Effect of Rapid Thermal Annealing on Sputtered CaCu<Subscript>3</Subscript>Ti<Subscript>4</Subscript>O<Subscript>12</Subscript> Thin Films

Calcium copper titanium oxide (CaCu₃Ti₄O₁₂, abbreviated to CCTO) films were deposited on Pt/Ti/SiO₂/Si substrates at room temperature (RT) by radiofrequency magnetron sputtering. As-deposited CCTO films were treated by rapid thermal annealing (RTA) at various temperatures and in various atmospheres. X-ray diffraction patterns and scanning electron microscope (SEM) images demonstrated that the crystalline structures and surface morphologies of CCTO thin films were sensitive to the annealing temperature and ambient atmosphere. Polycrystalline CCTO films could be obtained when the annealing temperature was 700°C in air, and the grain size increased signifi- cantly with annealing in O₂. The 0.8-μm CCTO thin film that was deposited at RT for 2 h and then annealed at 700°C in O₂ exhibited a high dielectric constant (ε′) of 410, a dielectric loss (tan δ) of 0.17 (at 10 kHz), and a leakage current density (J) of 1.28 × 10⁻⁵ A/cm² (at 25 kV/cm).     

Free-Standing PEDOT-PSS/Ca<Subscript>3</Subscript>Co<Subscript>4</Subscript>O<Subscript>9</Subscript> Composite Films as Novel Thermoelectric Materials

Free-standing poly(3,4-ethylenedioxythiophene)-poly(styrenesulfonate) (PEDOT- PSS)/Ca₃Co₄O₉ composite films have been successfully prepared by mechanically blending Ca₃Co₄O₉ powder and PEDOT-PSS solution (Baytron P) and casting the mixed solution on polypropylene (PP) film substrates. X-ray diffraction (XRD) and scanning electron microscopy (SEM) characterization indicated that the Ca₃Co₄O₉ particles were in the shape of sheets and composited well together with PEDOT-PSS. Thermoelectric (TE) measurements revealed that the Seebeck coefficient can be improved by increasing the Ca₃Co₄O₉ content in the composite films, with the largest enhancement being 24.8% compared with a free-standing PEDOT-PSS film. However, it is also shown that the power factor of the composite films decreases with increasing Ca₃Co₄O₉ content, mainly due to the decline of electrical conductivity and the limited improvement of the Seebeck coefficient.     

Effect of Ionization Characteristics on Electrochemical Migration Lifetimes of Sn-3.0Ag-0.5Cu Solder in NaCl and Na<Subscript>2</Subscript>SO<Subscript>4</Subscript> Solutions

Anodic dissolution characteristics and electrochemical migration (ECM) behavior of Sn-3.0Ag-0.5Cu solder in NaCl and Na₂SO₄ solutions were investigated using anodic polarization tests and water drop tests (WDT). The ECM lifetime of Sn-3.0Ag-0.5Cu solder in NaCl solution (42.4 s) was longer than that in Na₂SO₄ solution (34.8 s). The pitting potential of Sn-3.0Ag-0.5Cu solder in NaCl solution (135 mV, SCE) was higher than that in Na₂SO₄ solution (−367 mV, SCE). The passivity film (SnO₂) formed on Sn-3.0Ag-0.5Cu solder during WDTs in NaCl solution was thicker than that formed in Na₂SO₄ solution. Therefore, the longer ECM lifetime of Sn-3.0Ag-0.5Cu solder in NaCl solution than in Na₂SO₄ solution can be attributed to the higher pitting potential in the NaCl solution, which is ascribed to the formation of a thicker passivity film (SnO₂) in the former. It was confirmed that microelements such as Ag and Cu do not take part in ECM because they form chemically stable intermetallic compounds with Sn. We believe that Sn is the only element that contributes to ECM, and dissolution of Sn at the anode is possibly the rate-determining step of ECM of Sn-3.0Ag-0.5Cu solder.     

Optical and Dielectric Properties and Microstructures of rf-Magnetron Sputtered ZnO-Doped Zr<Subscript>0.8</Subscript>Sn<Subscript>0.2</Subscript>TiO<Subscript>4</Subscript> Films on Indium Tin Oxide/Glass Substrates

Optical and dielectric properties and microstructures of ZnO-doped (Zr_0.8Sn_0.2)TiO₄ thin films prepared by radiofrequency (rf)-magnetron sputtering on indium tin oxide/glass substrates at different rf powers and substrate temperatures have been investigated. Selected-area diffraction patterns showed that the deposited films exhibited a polycrystalline microstructure. All films exhibited the ZnO-doped (Zr_0.8Sn_0.2)TiO₄ structure with the (111) orientation perpendicular to the substrate surface. The grain size as well as the deposition rate of the film increased with an increase in both rf power and substrate temperature. At an annealing temperature of 700°C, the ZnO-doped (Zr_0.8Sn_0.2)TiO₄ film possessed a dielectric constant of 47 at 10 MHz, a dissipation factor of 0.02 at 10 MHz, a leakage current density of 7.35 × 10⁻⁹  A/cm² at an electrical field of 1 kV/cm, average transmission in the visible range of over 70%, and an optical bandgap of 3.6 eV. This film will allow fabrication of fully transparent semiconductor devices such as a resistive random-access memory (RRAM) and thin-film transistors (TFTs) completely based on ZnO-doped (Zr_0.8Sn_0.2)TiO₄ thin films.     

Charge transport in thin layers of ferroelectric Hf<Subscript>0.5</Subscript>Zr<Subscript>0.5</Subscript>O<Subscript>2</Subscript>

The mechanism responsible for the charge transport in thin ferroelectric Hf_0.5Zr_0.5O₂ films has been studied. It is shown that in these films the transport mechanism is phonon-assisted tunneling between the traps. The optimal thickness of dielectric film for TiN/Hf_0.5Zr_0.5O₂/Pt structures is determined. As a result of comparing the experimental current–voltage (I–V) characteristics of TiN/Hf_0.5Zr_0.5O₂/Pt structures with the calculated ones, the thermal and optical energies of the traps are determined and the concentration of the traps is estimated. A comparison between the transport properties of ferroelectric and amorphous Hf_0.5Zr_0.5O₂ films is carried out. It is shown that the charge transport mechanism in this dielectric does not depend on its crystalline phase. A method for decreasing leakage currents in Hf_0.5Zr_0.5O₂ is proposed. A study of the resource of repolarization cycles for TiN/Hf_0.5Zr_0.5O₂/TiN metal-dielectric-metal (MDM) structures fully grown by atomic layer deposition (ALD) has been carried out.     

Thermal Stability of Barium and Indium Double-Filled Skutterudite Ba<Subscript>0.3</Subscript>In<Subscript>0.2</Subscript>Co<Subscript>3.95</Subscript>Ni<Subscript>0.05</Subscript>Sb<Subscript>12</Subscript> Coated by SiO<Subscript>2</Subscript> Nanoparticles

Filled skutterudite thermoelectric (TE) materials have been extensively studied to search for better TE materials in the past decade. However, there is no detailed investigation about the thermal stability of filled skutterudite TE materials. The evolution of microstructure and TE properties of nanostructured skutterudite materials fabricated with Ba_0.3In_0.2Co_3.95Ni_0.05Sb₁₂/SiO₂ core–shell composite particles with 3 nm thickness shell was investigated during periodic thermal cycling from room temperature to 723 K in this work. Scanning electronic microscopy and electron probe microscopy analysis were used to investigate the microstructure and chemical composition of the nanostructured skutterudite materials. TE properties of the nanostructured skutterudite materials were measured after every 200 cycles of quenching in the temperature range from 300 K to 800 K. The results show that the microstructure and composition of Ba_0.3In_0.2Co_3.95Ni_0.05Sb₁₂/SiO₂ nanostructured skutterudite materials were more stable than those of single-phase Ba_0.3In_0.2Co_3.95Ni_0.05Sb₁₂ bulk materials. The evolution of TE properties indicates that the electrical and thermal conductivity decrease along with an increase in the Seebeck coefficient with increasing quenching up to 2000 cycles. As a result, the dimensionless TE figure of merit (ZT) of the nanostructured skutterudite materials remains almost constant. It can be concluded that these nanostructured skutterudite materials have good thermal stability and are suitable for use in solar power generation systems.     

Nitrogen-doped Ge<Subscript>2</Subscript>Sb<Subscript>2</Subscript>Te<Subscript>5</Subscript> films for nonvolatile memory

Nitrogen-doped Ge₂Sb₂Te₅ (GST) films for nonvolatile memories were prepared by reactive sputtering with a GST alloy target. Doped nitrogen content was determined by using x-ray photoelectron spectroscopy (XPS). The crystallization behavior of the films was investigated by analyzing x-ray diffraction (XRD) and differential scanning calorimetry (DSC). Results show that nitrogen doping increases crystallization temperature, crystallization-activation energy, and phase transformation temperature from fcc to hexagonal (hex) structure. Doped nitrogen probably exists in the grain vacancies or grain boundaries and suppresses grain growth. The electrical properties of the films were studied by analyzing the optical band gap and the dependence of the resistivity on the annealing temperature. The optical band gap of the nitrogen-doped GST film is slightly larger than that of the pure GST film. Energy band theory is used to analyze the effect of doped nitrogen on electrical properties of GST films. Studies reveal that nitrogen doping increases resistivity and produces three relatively stable resistivity states in the plot of resistivity versus annealing temperature, which makes GST-based multilevel storage possible. Current-voltage (I-V) characteristics of the devices show that nitrogen doping increases the memory’s dynamic resistance, which reduces writing current from milliampere to microampere.     

Effect of ZnO Nanoparticles on the Sintering Behavior and Physical Properties of Bi<Subscript>0.5</Subscript>(Na<Subscript>0.8</Subscript>K<Subscript>0.2</Subscript>)<Subscript>0.5</Subscript>TiO<Subscript>3</Subscript> Lead-Free Ceramics

Sintered Bi_0.5(Na_0.8K_0.2)_0.5TiO₃ + x wt.% ZnO nanoparticle (BNKT–xZnO_n) ceramics have been fabricated by conventional annealing with the aid of ultrasound waves for preliminary milling. Because of the presence of the liquid Bi₂O₃–ZnO phase at the eutectic point of 738°C, the sintering temperature decreased from 1150°C to 1000°C, and the morphology phase boundary of BNKT–xZnO_n ceramics can be clarified by two separated peaks at (002)_T and (200)_T of 2θ in the x-ray diffraction (XRD) patterns. The improvement of ferroelectric properties has been obtained for BNZT–0.2 wt.% ZnO_n ceramics by the increase of remanent polarization up to 20.4 μC/cm² and a decrease of electric coercive field down to 14.2 kV/cm. The piezoelectric parameters of the ceramic included a piezoelectric charge constant of d ₃₁ = 78 pC/N; electromechanical coupling factors k _p = 0.31 and k _t = 0.34, larger than the values of 42 pC/N, 0.12 and 0.13, respectively, were obtained for the BNKT ceramics.     

Low Fatigue in Epitaxial Pb(Zr<Subscript>0.2</Subscript>Ti<Subscript>0.8</Subscript>)O<Subscript>3</Subscript> on Si Substrates with LaNiO<Subscript>3</Subscript> Electrodes by RF Sputtering

Epitaxial PZT (001) thin films with a LaNiO₃ bottom electrode were deposited by radio-frequency (RF) sputtering onto Si(001) single-crystal substrates with SrTiO₃/TiN buffer layers. Pb(Zr_0.2Ti_0.8)O₃ (PZT) samples were shown to consist of a single perovskite phase and to have an (001) orientation. The orientation relationship was determined to be PZT(001)[110]∥LaNiO₃(001)[110]∥SrTiO₃ (001)[110]∥TiN(001)[110]∥Si(001)[110]. Atomic force microscope (AFM) measurements showed the PZT films to have smooth surfaces with a roughness of 1.15 nm. The microstructure of the multilayer was studied using transmission electron microscopy (TEM). Electrical measurements were conducted using both Pt and LaNiO₃ as top electrodes. The measured remanent polarization P _r and coercive field E _c of the PZT thin film with Pt top electrodes were 23 μC/cm² and 75 kV/cm, and were 25 μC/cm² and 60 kV/cm for the PZT film with LaNiO₃ top electrodes. No obvious fatigue after 10¹⁰ switching cycles indicated good electrical endurance of the PZT films using LaNiO₃ electrodes, compared with the PZT film with Pt top electrodes showing a significant polarization loss after 10⁸ cycles. These PZT films with LaNiO₃ electrodes could be potential recording media for probe-based high-density data storage.     

Memory Effect of Metal-Insulator-Silicon Capacitor with HfO<Subscript>2</Subscript>-Al<Subscript>2</Subscript>O<Subscript>3</Subscript> Multilayer and Hafnium Nitride Gate

Metal-insulator-silicon capacitors have been fabricated using novel insulators of SiO₂/HfO₂-Al₂O₃-HfO₂ (HAH)/Al₂O₃ and metallic HfN gate, exhibiting a program-erasable characteristic. The memory capacitor presents a large memory window of 2.4 V under +12 V program/–14 V erase for 10 ms, no erase saturation, and sufficient electron- and hole-trapping efficiencies such as an electron density of ∼7 × 10¹² cm^–2 under 13 V program for 0.5 ms and a hole density of ∼4 × 10¹² cm^–2 under –12 V erase for 0.5 ms. The observed properties are attributed to the introduction of high permittivity atomic-layer-deposited HAH/Al₂O₃ as well as high work function HfN gate. The related mechanism is addressed accordingly.     

Microwave Dielectric Properties of ZnO-2TiO<Subscript>2</Subscript>-Nb<Subscript>2</Subscript>O<Subscript>5</Subscript> Ceramics with BaCu (B<Subscript>2</Subscript>O<Subscript>5</Subscript>) Addition

The influence of BaCu(B₂O₅) (BCB) addition on the sintering temperature and microwave dielectric properties of ZnO-2TiO₂-Nb₂O₅ (ZTN) ceramic has been investigated using dilatometry, x-ray diffraction, scanning electron microscopy, and microwave dielectric measurements. A small amount of BCB addition to ZTN can lower the sintering temperature from 1100°C to 900°C. The reduced sintering temperature was attributed to the formation of the BCB liquid phase. The ZTN ceramics containing 3.0 wt.% BCB sintered at 900°C for 2 h have good microwave dielectric properties of Q × f = 19,002 GHz (at 6.48 GHz), ε _r = 45.8 and τ _f  = 23.2 ppm/°C, which suggests that the ceramics can be applied in multilayer microwave devices, provided that Ag compatibility exists.     

Self-limiting growth of ZrO<Subscript>2</Subscript> films on a Si(100) substrate using ZrCl<Subscript>4</Subscript> and O<Subscript>2</Subscript> under atmospheric pressure

The ZrO₂ films were deposited onto a Si(100) substrate using an alternate reaction of ZrCl₄ and O₂ under atmospheric pressure. It is found that the growth rate of ZrO₂ film depends on the growth conditions, such as growth temperature, partial pressure of the sources being supplied, and exposure time of the substrate to the gaseous sources. Self-limiting growth of the ZrO₂ was achieved in the range of the growth temperature of 673–923 K. The x-ray diffractogram of the ZrO₂ films showed a typical diffraction pattern assigned to the tetragonal polycrystalline phase. The obtained ZrO₂ films were of smooth and uniform surface. It was found that the [O]/[Zr] ratio of the ZrO₂ films are similar to that of the ZrO₂ bulk.     

High-Temperature Capacitor Materials Based on Modified BaTiO<Subscript>3</Subscript>

High-temperature capacitor materials sintered at 1120°C were prepared in a BaTiO₃ (BT)-Na_0.5Bi_0.5TiO₃ (NBT)-Nb₂O₅-ZnO-CaZrO₃ system. The Curie temperature of BaTiO₃ was increased by NBT doping, and a secondary phase occurred when adding ≥5 mol% NBT. The effects of Nb₂O₅, ZnO, and CaZrO₃ on the dielectric properties and the microstructure of BT ceramics doped with 1 mol% NBT were analyzed. The overall dielectric constant decreased when the Nb₂O₅ content increased, and increased when the ZnO content increased. The dielectric constant peak at the Curie temperature was effectively depressed, and a broad secondary dielectric constant peak appeared at 60°C when the ZnO concentration was ≥4.5 mol%. Significant grain growth was observed by scanning electron microscope (SEM) analysis as the amount of ZnO increased. The high-temperature capacitor specification (−55°C to +175°C, ΔC/C _25°C less than ±15%) is met when 7 mol% to 8 mol% CaZrO₃ is added.     

Superior suppression of gate current leakage in Al<Subscript>2</Subscript>O<Subscript>3</Subscript>/Si<Subscript>3</Subscript>N<Subscript>4</Subscript> bilayer-based AlGaN/GaN insulated gate heterostructure field-effect transistors

AlGaN/GaN-based metal-insulator-semiconductor heterostructure field-effect transistors (MIS-HFETs) with Al₂O₃/Si₃N₄ bilayer as insulator have been investigated in detail, and compared with the conventional HFET and Si₃N₄-based MIS-HFET devices. Al₂O₃/Si₃N₄ bilayer-based MIS-HFETs exhibited much lower gate current leakage than conventional HFET and Si₃N₄-based MIS devices under reverse gate bias, and leakage as low as 1×10⁻¹¹ A/mm at −15 V has been achieved in Al₂O₃/Si₃N₄-based MIS devices. By using ultrathin Al₂O₃/Si₃N₄ bilayer, very high maximum transconductance of more than 180 mS/mm with ultra-low gate leakage has been obtained in the MIS-HFET device with gate length of 1.5 μm, a reduction less than 5% in maximum transconductance compared with the conventional HFET device. This value was much smaller than the more than 30% reduction in the Si₃N₄-based MIS device, due to the employment of ultra-thin bilayer with large dielectric constant and the large conduction band offset between Al₂O₃ and nitrides. This work demonstrates that Al₂O₃/Si₃N₄ bilayer insulator is a superior candidate for nitrides-based MIS-HFET devices.     

Thermoelectric Properties of NdGd<Subscript>1+<Emphasis Type="Italic">x</Emphasis></Subscript>S<Subscript>3</Subscript> Prepared by CS<Subscript>2</Subscript> Sulfurization

Ternary rare-earth sulfides NdGd_1+x S₃, where 0 ≤ x ≤ 0.08, were prepared by sulfurizing Ln₂O₃ (Ln = Nd, Gd) with CS₂ gas, followed by reaction sintering. The sintered samples have full density and homogeneous compositions. The Seebeck coefficient, electrical resistivity, and thermal conductivity were measured over the temperature range of 300 K to 950 K. All the sintered samples exhibit a negative Seebeck coefficient. The magnitude of the Seebeck coefficient and the electrical resistivity decrease systematically with increasing Gd content. The thermal conductivity of all the sintered samples is less than 1.9 W K⁻¹ m⁻¹. The highest figure of merit ZT of 0.51 was found in NdGd_1.02S₃ at 950 K.     

Recent progress of (Ba,Sr)TiO<Subscript>3</Subscript> thin films for tunable microwave devices

The (Ba_1−xSr_x)TiO₃ (BST) ferroelectric thin films exhibit outstanding dielectric properties, even at high frequencies (>1 GHz), and large, electric-field dielectric tunability. This feature makes them suitable for developing a new class of tunable microwave devices. The dielectric properties and dielectric tuning property of BST thin films are closely related to the film compositions, substrate types, and post-deposition process. The successful implementation of BST films as high-frequency dielectrics in electrically tunable microwave devices requires a detailed understanding of both their processing and material properties. This paper will review the recent progress of BST thin films as active dielectrics for tunable microwave devices. The technical aspects of BST thin films, such as processing methods, post-annealing process, film compositions, film stress, oxygen defects, and interfacial structures between film and substrate, are briefly reviewed and discussed with specific samples from the recent literature. The major issues requiring additional investigations to improve the dielectric properties of BST thin films for tunable microwave applications are also discussed.     

Tailoring of LaxSr1‐xCoyFe1‐yO3‐δ Nanostructure by Pulsed Laser Deposition

Pulsed Laser Deposition (PLD) was used to prepare thin films with the nominal composition La_0.58Sr_0.4Co_0.2Fe_0.8O_3‐δ (LSCF). The thin film microstructure was investigated as a function of PLD deposition parameters such as: substrate temperature, ambient gas pressure, target‐to‐substrate distance, laser fluence and frequency. It was found that the ambient gas pressure and the substrate temperature are the key PLD process parameters determining the thin film micro‐ and nanostructure. A map of the LSCF film nanostructures is presented as a function of substrate temperature (25–700 °C) and oxygen background pressure (0.013–0.4 mbar), with film structures ranging from fully dense to highly porous. Fully crystalline, dense, and crack‐free LSCF films with a thickness of 300 nm were obtained at an oxygen pressure lower than 0.13 mbar at a temperature of 600 °C. The obtained knowledge on the structure allows for tailoring of perovskite thin film nanostructure, e.g., for solid oxide fuel cell cathodes. A simple geometrical model is proposed, allowing estimation of the catalytic active surface area of the prepared thin films. It is shown that voids at columnar grain boundaries can result in an increase of the surface area by approximately 25 times, when compared to dense flat films.     

Cathodoluminescence of ZnO/GaN/α-Al<Subscript>2</Subscript>O<Subscript>3</Subscript> heteroepitaxial structures grown by chemical vapor deposition

The cathodoluminescent properties of ZnO films in ZnO/GaN/α-Al₂O₃ and ZnO/α-Al₂O₃ heteroepitaxial structures grown by chemical vapor deposition in a low-pressure flowing-gas reactor were studied and compared. A superlinear dependence of the excitonic-band intensity in the cathodoluminescence spectrum of the ZnO/GaN/α-Al₂O₃ structures on the electron-beam current is ascertained, which indicates that the emission is stimulated for relatively low thresholds of the excitation intensity. It is shown that the ZnO films grown on the GaN substrates exhibit a much more effective cathodoluminescence compared to the cathodoluminescence in the films grown on α-Al₂O₃. It was observed that the luminescent properties of ZnO layers in the ZnO/GaN/α-Al₂O₃ structures subjected to long-term heat treatment at 750°C in an oxygen atmosphere exhibit a high thermal stability.     

Growth of Polarity-Controlled ZnO Films on (0001) Al<Subscript>2</Subscript>O<Subscript>3</Subscript>

The polarity control of ZnO films grown on (0001) Al₂O₃ substrates by plasma-assisted molecular-beam epitaxy (P-MBE) was achieved by using a novel CrN buffer layer. Zn-polar ZnO films were obtained by using a Zn-terminated CrN buffer layer, while O-polar ZnO films were achieved by using a Cr₂O₃ layer formed by O-plasma exposure of a CrN layer. The mechanism of polarity control was proposed. Optical and structural quality of ZnO films was characterized by high-resolution X-ray diffraction and photoluminescence (PL) spectroscopy. Low-temperature PL spectra of Zn-polar and O-polar samples show dominant bound exciton (I₈) and strong free exciton emissions. Finally, one-dimensional periodic structures consisting of Zn-polar and O-polar ZnO films were simultaneously grown on the same substrate. The periodic inversion of polarity was confirmed in terms of growth rate, surface morphology, and piezo response microscopy (PRM) measurement.     

Synthesis and Thermoelectric Properties of the Double-Filled Skutterudite Yb<Subscript>0.2</Subscript>In<Subscript><Emphasis Type="Italic">y</Emphasis></Subscript>Co<Subscript>4</Subscript>Sb<Subscript>12</Subscript>

Filled skutterudites have long been singled out as one of the prime examples of phonon glass electron crystal materials. Recently the double-filling approach in these materials has been attracting increased attention. In this study, Yb_0.2In _y Co₄Sb₁₂ (y = 0.0 to 0.2) samples have been prepared by a simple melting method and their thermoelectric properties have been investigated. The power factor is increased dramatically when increasing the In content, while the lattice thermal conductivity is lowered considerably, leading to a large increase of the ZT value. A state-of-the-art ZT value of 1.0 is attained in Yb_0.2In_0.2Co₄Sb₁₂ at 750 K.