Fabrication and positive temperature coefficient of resistivity properties of semiconducting ceramics based on the BaTiO3–(Bi1/2K1/2)TiO3 system

BaTiO₃–(Bi_1/2K_1/2)TiO₃ (BT–BKT) ceramics have a low ρ_RT of 10¹–10² Ω cm like that of semiconducting materials prepared by sintering in a N₂ flow with low O₂ concentration. By annealing in air, the BT–BKT ceramics show an abrupt increase in their resistivity near the T_c, namely, a positive temperature coefficient of resistivity (PTC) characteristic. With 5 mol% and 10 mol% BKT added to BT, the ceramics display the PTC characteristic at 155 °C and 165 °C, respectively. Furthermore, the ratio, ρ_max/ρ_RT, of the highest resistivity (ρ_max) and the resistivity at room temperature (ρ_RT) of the ceramics increased on adding a small amount of Mn and a sintering aid.     

Electrical resistivity of α-SiC ceramics sintered with Al2O3 or AlN additives

Highly resistive SiC ceramics were prepared by hot pressing α-SiC powders with Al₂O₃-Y₂O₃ additives with a 4:1 molar ratio. X-ray diffraction patterns, Raman spectra, electron probe microanalysis (EMPA), and scanning electron microscopy (SEM) images revealed that the bulk SiC ceramics consisted mostly of micron-sized 6H-SiC grains along with Y₂O₃ and Si clusters. As the additive content increased from 1 to 10 vol%, the electrical resistivity of the ceramics increased from 3.0 × 10⁶ to 1.3 × 10⁸ Ω cm at room temperature. Such high resistivity is ascribed to Al₂O₃ in which Al impurities substituting Si site act as deep acceptors for trapping carriers. More resistive α-SiC ceramics were produced by adding AlN instead of Al₂O₃. The highest resistivity (1.3 × 10¹⁰ Ω cm) was achieved by employing 3 vol% AlN-Y₃Al₅O₁₂ (yttrium aluminum garnet, YAG) as an additive.     

Electrical and thermal properties of SiC-Zr2CN composites sintered with Y2O3-Sc2O3 additives

SiC-Zr₂CN composites were fabricated from β-SiC and ZrN powders with 2 vol% equimolar Y₂O₃-Sc₂O₃ additives via conventional hot pressing at 2000 °C for 3 h in a nitrogen atmosphere. The electrical and thermal properties of the SiC-Zr₂CN composites were investigated as a function of initial ZrN content. Relative densities above 98% were obtained for all samples. The electrical conductivity of Zr₂CN composites increased continuously from 3.8 × 10³ (Ωm)⁻¹ to 2.3 × 10⁵ (Ωm)⁻¹ with increasing ZrN content from 0 to 35 vol%. In contrast, the thermal conductivity of the composites decreased from 200 W/mK to 81 W/mK with increasing ZrN content from 0 to 35 vol%. Typical electrical and thermal conductivity values of the SiC-Zr₂CN composites fabricated from a SiC-10 vol% ZrN mixture were 2.6 × 10⁴ (Ωm)⁻¹ and 168 W/m K, respectively.     

Preparation of highly oriented β-SiC bulks by halide laser chemical vapor deposition

Highly oriented β-SiC bulks with high hardness were fabricated by halide laser chemical vapor deposition (HLCVD) using SiCl₄, CH₄ and H₂ as precursors. The effects of total pressure (P_tot) and deposition temperature (T_dep) on the preferred orientation, microstructure, deposition rate (R_dep) and micro-hardness were investigated. The 〈110〉-oriented β-SiC bulks were obtained at low P_tot (2–4 kPa), non-oriented β-SiC bulks were obtained at mediate P_tot (6 kPa), and 〈111〉-oriented β-SiC bulks were obtained at high P_tot (10–40 kPa), exhibiting faceted, cauliflower-like and six-fold pyramid-like microstructure, respectively. The maximum R_dep of 〈111〉- and 〈110〉-oriented β-SiC bulks were 3600 and 1300 μm/h at, respectively. The activation energy obtained by the plot of lgR_dep-T_dep⁻¹ is 170 to 280 kJ mol⁻¹, showing an exponential relation with P_Si. The Vickers micro-hardness of β-SiC bulks increased with increasing P_tot and showed the highest value of 35 GPa at P_tot = 40 kPa with a complete 〈111〉 orientation.     

Electrical properties and microstructural evolution of ZrO2–Al2O3–TiN nanocomposites prepared by spark plasma sintering

Electroconductive ZrO₂–Al₂O₃–25 vol% TiN ceramic nanocomposites were prepared by spark plasma sintering at 1200 °C for 3 min. The electrical resistivity of the composites decreased from 4.5 × 10^?4 Ω m to 3 × 10^?5 Ω m as the Al₂O₃ content in the ZrO₂–Al₂O₃ matrix increased from 0 to 100 vol%. SEM images graphically presented the microstructural evolution of the composites and a geometrical percolation model was applied to investigate the relationship between the electrical property and the microstructure. The results indicated that the addition of Al₂O₃ to ZrO₂–TiN improved the electrical conductivity of the material by tailoring the structure from “nano–nano” type for ZrO₂–TiN to “micro–nano” type for ZrO₂–Al₂O₃–TiN.     

Electrically conductive ZrO2–TiN composites

1.75 mol% Y₂O₃-stabilized ZrO₂–TiN composites could be fully densified by hot pressing for 1 h at 1550 °C in vacuum under a mechanical pressure of 28 MPa. Composites with 35–95 vol% TiN were investigated and the best mechanical properties, i.e., a Vickers hardness of 14.7 GPa, an indentation toughness of 5.9 MPa m^1/2 and an excellent bending strength of 1674 MPa were obtained with 40 vol% TiN. The active toughening mechanisms were identified and their contribution to the overall composite toughness as function of the TiN content was modelled, experimentally verified and discussed. Transformation toughening was found to be the primary toughening mechanism. The TiN grain size was found to increase with increasing TiN content, resulting in a decreasing hardness and strength. A maximum strength was obtained at 40 vol% TiN. The electrical resistivity of the composites decreases exponentially with increasing TiN content and correlates well with the Polder-Van Santen mixture rule. Thus at around 40 vol% TiN, the conductivity is high enough to allow EDM machining of the composite, therefore avoiding the expensive grinding operation for final shaping and surface finishing of components.     

Highly resistive SiC ceramics sintered with Al2O3-AlN-Y2O3 additions

A polycrystalline SiC ceramic prepared by pressureless sintering of α-SiC powders with 3 vol% Al₂O₃-AlN-Y₂O₃ additives in an argon atmosphere exhibited a high electrical resistivity of ~10¹³ Ω cm at room temperature. X-ray diffraction revealed that the SiC ceramics consisted mainly of 6H- and 4H-SiC polytypes. Scanning electron microscopy and high resolution transmission electron microscopy investigations showed that the SiC specimen contained micron-sized grains surrounded by an amorphous Al-Y-Si-O-C-N film with a thickness of ~4.85 nm. The thick boundary film between the grains contributed to the high resistivity of the SiC ceramic.     

TiN modified SiC with enhanced strength and electrical properties

SiC based composites were manufactured with varying TiN content (0–50 V%) using Al₂O₃ and Y₂O₃ sintering aids. Basic dilatometry measurements were performed to determine when densification begins within the composite system. Samples were consolidated via uni-axial hot pressing at 1900 °C to produce ceramic composites with >98% theoretical density. Electrical measurements show increasing TiN additions reduce resistivity and begin to plateau at 40–50V%. Resistivity decreased from 2.0 × 10⁵ Ω − cm (0% TiN) to 2.0 × 10⁻⁴ Ω − cm (50V% TiN). Flexural strengths were characterized and compared against a baseline (0% TiN) SiC. Strengths increased gradually with TiN content. A maximum strength 921 MPa was observed at 40V% TiN content vs. 616 MPa for the baseline SiC. This was a gain of 50% over baseline. Additions beyond that range did not produce further gains in strength.     

Electrical resistivity of silicon carbide ceramics sintered with 1 wt% aluminum nitride and rare earth oxide

The influence of additive composition on the electrical resistivity of hot-pressed liquid-phase sintered (LPS)-SiC was investigated using AlN–RE₂O₃ (RE = Sc, Nd, Eu, Gd, Ho, Er, Lu) mixtures at a molar ratio of 60:40. It was found that all specimens could be sintered to densities >95% of the theoretical density by adding 5 wt% in situ-synthesized nano-sized SiC and 1 wt% AlN–RE₂O₃ additives. Six out of seven SiC ceramics showed very low electrical resistivity on the order of 10^?4 Ω m. This low electrical resistivity was attributed to the growth of nitrogen-doped SiC grains and the confinement of non-conducting RE-containing phases in the junction areas. The SiC ceramics sintered with AlN–Lu₂O₃ showed a relatively high electrical resistivity (～10^?2 Ω m) due to its lower carrier density (～10¹⁷ cm^?3), which was caused by the growth of faceted grains and the resulting weak interface between SiC grains.     

Electrical properties of [Li0.04(K0.5Na0.5)0.96−xAgx](Nb1−ySby)O3 ceramics

Dependence of electrical properties on the structural characteristics of Li_0.04(K_0.5Na_0.5)_0.96(Nb_1?ySb_y)O₃ (LKNNS (x = 0, 0.00 ≤ y ≤ 0.10)) and [Li_0.04(K_0.5Na_0.5)_0.96?xAg_x](Nb_0.925Sb_0.075)O₃ (LKNANS (0.01 ≤ x ≤ 0.05, y = 0.075)) were investigated. The oxygen octahedral distortion was dependent on Ag⁺ and/or Sb⁵⁺ content which affected to the phase transition temperature of LKNNS and LKNANS ceramics. The orthorhombic–tetragonal and tetragonal–cubic phase transition temperatures (T_O–T, T_C) of the specimens were decreased with increasing of average octahedral distortion. With increasing of Sb⁵⁺ content, the electromechanical coupling factor (k_p), piezoelectric constant (d₃₃) and dielectric constant (?_r) of the sintered specimens were increased up to y = 0.075, and then decreased. These results could be attributed to the shift of T_O–T to near room temperature for Li_0.04(K_0.5Na_0.5)_0.96(Nb_0.0925Sb_0.075)O₃.     

B deficiency in TiB2 and B solid solution in TiN in TiN–TiB2 composites prepared by spark plasma sintering

Dense TiN–TiB₂ composites were prepared by spark plasma sintering at 2573 K using TiN and TiB₂ powders. With increasing TiN content from 60 to 90 vol%, the c-axis length of TiB₂ in the TiN–TiB₂ composites decreased from the stoichiometric value (0.3230 nm) to 0.3227 nm because of B deficiency in TiB₂, whereas the a-axis length of TiB₂ was unchanged from the stoichiometric value of 0.3031 nm. The lattice parameter of TiN increased from the stoichiometric value (0.4243 nm) to 0.4250 nm with increasing TiB₂ content from 0 to 60 vol% because of B solid solution in TiN.     

Spark plasma sintering of TiN–TiB2 composites

TiN–TiB₂ composites were fabricated by spark plasma sintering at 1773–2573 K. Effects of TiN and TiB₂ content on relative density, microstructure, and mechanical properties were investigated. Above 2373 K, TiN–TiB₂ composites exhibited relative densities over 95%. A high density of 99.7% was obtained at 2573 K with 20–30 vol% TiB₂. Shrinkage of the TiN–70 vol% TiB₂ composite was the highest at 1573–2473 K. For the TiN–70 vol% TiB₂ composite prepared at 1973–2373 K, TiN grains were small, while at 2573 K, TiB₂ became a continuous matrix, in which irregular-shaped TiN dispersed. hBN was formed in the TiN–TiB₂ composite containing 50–60 vol% TiB₂ above 2373 K. The maximum Vickers hardness and fracture toughness obtained for the TiN–80 vol% TiB₂ composite sintered at 2473 K was 26.3 GPa and 4.5 MPa m^1/2, respectively.     

Electrical properties of CaBi4Ti4O15–Bi4Ti3O12 piezoelectric ceramics

CaBi₄Ti₄O₁₅–Bi₄Ti₃O₁₂ (CBT–BIT) ceramics were synthesized using a solid state reaction method. The X-ray diffraction (XRD) analysis revealed the existence of bismuth layered perovskite phase with orthorhombic crystal structure. High-resolution transmission electron microscopy (HRTEM) confirmed the alternate arrangement of CBT part and BIT part along c axis in the intergrowth structure. CBT–BIT ceramics showed excellent thermal stability of the dielectric loss (tan δ), but the relaxation of dielectric loss in the 100 Hz to 1 MHz frequency range had been observed. Meanwhile, an enhanced piezoelectric constant (d₃₃) value of 15 pC/N was observed without degradation even the temperature up to 650 °C. The dc resistivity (ρ_dc) of CBT–BIT performed a high value of 5.68×10¹⁴ (Ω cm) at room temperature (RT). In addition, the ρ_dc values of CBT–BIT within the temperature range of 100–450 °C were close to those of CBT and kept almost one hundred times higher than those of BIT.     

Effects of oxidation curing and sintering temperature on the microstructure formation and heat transfer performance of freestanding polymer-derived SiC films for high-power LEDs

Effects of oxidation cross-linking and sintering temperature on the microstructure evolution, thermal conductivity and electrical resistivity of continuous freestanding polymer-derived SiC films were investigated. The as-received films consisting of β-SiC nanocrystals embedded in amorphous SiO_xC_y and free carbon nanosheets were fabricated via melt spinning of polycarbosilane (PCS) precursors and cured for 3 h/10 h followed by pyrolysis from 900 °C to 1200 °C. Results reveal that nanoscale structure (β-SiC/SiO_xC_y/C_free) provides an ingenious strategy for constructing highly thermal conductive, highly insulating and highly flexible complexes. In particular, the 3 h-cured films sintered at 1200 °C with satisfying thermal conductivity (46.8 W m^?1 K^?1) and electrical resistivity (2.1 × 10⁸ Ω m) are suitable for the realization of high-performance substrates. A remarkable synergistic effect (lattice vibration of β-SiC nanocrystals and close-packed SiO_xC_y, free-electron heat conduction of β-SiC and free carbon, and supporting role of oxygen vacancy) contributing to thermal conductivity improvement is proposed based on the analysis of microstructure, intrinsic properties and simulations. Eventually, the SiC films without additional dielectric layers are directly silk-screen printed with high-temperature silver paste and used as heat dissipation substrates for high-power LED devices via chip-on-board (COB) package. The final devices can emit bright light with low-junction temperature (52.6 °C) and good flexibility owing to the mono-layer SiC substrate with low thermal resistance and desirable mechanical properties. This work offers an effective approach to design and fabricate flexible heat dissipation ceramic substrates for thermal management in advanced electronic packaging fields.     

Low threshold field emission from nitrogen-incorporated carbon nanowalls

Field emission performance of nitrogen-incorporated vertically-aligned graphene layers, so called “carbon nanowalls (CNWs)”, is found to depend upon their electrical conduction properties. The CNW samples with n-type conduction exhibit near-ideal Ohmic contacts with various metals such as Cu, Ti, and Au, regardless of the work function of the metals. The high resistivity CNWs for lower deposition temperatures (T_D) show semiconducting behavior in the Arrhenius plots, while the low resistivity CNWs for higher T_D show semi-metallic behavior. The emission turn-on field versus T_D has a very similar trend to the bulk resistivity versus T_D, and is reduced down to about 3 V/μm when the resistivity reaches a minimum (3.0 × 10^? 3 Ω cm). The lower turn-on field for semi-metallic CNWs is attributed to an upward shift of the emission level, which is responsible for a decrease in the surface potential barrier height for emission.     

Electrical and mechanical properties of pressureless sintered SiC-Ti2CN composites

Highly conductive SiC-Ti₂CN composites were fabricated from β-SiC and TiN powders with 10?vol% Y₂O₃-AlN additives via pressureless sintering. The effect of initial TiN content on the microstructure, and electrical and mechanical properties of the SiC-Ti₂CN composites was investigated. It was found that all specimens could be sintered to ≥98% of the theoretical density. The electrical resistivity of the SiC-Ti₂CN composites decreased with increasing initial TiN content. The SiC-Ti₂CN composites prepared from 25?vol% TiN showed the highest electrical conductivity (～1163 (Ω?cm)^?1) for any pressureless sintered SiC ceramics thus far. The high electrical conductivity of the composites was attributed to the in situ-synthesis of an electrically conductive Ti₂CN phase and the growth of N-doped SiC grains during pressureless sintering. The flexural strength, fracture toughness, and Vickers hardness of the composite fabricated with 25?vol% TiN were 430?MPa, 4.9?MPa?m^1/2, and 23.1?GPa, respectively, at room temperature.     

Frequency scaling of ac hopping transport in amorphous carbon nitride

The dynamics of hopping transport in amorphous carbon nitride is investigated in both Ohmic and non-linear regimes. Dc current and ac admittance were measured in a wide range of temperatures (90 K < T < 300 K), electric fields (F < 2 × 10⁵ V cm^− 1) and frequencies (10² < f < 10⁶ Hz).The dc Ohmic conductivity is described by a Mott law, i.e. a linear ln(σ_OHMIC) vs T^− 1/4 dependence. The scaling of field-enhanced conductivity as ln(σ / σ_OHMIC) = ϕ[F^S / T] with S ≈ 2/3, observed for F > 3 × 10⁴ V cm^− 1 over 5 decades in σ(T,F), is explained by band tail hopping transport; the filling rate, Γ_F(E_DL), of empty states at the transport energy is obtained with a “filling rate” method which incorporates an exponential distribution of localized states, with a non-equilibrium band tail occupation probability f(E) parametrized by an electronic temperature T_EFF (F).As the ac frequency and temperature increase, the increase in conductance G is accurately described by Dyre's model for hopping transport within a random spatial distribution of energy barriers. This model predicts a universal dependence of the complex ac conductivity of the form σ_ac = σ(0)[iωτ / ln(1 + iωτ)], where σ(0) is the zero frequency ac conductivity and τ(T,F) is a characteristic relaxation time. We find that the inverse characteristic time 1 / τ can also be described by a Mott law. It is compatible with the filling rate Γ_F(E_DL) at the transport energy, which governs the dc conductivity; this rate increases with increasing dc field, as more empty states become available in the band tail for hopping transitions. This “universal” scaling law for the ac conductance provides a scaling parameter K(T,F) = τ(T,F) σ(T,F,ω = 0) / ɛ which is found to decrease with increasing electric field from 5 to 0.5, depending weakly on temperature. Our band tail hopping model predicts a high-field value of K(T,F) smaller than the Ohmic value, under the condition (eFγ^− 1 / E°) ≤ (kT / E°)^1/4, where γ^− 1 is the localization radius and E° the disorder energy of the band tail distribution.     

Effect of CH4/SiCl4 ratio on the composition and microstructure of 〈110〉-oriented β-SiC bulks by halide CVD

Halide chemical vapor deposition process was carried out for fast fabricating oriented stoichiometric β-SiC through controlling flow rate of precursors (SiCl₄ and CH₄). The effects of molar ratio of C and Si precursors (R_C/Si) on composition, preferred orientation, microstructure and deposition rate (R_dep) were investigated. The deposits transformed from silicon-rich to stoichiometric β-SiC to carbon-rich with increasing R_C/Si. 〈110〉-oriented stoichiometric β-SiC with lower density of defects were obtained at R_C/Si in the range of 0.86–1.00, where the maximum R_dep was 883 μm/h at R_C/Si = 1.00, leading to a thickness of 1.7 mm in 2 h deposition. Formation of ridge-like morphology has been discussed based on a twin plane propagation model.     

Studies on the properties of Ni0.6Cu0.4Mn2O4 NTC ceramic due to Fe doping

The influence of the Fe on the microstructure, electrical and dielectric properties of Ni_0.6Cu_0.4Fe_yMn_2?yO₄ (0.1 ≤ y ≤ 0.5) negative temperature coefficient (NTC) thermistors prepared by well known simple chemical co-precipitation method were studied. The replacement of manganese by iron plays an important role in changing the lattice parameter, X-ray density, sintered density, porosity, DC resistivity at different temperatures and dielectric properties at different frequencies. The X-ray and sintered density increased linearly and porosity decreased with iron. The room temperature resistivity of nickel copper manganite NTC ceramic decreased from 1 MΩ cm to 68 KΩ cm and dielectric constant increased from ～9 × 10⁷ to 1.5 × 10⁹ at 20 Hz as iron content increased.     

Densification and mechanical properties of cBN–TiN–TiB2 composites prepared by spark plasma sintering of SiO2-coated cBN powder

cBN–TiN–TiB₂ composites were fabricated by spark plasma sintering at 1773–1973 K using cubic boron nitride (cBN) and SiO₂-coated cBN (cBN(SiO₂)) powders. The effect of SiO₂ coating, cBN content and sintering temperature on the phase composition, densification and mechanical properties of the composites was investigated. SiO₂ coating on cBN powder retarded the phase transformation of cBN in the composites up to 1873 K and facilitated viscous sintering that promoted the densification of the composites. Sintering at 1873 K, without the SiO₂ coating, caused the relative density and Vickers hardness of the composite to linearly decrease from 96.2% to 79.8% and from 25.3 to 4.4 GPa, respectively, whereas the cBN(SiO₂)–TiN–TiB₂ composites maintained high relative density (91.0–96.2%) and Vickers hardness (17.9–21.0 GPa) up to 50 vol% cBN. The cBN(SiO₂)–TiN–TiB₂ composites had high thermal conductivity (60 W m⁻¹ K⁻¹ at room temperature) comparable to the TiN–TiB₂ binary composite.