Metal Organic Decomposition Research Articles

Laser Sintering by Spot and Linear Optics for Inkjet-Printed Thin-Film Conductive Silver Patterns with the Focus on Ink-Sets and Process Parameters

The implementation of the laser sintering for inkjet-printed nanoparticles and metal organic decomposition (MOD) inks on a flexible polymeric film has been analyzed in detail. A novel approach by implementing, next to a commonly 3.2 mm diameter spot laser optic, a line laser optic with a laser beam area of 2 mm × 80 mm, demonstrates the high potential of selective laser sintering to proceed towards a fast and efficient sintering methodology in printed electronics. In this work, a multiplicity of laser parameters, primary the laser speed and the laser power, have been altered systematically to identify an optimal process window for each ink and to convert the dried and non-conductive patterns into conductive and functional silver structures. For each ink, as well as for the two laser optics, a suitable laser parameter set has been found, where a conductivity without any damage to the substrate or silver layer could be achieved. In doing so, the margin of the laser speed for both optics is ranging in between 50 mm/s and 100 mm/s, which is compatible with common inkjet printing speeds and facilitates an in-line laser sintering approach. Considering the laser power, the typical parameter range for the spot laser lays in between 10 W and 50 W, whereas for the line optics the full laser power of 200 W had to be applied. One of the nanoparticle silver inks exhibits, especially for the line laser optic, a conductivity of up to 2.22 × 107 S‧m−1, corresponding to 36% of bulk silver within a few seconds of sintering duration. Both laser sintering approaches together present a remarkable facility to use the laser either as a digital tool for sintering of defined areas by means of a spot beam or to efficiently sinter larger areas by means of a line beam. With this, the utilization of a laser sintering methodology was successfully validated as a promising approach for converting a variety of inkjet-printed silver patterns on a flexible polymeric substrate into functionalized conductive silver layers for` applications in the field of printed electronics.

Thermal decomposition temperature-dependent bonding performance of Ag nanostructures derived from metal–organic decomposition

In wide-bandgap semiconductor power device packaging, die bonding refers to attaching the die to substrate. Thereby, the process temperature of Ag sintering for the die bonding should be low to prevent damage to fragile dies. Herein, an organic-free strategy using Ag nanostructures derived from the thermal decomposition of metal–organic decomposition (MOD) was proposed to achieve low-temperature bonding. Significant effects on bonding performance were determined by the thermal decomposition temperature, which in turn determined the organic content and sintering degree of Ag nanostructures. At a low thermal decomposition temperature of 160 °C, incomplete decomposition resulted in high organic content in the Ag nanostructures, causing large pores inside the Ag joints owing to the generation of gaseous products. Owing to the Ag particles with naked surfaces and wide size distribution, the Ag nanostructure obtained at 180 °C showed an excellent bonding performance, resulting in a high shear strength of 31.1 MPa at a low bonding temperature of 160 °C. As the thermal decomposition temperature was 200 °C, sintering among Ag particles increased the particle size, resulting in a reduction of surface energy and driving force for sintering. We think that uncovering this underlying mechanism responsible for the bonding performance will promote the application of Ag MOD in the die bonding of WBG power devices.Graphical abstract

Anomalous Temperature Effect on the Deposition Morphology in Reactive Inkjet Printing

Reactive inkjet (RIJ) printing represents an important approach for printed electronics. Different from the traditional inkjet printing of colloidal inks with nanosized metal particles, RIJ prints the solution of metal organic compound, that is, metal‐organic decomposition (MOD) ink, and reduces it to the pure metal during the post‐treatment to form conductive electrodes. Successful RIJ printing of MOD inks has been demonstrated; however, the fundamental understanding of droplet deposition involved in RIJ printing is lacking. Herein, the effect of substrate temperature and nozzle temperature during inkjet printing of copper MOD ink on the deposition morphology is investigated. It exhibits distinct behaviors in the deposition morphology at elevated temperatures when compared with the ones at room temperature. The different deposition morphology of the copper ink at various temperatures is attributed to the generation of a localized seeding layer which attracts the copper ions to deposit. In addition, the copper MOD ink printing is compared with a silver MOD ink. The different deposition morphology between the copper ink and silver ink is due to the solvent system. Understanding the deposition mechanism for reactive inks provides valuable information and guidance in the fabrication of printed functional devices using particle‐free reactive inks.

Laser-Assisted Photo-Thermal Reaction for Ultrafast Synthesis of Single-Walled Carbon Nanotube/Copper Nanoparticles Hybrid Films as Flexible Electrodes.

The hybridization of single-walled carbon nanotubes (SWCNTs) and Cu nanoparticles offers a promising strategy for creating highly conductive and mechanically stable fillers for flexible printed electronics. In this study, we report the ultrafast synthesis of SWCNT/Cu hybrid nanostructures and the fabrication of flexible electrodes under ambient conditions through a laser-induced photo-thermal reaction. Thermal energy generated from the nonradiative relaxation of the π-plasmon resonance of SWCNTs was utilized to reduce the Cu-complex (known as a metal-organic decomposition ink) into Cu nanoparticles. We systematically investigated the effects of SWCNT concentration and output laser power on the structural and electrical properties of the SWCNT/Cu hybrid electrodes. The SWCNT/Cu electrodes achieved a minimum electrical resistivity of 46 μohm·cm, comparable to that of the metal-based printed electrodes. Mechanical bending tests demonstrated that the SWCNT/Cu electrodes were highly stable and durable, with no significant deformation observed even after 1000 bending cycles. Additionally, the electrodes showed rapid temperature increases and stable Joule heating performance, reaching temperatures of nearly 80 °C at an applied voltage of less than 3.5 V.

On the thermodynamics of Barium Oxyfluoride precursor in YBCO growth via the MOD process

Abstract Barium Oxyfluoride plays an important role, as a precursor species, in the nucleation and growth of YBa2Cu3O7−δ (YBCO) via the low fluorine metal organic decomposition (MOD low-fluorine) route. In this contribution, we present a study on the thermodynamics of oxyfluoride by processing experimental data on YBCO growth on LaAlO3 (LAO) substrates. The analysis allows one to determine the standard enthalpy and the standard entropy changes for oxyfluoride formation from barium oxide and barium fluoride. To identify the thermodynamically more favorable route to oxyfluoride formation in the MOD low-fluorine process, the free energy change for the formation of the precursor, through reactions involving gas water, has been determined. The free energy of formation via fluoride and water indicates higher stability of oxygen rich oxyfluoride for P HF 2 P H 2 O < 10 − 6 . In the framework of nucleation theory, the present results are needed to study the effect of precursor composition on film orientation.

Low-Temperature Fabrication of BiFeO3 Films on Aluminum Foils under a N2-Rich Atmosphere.

To be CMOS-compatible, a low preparation temperature (<500 °C) for ferroelectric films is required. In this study, BiFeO3 films were successfully fabricated at a low annealing temperature (<450 °C) on aluminum foils by a metal-organic decomposition process. The effect of the annealing atmosphere on the performance of BiFeO3 films was assessed at 440 ± 5 °C. By using a N2-rich atmosphere, a large remnant polarization (Pr~78.1 μC/cm2 @ 1165.2 kV/cm), and a high rectangularity (~91.3% @ 1165.2 kV/cm) of the P-E loop, excellent charge-retaining ability of up to 1.0 × 103 s and outstanding fatigue resistance after 1.0 × 109 switching cycles could be observed. By adopting a N2-rich atmosphere and aluminum foil substrates, acceptable electrical properties (Pr~70 μC/cm2 @ 1118.1 kV/cm) of the BiFeO3 films were achieved at the very low annealing temperature of 365 ± 5 °C. These results offer a new approach for lowering the annealing temperature for integrated ferroelectrics in high-density FeRAM applications.

A novel approach to the synthesis of superionic LaF3-based multicomponent nanofluorides via trifluoroacetate precursor decomposition

In this study, an approach for the facile and versatile synthesis of multicomponent superionic nanofluorides is proposed. The results of synthesis optimization of the tysonite-type LaF3 and La0.95Sr0.05F2.95 (sp. gr. P3‾c1) nanopowders with a particle size up to 100 nm by the trifluoroacetate precursors thermal decomposition under various conditions (dynamic vacuum and ambient atmosphere) are presented. The produced samples are characterized by X-ray diffraction, electron microscopy, and differential scanning calorimetry. Decarbonization annealing of the initial nanopowders in air at 773 K is urgent for the effective elimination of amorphous carbon formed as a result of the metal-organic precursors decomposition. The nanoceramics were pressed to a theoretical density of 75–80 % and their ion-conducting properties were measured using impedance spectroscopy. The conductivity of decarbonized La0.95Sr0.05F2.95 composition, obtained in a dynamic vacuum, is 1 × 10−3 S/cm at 500 K, which exceeds the performance of undoped LaF3 ceramics by approximately 60 times. The conductive properties of nanoceramics, produced from decarbonized vacuum-synthesized powders, are 5 times higher (1 × 10−3 Sm/cm) compared to mechanochemically fabricated ones. Air-synthesized (773 K) La0.95Sr0.05F2.95 ceramics are conducted significantly worse, although no traces of pyrohydrolysis were detected. Thus, the precursors thermal decomposition method opens up great prospects for the advanced production of ion-conducting nanomaterials based on multicomponent fluoride compounds for solid electrolyte design.

Multi-layer structured AlN/Er2O3 coating: Enhanced thermal stability and hydrogen isotope permeation resistance

AlN/Er2O3 multi-layer coatings, as a novel hydrogen isotope permeation barrier for nuclear reactor and hydrogen energy field, were prepared by magnetron sputtering coupled with metal-organic decomposition on the surface of reduced activation ferrite/martensitic steel. The thickness of the Er2O3 layers was adjusted by spin coating several times, the adhesion of the layers was tested with a micron scratch tester, and the microstructure and surface composition of the layers were analyzed by TEM and XPS. The results indicate the absence of evident crack holes on the coating surface, uniform distribution of elements without segregation, and satisfactory densification. In comparison with the individual Er2O3 coating, the multi-layer coating incorporating AlN as the interlayer exhibits enhanced adhesion strength, which could effectively mitigate the thermal mismatch phenomenon of Er2O3 under high temperature conditions. Electrochemical hydrogen permeation and high temperature gas pressure driven deuterium permeation tests demonstrated that the permeability resistance of the AlN/Er2O3 coating does not linearly increase with its thickness. The hydrogen permeation reduced factor of the coating reaches its maximum value when the thickness of the Er2O3 coating is 1500 nm.

Constructing phonon transport bridges via low-temperature sintering in Diamond@Ag/EP composite to achieve efficient 3D networks structure

The rapid advancement of integrated circuits and electronic devices presents challenges to traditional epoxy molding compound (EMC), necessitating the demand for highly thermally conductive yet electrically insulating composites to address the “hotspot issues” in high-power chips. Here, a low-temperature sintering technology based on metal–organic decomposition is developed to fabricate a three-dimensional interconnected networks structure composite (3D-Diamond@Ag/EP). The in-situ decomposition of the silver amine complex on the surface of the Diamond@Ag hybrid filler forms nano-silver bridges, which facilitate the successful construction of the three-dimensional networks structure. When the Ag reaches 4.0 vol%, the thermal conductivity of the composite (reaches 6.42 W/m·K) breaks out of the low numerical blockade of the epoxy resin (0.18 W/m·K), while maintaining excellent insulation performance. It is noteworthy that the great improvement of thermal conductivity is achieved by the synergistic effect of sufficient thermal pathways and minimizing interfacial thermal resistance along these paths. Moreover, this work obtained composite exhibits other excellent thermal characteristics. It provided a practical route to produce high thermal conductivity polymer-based composites with electrical insulation for heat management in modern electronic devices.

Spin thermoelectric and spin transport in YIG films fabricated by chemical method

Spin transport in heterojunctions between magnetic insulators and heavy metals has garnered significant attention due to its potential in spintronics applications. In this study, we employed the metal-organic decomposition (MOD) method to fabricate high-quality yttrium iron garnet (Y3Fe5O12-YIG) films on (111)-oriented gadolinium gallium iron garnet (Gd3Ga5O12-GGG) substrate. We conducted a thorough characterization of the crystallinity, surface morphology, and magnetic properties of the YIG films at various thicknesses. The obtained samples exhibited smooth surfaces with roughness mean-square (RMS) below 0.6 nm. Epitaxial growth was maintained for films up to 116 nm in thickness but deteriorated beyond that. The magnetic anisotropy demonstrated an easy axis in the in-plane direction, accompanied by a low coercivity of 4.8 ± 0.4 Oe. The spin Seebeck effect voltage measurement shows the highest signal for 366 nm thick film and is reduced if the thickness increases. Furthermore, we investigated spin transport across the YIG/Pt interface using spin Hall magnetoresistance. The average spin-mixing conductance (Gr) was determined to be 5.79 ± 0.54 × 1014 Ω−1m−2, a value comparable to those reported in previous studies.

Extraordinary enhancement of magneto-optical Faraday rotation angle in Bi-YIG/Pt/glass prepared by metal organic decomposition method

We achieve the extraordinary enhancement of magneto-optical Faraday rotation angle for bismuth-substituted yttrium iron garnet (Bi-YIG) using the metal-organic decomposition method, by introducing a Pt underlayer. The Faraday rotation angle reaches -25°/μm for the sample with a Pt thickness of 45 nm, which is 5 times higher than that of a bare thin film, setting a new record value for chemically synthesized Bi-YIG films. Through X-ray diffractometer, vibrating sample magnetometer, and energy dispersive X-ray spectroscopy analyses, we found that this enhancement is attributed to improved crystallinity, saturation magnetization, and the formation of a PtBi alloy phase, facilitated by Pt acting as an absorbing layer of Bi. We propose that the Bi-YIG/Pt film structure, with an optimum thickness of Pt underlayer, shows great promise for applications in various magneto-optical devices that require high detection sensitivity for small signals.

Fungal biomineralization of toxic metals accelerates organic pollutant removal

Fungal biomineralization plays an important role in the biogeochemical cycling of metals in the environment and has been extensively explored for bioremediation and element biorecovery. However, the cellular and metabolic responses of fungi in the presence of toxic metals during biomineralization and their impact on organic matter transformations are unclear. This is an important question because co-contamination by toxic metals and organic pollutants is a common phenomenon in the natural environment. In this research, the biomineralization process and oxidative stress response of the geoactive soil fungus Aspergillus niger were investigated in the presence of toxic metals (Co, Cu, Mn, and Fe) and the azo dye orange II (AO II). We have found that the co-existence of toxic metals and AO II not only enhanced the fungal biomineralization of toxic metals but also accelerated the removal of AO II. We hypothesize that the fungus and in situ mycogenic biominerals (toxic metal oxalates) constituted a quasi-bioreactor, where the biominerals removed organic pollutants by catalyzing reactive oxygen species (ROS) generation resulting from oxidative stress. We have therefore demonstrated that a fungal/biomineral system can successfully achieve the goal of toxic metal immobilization and organic pollutant decomposition. Such findings inform the potential development of fungal-biomineral hybrid systems for mixed pollutant bioremediation as well as provide further understanding of fungal organic-inorganic pollutant transformations in the environment and their importance in biogeochemical cycles.

The Influence of Ink Chemistry on the Microstructure Evolution and GHz RF Response of Printed Ag Transmission Lines.

High-frequency transmission is limited to the skin depth in metals. Because poor conductivity cannot be compensated for by increasing the conductor thickness as with DC, optimal transport properties are prerequisites for radio frequency (RF) use. Structural and chemical analyses of transmission lines printed using a traditional ink consisting of Ag nanoflakes in a dispersing phase revealed that optimized thermal treatments yielded thorough burnout of the binder, significant grain growth, elimination of the pore volume, and electrical responses that were comparable to values obtained for thermally evaporated, fully dense Ag controls. Specifically, a low DC resistivity of 2.3 μΩ·cm (1.4× bulk Ag) and RF transmission coefficients of 0.87 and 0.75 at 5 GHz and 10 GHz, respectively, were measured in the nanoflake Ag prints. Conversely, in transmission lines printed from a metal-organic decomposition ink, residual chemical contamination impeded diffusion and densification, yielding greater porosity, small grains that are pinned, and a degraded RF response. Reasonably good porosity approximations were obtained from a model based on percolation theory. The results indicate that contaminants at interfaces and pore surfaces impede diffusion, pore elimination, and full densification, and further, alter carrier dynamics and degrade RF response.

Magneto-Conductive and Magnetic Properties in La&lt;sub&gt;1-&lt;i&gt;x&lt;/i&gt;&lt;/sub&gt;Sr&lt;i&gt;&lt;sub&gt;x&lt;/sub&gt;&lt;/i&gt;MnO&lt;sub&gt;3 &lt;/sub&gt;Thin Films on a-SiO&lt;sub&gt;2&lt;/sub&gt; Substrates Produced by Metal Organic Decomposition Method

We have studied magneto-conductive and magnetic properties of La1-xSrxMnO3 (LSMO) thin films on a-SiO2 substrates produced by the metal organic decomposition (MOD) method. LSMO thin films for x = 0, 0.15 and 0.3 have been produced in a pure O2 gas atmosphere. Although LaMnO3 (LMO) single crystal is an antiferromagnetic insulator (AFI), LMO thin films we have produced show ferromagnetic metal (FM) properties for suitable heat treatment conditions. We consider that the excess of O2- ions in LMO thin films produced in a pure O2 gas atmosphere induces the strong hole self-doping into those and the LMO thin films change from AFI to FM. Whereas, the ordinary hole doping is also occurred in LSMO thin films at x &gt; 0. Thus, the carrier doping for LSMO thin films at x &gt; 0 is caused by the hole self-doping by O2- ions and the ordinary hole doping by the replacement of La3+ ions by Sr2+ ones. To investigate the crystallographic and surface structures of the LSMO thin films, X-ray diffraction and SEM measurements have been performed, respectively. From the X-ray diffraction measurement, we have found that all LSMO thin films have perovskite structure and are polycrystalline. From the SEM measurement, we have seen that the LSMO thin films are formed of the aggregation of LSMO fine particles. Electrical resistivities (ERs) and magneto-resistivity (MR) ratios of the LSMO thin films have been measured on the temperature dependence (4K-300K). From MR ratio measurements, the coercive forces of them have been obtained as a function of temperature, and the Curie temperatures have been estimated from the temperature dependences of the coercive forces. We have discussed the origin of the magneto-conductive and magnetic properties of LSMO thin films.

Fabrication and characterization of zirconium oxide coating on tubular steel by metal organic decomposition

In fusion reactor blankets, multifunctional ceramic coatings fabricated on structural materials have been investigated for tritium permeation reduction, electrical insulation, and corrosion protection. However, it has been challenging to manufacture a homogeneous coating on the complicated components in the blanket breeder, such as ducts. In terms of sustainable development, it is crucial to establish a ceramic coating technique on the inner walls of fuel pipes in liquid blanket systems. In this study, we applied the metal organic decomposition method to fabricate zirconium oxide coatings on 316L austenitic stainless steel tubes and characterized their properties as liquid tritium breeding pipes. Homogeneous zirconium oxide coatings with a thickness of 395 ± 12 nm have formed on the inner walls of SS316L tubes. The compatibility of the coated tubes with liquid lithium-lead was examined under static and flowing conditions at 550–600 °C for prolonged exposure of up to 2000 h. Under static conditions, ZrO2 coatings demonstrated exceptional compatibility with the liquid Li-Pb as they protected structural material from corrosion. At a flow rate of 0.16 m/s, the coatings were partly delaminated due to different thermal expansion coefficients of the coating and substrate and acceleration under a dynamic system. The coating thickness increased up to 650 ± 26 nm after exposure for 2000 h, which indicated ZrO2 coatings reacted with Li-Pb to form corrosion products. Besides, ZrO2 coatings achieved the insulating requirements of magnetohydrodynamic insulators as their electrical resistivities were on the order of 104–106 Ω m at the temperature range of 250–550 °C.

Unlocking the True Power of Additive Manufacturing for EMI Shielding

Miniaturization trends in electronic packaging led to reduced spacing of individual packages on the printed circuit boards and thus increased the overall electromagnetic interference (EMI) levels within a device. State-of-the-art conformal coatings as EMI shielding layers are typically applied via sputter technology and offer design limitations with respect to coating selectivity on individual positions of the overall package. Our new technology of additively Ag layer application via inkjet printing overcomes today’s design limitations and is key enabler for next generations packaging designs. In this study, we compare the shielding effectiveness (S.E.) on specifically designed transmission line emitter samples coated with state-of-the-art sputtered conformal layers against silver coatings applied via inkjet printing of particle free metal organic decomposition inks to evaluate the new technology for its potential on package level shielding performance. Mechanical and electrical characterization of the silver coatings indicate appropriate tools to specify layer characteristics and ensure S.E. of 40 dB or higher at frequencies of 800 MHz and higher. The suitability of our well-tailored silver coatings to match typical S.E. requirements is shown with even much thinner layer thickness as compared to state-of-the-art coatings.

Enhancing the Interaction of Carbon Nanotubes by Metal–Organic Decomposition with Improved Mechanical Strength and Ultra-Broadband EMI Shielding Performance

HighlightsA strategy based on metal-organic decomposition is proposed to enhance the tube-tube interactions of carbon nanotubes (CNTs).The robust tube-tube interactions of CNTs enhance both EMI shielding performance and mechanical properties of CNT film.This innovative approach provides an effective way to obtain high-performance CNT film.

Deuterium permeation and lithium‑lead corrosion behaviors of ceramic‑iron joint coating

In fusion reactor blanket design, the main challenges are to control the permeation of tritium and prevent the corrosion of the structural materials. This study focuses on investigating the behavior of ceramic‑iron joint coatings in terms of deuterium permeation and Li-Pb corrosion aiming to develop effective barriers against permeation while providing corrosion protection. The research involved fabricating ZrO2 and Fe2O3 ceramic coatings on F82H steel substrates using metal-organic decomposition followed by joining the coated samples with Fe foils using a hot press machine. Deuterium permeation measurements were conducted to assess the effectiveness of the coating, and liquid Li-Pb exposure tests in a flow environment were performed to evaluate its resistance against corrosion. The results showed that the coating reduced deuterium permeation flux by a factor of 2000 at 400 °C and 7000 at 550 °C compared to uncoated samples suggesting an improved crystallinity or grain growth without degradation due to the joining process. Furthermore, the corrosion layers formed on the surface of the Fe layer after the flowing Li-Pb exposure test. Although this layer gradually decreased in thickness over time while not significantly affecting the underlying Fe layer's thickness. This observation indicates that the corrosion layer performed mitigating the corrosion rate of the Fe layer. This paper aims to demonstrate how ceramic‑iron joint coatings can be compatible with the advanced fusion reactors.

Functionalization of micro-size garnet at the end of optical fiber for magneto-optical applications

We utilized a metal propionate solution to prepare polycrystalline bismuth-substituted yttrium iron garnets through the metal-organic decomposition process. After conducting thorough optimization, we successfully synthesized a garnet that exhibited a high magneto-optic response directly at the end of an optical fiber. A notable achievement of our work lies in the ability to restrict the size and position of the garnet to match the dimensions of the fiber's core. The functionalized fiber was integrated into a magneto-optical sensor setup, offering the flexibility to operate either in the Faraday rotation or magnetic circular dichroism mode.

Fabrication of V1−x Ti x O2 microbolometers on Si3N4/SiO2 membranes

V1−x Ti x O2 thin films have been prepared on Si3N4/SiO2/Si substrates by the two-step process of (1) growth of VO2/TiO2 thin films by metal-organic decomposition with carbothermal reduction, and (2) the interdiffusion between V and Ti atoms at the interface between the VO2 and TiO2 thin films during the growth of the VO2 thin film. The abrupt resistance change and the thermal hysteresis due to the metal-insulator transition were gradually suppressed with increasing the firing temperature, and they completely disappeared for the V0.65Ti0.35O2 thin film prepared at 650 °C. A relatively high TCR of −4.2%/K was obtained from the film over a wide temperature range of 20 °C–90 °C. V0.65Ti0.35O2 microbolometers with a size of 5 μm × 15 μm were fabricated by photolithography and Ar ion milling, and a Si3N4/SiO2 membrane under the microbolometer was formed with an aqueous KOH solution. The DC sensitivity of the fabricated microbolometer on the membrane was estimated to be 9876 W−1 and 20 times higher than that of the microbolometer on the Si3N4/SiO2/Si substrate. The V0.65Ti0.35O2 microbolometer on the membrane is available for a terahertz detector operating over the wide temperature range.