continuous active layer. In the present work, we investigated the material properties of a multiscale porous zeolitic imidazolate framework, [Zn(2-methylimidazole)2]n (ZIF-8), and examined its potential as an analyte channel material inserted at an organic-transistor active layer. A series of carbonized zeolitic imidazolate frameworks (ZIFs) were prepared by thermal conversion of ZIF-8 and also studied for comparison. The microstructures, morphologies, and optical/electrical characteristics of polythiophene/ZIF-8 hybrid films were systematically investigated. Organic-transistor-type nitrogen dioxide sensors based on the polythiophene/ZIF-8 hybrid films showed substantially improved sensing properties, including responsivity, response rate, and recovery rate. The electrical conductivity of the carbonized ZIF-8s enhanced the field-effect mobility of the organic transistors; however, the sensing performance was not improved, because of the closed pore structures resulting from the carbonization. These results provide invaluable information and useful insights into the design of transistor-type gas sensors based on organic semiconductor/metal-organic framework hybrid films.

π-Extended Thiazole-Containing Polymer Semiconductor for Balanced Charge-Carrier Mobilities.

A low-band gap semiconducting polymer with an acceptor-donor-acceptor architecture is newly designed and synthesized by incorporating a π-extended thiazole-vinylene-thiazole unit. The resulting thiazole-containing diketopyrrolopyrrole copolymer exhibits well-balanced ambipolar characteristics with hole mobility of up to 0.11 cm2 V-1 s-1 and electron mobility of up to 0.30 cm2 V-1 s-1 , which are suitable for applications in polymer electronics.

Charge Trapping in a Low-Crystalline High-Mobility Conjugated Polymer and Its Effects on the Operational Stability of Organic Field-Effect Transistors.

The effects of the microstructure of conjugated polymer thin films on charge trapping and operational stability of organic field-effect transistors (OFETs) are investigated. Device characteristics of OFETs based on two model conjugated polymers, poly(3-hexylthiophene) (P3HT) and a random 3-hexylthiophene-thiophene copolymer (RP33), are compared. P3HT films have high crystallinity and long-range molecular order, whereas RP33 films have low crystallinity and short-range molecular order as well as enhanced polymer backbone planarity. Experimental evidence shows that although the microstructure of the RP33 film provides efficient charge transport pathways, its high degree of structural disorder causes severe shallow trapping of charge carriers, which results in its inferior stability under bias stress. This study demonstrates that low-crystalline conjugated polymers with short-range order can provide a high charge-carrier mobility but at the same time be inappropriate for practical OFETs because of their poor intrinsic operational stability.

Formation of Large Crystalline Domains in a Semiconducting Polymer with Semi-fluorinated Alkyl Side Chains and Application to High-Performance Thin-Film Transistors.

The semi-fluorinated alkyl (SFA) side chain introduced thienylenevinylene (TV)-based p-type polymer, PC12TVC5F7T, was synthesized for use in organic thin-film transistors (OTFTs). Herein, we investigated the influence of SFA side chains on the morphology, molecular orientation, and crystalline structure using a combination of atomic force microscopy (AFM), scanning electron microscopy (SEM), two-dimensional (2D) grazing-incidence wide-angle X-ray scattering (GIWAXS), and density functional theory (DFT) calculations. Interestingly, the incorporation of SFA side chains led to the evolution of plate-like large-sized domains and also strongly intermolecular stacked high crystalline structures. Furthermore, due to the strong interactions between SFA side chains, several (00h) peaks could be observed for PC12TVC5F7T, in spite of their fairly large dihedral angle. As a result, due to the well-developed microstructure of PC12TVC5F7T, the OTFT devices based on it exhibited a high hole mobility of 1.91 cm2 V-1 s-1, which is an outstanding value among the poly(thiophene) derivative polymers. These observations indicate that large-sized domains and strongly intermolecular stacked high crystalline structures, which are beneficial for charge carrier transport, could be attained by the introduction of SFA side chains, further enhancing the performance of the OTFTs.

Anisotropy of Charge Transport in a Uniaxially Aligned Fused Electron-Deficient Polymer Processed by Solution Shear Coating.

Precise control of the microstructure in organic semiconductors (OSCs) is essential for developing high-performance organic electronic devices. Here, a comprehensive charge transport characterization of two recently reported rigid-rod conjugated polymers that do not contain single bonds in the main chain is reported. It is demonstrated that the molecular design of the polymer makes it possible to achieve an extended linear backbone structure, which can be directly visualized by high-resolution scanning tunneling microscopy (STM). The rigid structure of the polymers allows the formation of thin films with uniaxially aligned polymer chains by using a simple one-step solution-shear/bar coating technique. These aligned films show a high optical anisotropy with a dichroic ratio of up to a factor of 6. Transport measurements performed using top-gate bottom-contact field-effect transistors exhibit a high saturation electron mobility of 0.2 cm2 V-1 s-1 along the alignment direction, which is more than six times higher than the value reported in the previous work. This work demonstrates that this new class of polymers is able to achieve mobility values comparable to state-of-the-art n-type polymers and identifies an effective processing strategy for this class of rigid-rod polymer system to optimize their charge transport properties.