Preparation and Characterization of Epitaxial Conductive Nb-SrTiO<Subscript>3</Subscript> Thin Films on Si Substrates

Epitaxial Nb-doped SrTiO₃ (001) thin films have been integrated on Si(001) single-crystal substrates with a TiN template layer by radio-frequency (RF) sputtering. The epitaxial growth of Nb-SrTiO₃ was achieved in an Ar environment at a substrate temperature of 540°C. The orientation relationship was determined to be simply cube-on-cube as Nb-SrTiO₃ (001)[110]||TiN(001) [110]||Si(001)[110]. The deposited Nb-SrTiO₃ films show a smooth and featureless surface with roughness below 1 nm. These smooth Nb-doped SrTiO₃/TiN/Si films have a conductivity of 500 S/cm and could be promising electrodes for subsequent ferroelectric thin films.     

Microgenerator Using BiSbTe-Pt Thermopile and Pt-Al<Subscript>2</Subscript>O<Subscript>3</Subscript> Ceramic Combustor

The performance of a microcombustor thermoelectric generator device based on a thermopile using p-type Bi_0.3Sb_1.7Te₃ (BST) and n-type Pt films has been investigated. The BST films were prepared by two different methods—pulsed laser deposition (PLD) and sputter deposition—on Si₃N₄/SiO₂ multilayers on Si substrate. The ceramic catalyst combustor was patterned on the thermopile end on a thin membrane fabricated by back-side bulk etching of the silicon substrate. At 138°C the thermoelectric power factors of the PLD and sputter-deposited films were 3.6 × 10⁻³ W/mK² and 0.22 × 10⁻³ W/mK², respectively. The power from the generator with the sputter-deposited film was 0.343 μW, which was superior to that of the device with the PLD film, which provided 0.1 μW, for combustion of a 200 sccm flow of 3 v/v% hydrogen in air.     

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).     

Impedance Spectroscopy of Dielectric BaTi<Subscript>5</Subscript>O<Subscript>11</Subscript> Film Prepared by Laser Chemical Vapor Deposition Method

BaTi₅O₁₁ film was prepared on Pt/Ti/SiO₂/Si substrate by the laser chemical vapor deposition method. A single-phase BaTi₅O₁₁ film with ([`3] 22)/([`2] 23) (\overline{3} 22)/(\overline{2} 23) preferred orientation and columnar cross-section was obtained at high deposition rate (154.8 μm h⁻¹). The dielectric constant (ε _r) of the BaTi₅O₁₁ film was 21, measured at 300 K and 1 MHz. The electrical properties of the BaTi₅O₁₁ film were investigated by ac impedance spectroscopy from 300 K to 1073 K at 10² Hz to 10⁷ Hz. Plots of the real and imaginary parts of the impedance (Z′ and Z″) and electrical modulus (M′ and M″) in the above frequency and temperature range suggested the presence of two relaxation regimes, which were attributed to grain and grain boundary responses. The ac conductivity plots as a function of frequency showed three types of conduction process at elevated temperature. The frequency-independent plateau at low frequency was due to dc conductivity. The mid-frequency conductivity was due to grain boundaries, while the high-frequency conductivity was due to grains.     

Crystallization behavior and ferroelectric properties of PbTiO<Subscript>3</Subscript>/Ba<Subscript>0.85</Subscript>Sr<Subscript>0.15</Subscript>TiO<Subscript>3</Subscript>/PbTiO<Subscript>3</Subscript> sandwich thin film on Pt/Ti/SiO<Subscript>2</Subscript>/Si substrates

A PbTiO₃/Ba_0.85Sr_0.15TiO₃/PbTiO₃ (PT/BST15/PT) sandwich thin film has been prepared on Pt/Ti/SiO₂/Si substrates by an improved sol-gel technique. It is found that such films under rapid thermal annealing at 700°C crystallize more favorably with the addition of a PbTiO₃ layer. They possess a pure, perovskite-phase structure with a random orientation. The polarization-electric field (P-E) hysteresis loop and current-voltage (I-V) characteristic curves reveal that a PT/BST15/PT film exhibits good ferroelectricity at room temperature. However, no sharp peak, only a weak maximum, is observed in the curves of the dielectric constant versus temperature. The dielectric constant, loss tangent, leakage current density at 20 kV/cm, remnant polarization, and coercive field of the PT/BST15/PT film are 438, 0.025, 1.3 × 10⁻⁶ Acm⁻², 2.46 μCcm⁻², and 41 kVcm⁻¹, respectively, at 25°C and 10 kHz. The PT/BST15/PT film is a candidate material for high sensitivity elements for uncooled, infrared, focal plane arrays (UFPAs) to be used at near ambient temperature.     

Electrodeposition of <Emphasis Type="Italic">p</Emphasis>-Type Sb<Subscript><Emphasis Type="Italic">x</Emphasis></Subscript>Te<Subscript><Emphasis Type="Italic">y</Emphasis></Subscript> Thermoelectric Films

Thermoelectric Sb _x Te _y films were potentiostatically electrodeposited in aqueous nitric acid electrolyte solutions containing different concentrations of TeO₂. Stoichiometric Sb _x Te _y films were obtained by applying a voltage of −0.15 V versus saturated calomel electrode (SCE) using a solution consisting of 2.4 mM TeO₂, 0.8 mM Sb₂O₃, 33 mM tartaric acid, and 1 M HNO₃. The nearly stoichiometric Sb₂Te₃ films had a rhombohedral structure, R[`3]m R\bar{3}m , with a preferred orientation along the (015) direction. The films had hole concentration of 5.8 × 10¹⁸/cm³ and exhibited mobility of 54.8 cm²/Vs. A more negative potential resulted in higher Sb content in the deposited Sb _x Te _y films. Furthermore, it was observed that the hole concentration and mobility decreased with increasingly negative deposition potential, and eventually showed insulating properties, possibly due to increased defect formation. The absolute value of the Seebeck coefficient of the as-deposited Sb₂Te₃ thin film at room temperature was 118 μV/K.     

LaAlO<Subscript>3</Subscript>/SrTiO<Subscript>3</Subscript> Epitaxial Heterostructures by Atomic Layer Deposition

Thin films of LaAlO₃ were deposited on TiO₂-terminated (100) SrTiO₃ crystals by atomic layer deposition (ALD), using tris(iso-propylcyclopentadienyl)lanthanum and trimethyl aluminum precursors. Water was used as the oxidizer. The film composition was shown to be controlled by the ratio of La/Al precursor pulses during ALD, with near-stoichiometric LaAlO₃ resulting at precursor pulse ratios of 4/1 to 5/1. Films near the stoichiometric LaAlO₃ composition were shown to crystallize on subsequent annealing to form epitaxial LaAlO₃/SrTiO₃ heterostructures. Electrical characterization of these structures was done by two-terminal direct-current (DC) current–voltage scans at room temperature and under high-vacuum conditions. The results show electrical conductivity for the ALD-deposited epitaxial LaAlO₃/SrTiO₃ heterostructures, which turns on for thickness above four unit cells for the LaAlO₃ film.     

Ultraviolet Photodetection Properties of a Pt Contact on a Mg<Subscript>0.1</Subscript>Zn<Subscript>0.9</Subscript>O/ZnO Composite Film

We report on the ultraviolet (UV) photodetection properties of a Pt contact on a sol-gel Mg_0.1Zn_0.9O/ZnO composite structure on a glass substrate. In the dark, the current–voltage (I–V) characteristics between the Pt and Ag contacts on the top of the ZnO film were linear while that on the Mg_0.1Zn_0.9O/ZnO composite film were rectifying, suggesting the formation of a Schottky diode on the latter. The ideality factor, n, and the reverse leakage current density, J _R , of the Schottky diode were greater than 2 and 2.36 × 10⁻² A cm⁻² at −5 V, respectively. Under ultraviolet light, the I–V characteristics become linear. The maximum photo-to-dark current ratio observed was about 63. The composite film showed good sensitivity to UV light with wavelengths of less than 400 nm, though the photoresponse process was found to be slow.     

Thermoelectric Properties of Ag-doped Mg<Subscript>2</Subscript>Ge Thin Films Prepared by Magnetron Sputtering

Silver doped p-type Mg₂Ge thin films were grown in situ at 773 K using magnetron co-sputtering from individual high-purity Mg and Ge targets. A sacrificial base layer of silver of various thicknesses from 4 nm to 20 nm was initially deposited onto the substrate to supply Ag atoms, which entered the growing Mg₂Ge films by thermal diffusion. The addition of silver during film growth led to increased grain size and surface microroughness. The carrier concentration increased from 1.9 × 10¹⁸ cm⁻³ for undoped films to 8.8 × 10¹⁸ cm⁻³ for the most heavily doped films, but it did not reach saturation. Measurements in the temperature range of T = 200–650 K showed a positive Seebeck coefficient for all the films, with maximum values at temperatures between 400 K and 500 K. The highest Seebeck coefficient of the undoped film was 400 μV K⁻¹, while it was 280 μV K⁻¹ for the most heavily doped film at ∼400 K. The electrical conductivity increased with silver doping by a factor of approximately 10. The temperature effects on power factors for the undoped and lightly doped films were very limited, while the effects for the heavily doped films were substantial. The power factor of the heavily doped films reached a non-optimum value of ∼10⁻⁵ W cm⁻¹ K⁻² at 700 K.     

Electrodeposition and Thermoelectric Characteristics of Bi<Subscript>2</Subscript>Te<Subscript>3</Subscript> and Sb<Subscript>2</Subscript>Te<Subscript>3</Subscript> Films for Thermopile Sensor Applications

A thermopile sensor was processed on a glass substrate by electrodeposition of n-type bismuth telluride (Bi-Te) and p-type antimony telluride (Sb-Te) films. The n-type Bi-Te film electrodeposited at −50 mV in a 50 mM electrolyte with a Bi/(Bi + Te) mole ratio of 0.5 exhibited a Seebeck coefficient of −51.6 μV/K and a power factor of 7.1 × 10⁻⁴ W/K² · m. The p-type Sb-Te film electroplated at 20 mV in a 70 mM solution with an Sb/(Sb + Te) mole ratio of 0.9 exhibited a Seebeck coefficient of 52.1 μV/K and a power factor of 1.7 × 10⁻⁴ W/K² · m. A thermopile sensor composed of 196 pairs of the p-type Sb-Te and the n-type Bi-Te thin-film legs exhibited sensitivity of 7.3 mV/K.     

Development of (Bi,Sb)<Subscript>2</Subscript>(Te,Se)<Subscript>3</Subscript>-Based Thermoelectric Modules by a Screen-Printing Process

In major applications, optimal power will be achieved when thermoelectric films are at least 100 μm thick. In this paper we demonstrate that screen-printing is an ideal method to deposit around 100 μm of (Bi,Sb)₂(Te,Se)₃-based films on a rigid or flexible substrate with high Seebeck coefficient value (90 μV K⁻¹ to 160 μV K⁻¹) using a low-temperature process. Conductive films have been obtained after laser annealing and led to acceptable thermoelectric performance with a power factor of 0.06 μW K⁻² cm⁻¹. While these initial material properties are not at the level of bulk materials, the complete manufacturing process is cost-effective, compatible with large surfaces, and affords a mass-production technique.     

Dielectric properties of low loss Ba<Subscript>6−3x</Subscript>Nd<Subscript>8+2x</Subscript>Ti<Subscript>18</Subscript>O<Subscript>54</Subscript> thin films prepared by pulsed laser deposition for microwave applications

Ba_6−3xNd_8+2xTi₁₈O₅₄ with x=0.25 (BNT-0.25, or simply, BNT) dielectric thin films with a thickness of 320 nm have been prepared on Pt-coated silicon substrates by pulsed laser deposition (PLD) at the substrate temperature of 650°C in 20 Pa oxygen ambient. X-ray analysis showed that the as-deposited films are amorphous and the films remain amorphous after a postannealing at 750°C for 30 min. The dielectric constant of the BNT films has been determined to be about 80 with a low loss tan δ of about 0.006 at 1 MHz. The capacitance-voltage (C-V), capacitance-frequency, and capacitance-temperature characteristics of a BNT capacitor with Pt top electrode were measured. A low leakage-current density of 4×10⁻⁶ A/cm² at 6 V was measured, and a preliminary discussion of the leakage-current mechanism is also given. It is proposed that amorphous BNT-0.25 thin films will be a potential dielectric material for microwave applications.     

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.     

Thermoelectric Properties of Zr<Subscript>3</Subscript>Mn<Subscript>4</Subscript>Si<Subscript>6</Subscript> and TiMnSi<Subscript>2</Subscript>

The Seebeck coefficient, electrical resistivity, and thermal conductivity of Zr₃Mn₄Si₆ and TiMnSi₂ were studied. The crystal lattices of these compounds contain relatively large open spaces, and, therefore, they have fairly low thermal conductivities (8.26 Wm⁻¹ K⁻¹ and 6.63 Wm⁻¹ K⁻¹, respectively) at room temperature. Their dimensionless figures of merit ZT were found to be 1.92 × 10⁻³ (at 1200 K) and 2.76 × 10⁻³ (at 900 K), respectively. The good electrical conductivities and low Seebeck coefficients might possibly be due to the fact that the distance between silicon atoms in these compounds is shorter than that in pure semiconductive silicon.     

Thermoelectric Performance of Zn and Nd Co-doped In<Subscript>2</Subscript>O<Subscript>3</Subscript> Ceramics

Polycrystalline In₂O₃ ceramics co-doped with Zn and Nd were prepared by the spark plasma sintering (SPS) process, and microstructure and thermoelectric (TE) transport properties of the ceramics were investigated. Our results indicate that co-doping with Zn²⁺ and Nd³⁺ shows a remarkable effect on the transport properties of In₂O₃-based ceramics. Large electrical conductivity (~130 S cm⁻¹) and thermopower (~220 μV K⁻¹) can be observed in these In₂O₃-based ceramic samples. The maximum power factor (PF) reaches 5.3 × 10⁻⁴ W m⁻¹ K⁻² at 973 K in the In_1.92Nd_0.04Zn_0.04O₃ sample, with a highest ZT of ~0.25.     

Interface-Charge-Coupled Polarization Response of Pt-BaTiO<Subscript>3</Subscript>-ZnO-Pt Heterojunctions: A Physical Model Approach

Heterojunctions composed of wurtzite-structure (piezoelectric) ZnO and perovskite-structure (ferroelectric) BaTiO₃ are very interesting because of the previously observed ionic lattice polarization coupling at their interfaces. We report electric Sawyer-Tower polarization hysteresis measurements and analysis of a ZnO-BaTiO₃ heterostructure with Pt front and back contacts deposited by pulsed laser deposition onto a (001) silicon substrate. The ZnO layer is n-type (N _c = 5.5 × 10¹⁶ cm⁻³), and the BaTiO₃ (BTO) layer is highly resistive. We observe a strong asymmetric ferroelectric hysteresis, which we attribute to a rectifying depletion layer formation between the ZnO and BaTiO₃ layers. The coupling between the wurtzite-structure and perovskite-structure interface polarization influences the depletion layer formation. We develop a physical model for the electric Sawyer-Tower measurements. Our model includes the effects of the depletion layer formation inside the ZnO layer, the interface charge coupling between the ZnO and BaTiO₃ layers, and the field-dependent ferroelectric polarization inside the BTO. We obtain a very good agreement between our model-generated data and our experiment. We identify voltages in forward and reverse direction at which the depletion layer opens or closes. These voltages are asymmetric, and reveal the effect of the spontaneous piezoelectric (nonswitchable) interface charge of ZnO, which we determine from our analysis here as P _sz = −4.1 μC/cm².     

Vapor Annealing as a Post-Processing Technique to Control Carrier Concentrations of Bi<Subscript>2</Subscript>Te<Subscript>3</Subscript> Thin Films

This article demonstrates that carrier concentrations in bismuth telluride films can be controlled through annealing in controlled vapor pressures of tellurium. For the bismuth telluride source with a small excess of tellurium, all the films reached a steady state carrier concentration of 4 × 10¹⁹ carriers/cm³ with Seebeck coefficients of −170 μV K⁻¹. For temperatures below 300°C and for film thicknesses of 0.4 μm or less, the rate-limiting step in reaching a steady state for the carrier concentration appeared to be the mass transport of tellurium through the gas phase. At higher temperatures, with the resulting higher pressures of tellurium or for thicker films, it was expected that mass transport through the solid would become rate limiting. The mobility also changed with annealing, but at a rate different from that of the carrier concentration, perhaps as a consequence of the non-equilibrium concentration of defects trapped in the films studied by the low temperature synthesis approach.     

Thermal Stability of Ge<Subscript>2</Subscript>Sb<Subscript>2</Subscript>Te<Subscript>5</Subscript> in Contact with Ti and TiN

The thermal stability of a Ge₂Sb₂Te₅ chalcogenide layer in contact with titanium and titanium nitride metallic thin films has been investigated mainly using x-ray diffraction and elastic nuclear backscattering techniques. Without breaking vacuum, Ti and TiN have been deposited on Ge₂Sb₂Te₅ material using magnetron sputtering. Thermal treatments have been performed in a 10⁻⁷ mbar vacuum furnace. On annealing up to 450°C, the TiN metallic film does not interact with the chalcogenide film, but at the same time adhesion problems and instabilities in contact resistance arise. To improve the adhesion and eventually stabilize the contact resistance, an interfacial Ti layer has been considered. At 300°C, a TiTe₂ compound is formed by interacting with Te segregated from the Ge₂Sb₂Te₅ layer. At higher temperatures, the Ti layer decomposes the chalcogenide film, forming several compounds tentatively identified as GeTe, Ge₃Ti₅, Ge₅Ti₆, TiTe_2,, and Sb₂Te₃. It has been found that the properties of the Ge₂Sb₂Te₅ film can be retained by controlling the decomposition rate of the chalcogenide layer, which is achieved by providing a limited supply of Ti and/or by depositing a Te-rich Ge₂Sb₂Te₅ film.     

Preparation and Thermoelectric Properties of LaGd<Subscript>1+<Emphasis Type="Italic">x</Emphasis></Subscript>S<Subscript>3</Subscript> and SmGd<Subscript>1+<Emphasis Type="Italic">x</Emphasis></Subscript>S<Subscript>3</Subscript>

Thermoelectric materials are attractive since they can recover waste heat directly in the form of electricity. In this study, the thermoelectric properties of ternary rare-earth sulfides LaGd_1+x S₃ (x = 0.00 to 0.03) and SmGd_1+x S₃ (x = 0.00 to 0.06) were investigated over the temperature range of 300 K to 953 K. These sulfides were prepared by CS₂ sulfurization, and samples were consolidated by pressure-assisted sintering to obtain dense compacts. The sintered compacts of LaGd_1+x S₃ were n-type metal-like conductors with a thermal conductivity of less than 1.7 W K⁻¹ m⁻¹. Their thermoelectric figure of merit ZT was improved by tuning the chemical composition (self-doping). The optimized ZT value of 0.4 was obtained in LaGd_1.02S₃ at 953 K. The sintered compacts of SmGd_1+x S₃ were n-type hopping conductors with a thermal conductivity of less than 0.8 W K⁻¹ m⁻¹. Their ZT value increased significantly with temperature. In SmGd_1+x S₃, the ZT value of 0.3 was attained at 953 K.     

How r-Plane Al<Subscript>2</Subscript>O<Subscript>3</Subscript> Surface Modifications Impact the Growth of Epitaxial (001) CeO<Subscript>2</Subscript> Thin Films

We present evidence that it is the presence or absence of atomic terraces with a specific crystallographic orientation on the (102) Al₂O₃ surface that promotes growth of single-crystal (001) CeO₂ films over polycrystalline (111) CeO₂ films. The CeO₂ film nucleates so that the [010] and [100] directions of the film align parallel and perpendicular to the terrace edges. In the absence of terraces, multidomain (111) CeO₂ films result in which the in-plane orientation of the two domains are rotated by 85.71°, so that a [110] CeO₂ direction aligns parallel to either the or Al₂O₃ direction.