Fast and wide-band response infrared detector using porous PZT pyroelectric thick film

Porous lead zirconate titanate (PbZr_0.3Ti_0.7O₃, PZT30/70) thick films and detectors for pyroelectric applications have been fabricated on alumina substrates by screen-printing technology. Low temperature sintering of PZT thick films have been achieved at 850 °C by using Li₂CO₃ and Bi₂O₃ sintering aids. The microstructure of PZT thick film has been investigated by X-ray diffraction (XRD) and scanning electron microscopy (SEM). The dielectric properties were measured using HP 4284 at 1 kHz under 25 °C. The permittivity and loss tangent of the thick films were 94 and 0.017, respectively. Curie temperature of PZT thick film was 425 °C as revealed by dielectric constant temperature measurement. The pyroelectric coefficient was determined to be 0.9 × 10⁻⁸ Ccm⁻² K⁻¹ by dynamic current measurement. Infrared detector sensitive element of dual capacitance was fabricated by laser directly write technology. Detectivity of the detectors were measured using mechanically chopped blackbody radiation. Detectivity ranging from 1.23 × 10⁸ to 1.75 × 10⁸ (cm Hz^1/2 W⁻¹) was derived at frequency range from 175.5 Hz to 1367 Hz, and D^*’s −3 dB cut-off frequency bandwidth was 1.2 kHz. The results indicate that the infrared detectors based on porous thick films have great potential applications in fast and wide-band frequency response conditions.     

An infrared pyroelectric detector improved by cool isostatic pressing with cup-shaped PZT thick film on silicon substrate

In this paper, we presented a new pyroelectric detector with back to back silicon cups and micro-bridge structure. The PZT thick film shaped in the front cup was directly deposited with designed pattern by electrophoresis deposition (EPD). Pt/Ti Metal film, which was fabricated by standard photolithography and lift-off technology, was sputtered to connect the top electrode and the bonding pad. The cold isostatic press (CIP) treatment could be applied to improve the pyroelectric properties of PZT thick film. The infrared (IR) properties the CIP-optimized detector were measured. The voltage responsivity (R_V) was 4.5 × 10² V/W at 5.3 Hz, the specific detectivity (D^*) was greater than 6.34 × 10⁸ cm Hz^1/2 W⁻¹ (frequency > 110 Hz), and the thermal time constant was 51 ms, respectively.     

In situ TEM study of stability of TaRhx diffusion barriers using a novel sample preparation method

The atomic diffusion mechanisms associated with metallurgical failure of TaRh_x diffusion barriers for Cu metallizations were studied by in situ transmission electron microscopy (TEM). The issues related to in situ heating of focused ion beam (FIB) prepared cross-sectional TEM samples that contain Cu thin films are discussed. The Cu layer in Si/(13 nm)TaRh_x/Cu stacks showed grain growth and formation of voids at temperatures exceeding 550 °C. For Si/(43 nm)TaRh_x/Cu stacks, grain growth of Cu was delayed to higher temperatures, i.e., 700 °C, and void formation was not observed. Extensive surface diffusion of Cu, however, preceded bulk diffusion. Therefore, a 10 nm film of electron beam evaporated C was deposited on both sides of the TEM lamellae to limit surface diffusion. This processing technique allowed for direct observation of atomic diffusion and reaction mechanisms across the TaRh_x interface. Failure occurred by nucleation of orthorhombic RhSi particles at the Si/TaRh_x interface. Subsequently, the barrier at areas adjacent to RhSi particles was depleted in Rh. This created lower density areas in the barrier, which facilitated diffusion of Cu to the Si substrate to form Cu₃Si. The morphology of an in situ annealed lamella was compared with an ex situ bulk annealed sample, which showed similar reaction morphology. The sample preparation method developed in this study successfully prevented surface diffusion/delamination of the Cu layer and can be employed to understand the metallurgical failure of other potential diffusion barriers.     

Nb doping effect on TiO2−x films for bolometer applications

Nb-doped TiO_2−x thin films were deposited using a 1 at% niobium doped titanium target by RF reactive magnetron sputtering at various oxygen partial pressures (pO₂). The films appeared amorphous in the pO₂ range of 4.4–4.7% with resistivity ranging from 0.39 Ω cm to 2.48 Ω cm. Compared to pure TiO_2−x films, the resistivity of the Nb-doped TiO_2−x films did not change sensitively with the oxygen partial pressure, indicating that the resistivity of the films can be accurately controlled. 1/f noise parameter of Nb-doped TiO_2−x films were found to decrease largely while the measured temperature coefficient of resistance (TCR) of the films was still high. The obtained results indicate that Nb-doped TiO_2−x films have great potential as an alternative bolometric material.     

Annealing effect of platinum-based electrodes on physical properties of PZT thin films

This study examined the crystal structure and surface morphology, including the Ti segregation mechanism on the surface due to the inter-diffusion between Pt, Ti and TiO_x as a glue layer, according to the annealing temperature and growth orientation of a Pt film. In addition, the fatigue mechanism of ferroelectric PZT thin films deposited on a Pt-based electrode was also investigated. The nano-structure, orientation mapping, and micro-morphologies of the triangular Pt hillocks were investigated by scanning electron microscopy with an electron backscatter diffraction (EBSD) function. The D–E hysteresis loop of the ferroelectric films was measured using a Sawyer–Tower circuit at 1 kHz to obtain the remanent polarization and coercive field.     

The initial growth structure of Ni1-xFex (x=0.6–0.8) films dc-biased plasma-sputter-deposited on Ni/MgO(0 0 1), and on Fe/MgO(0 0 1)

Cross sectional and plane-view transmission electron microscopy (X- and PV-TEM) were used to investigate the initial growth phase of 5, 10, 20 and 40 nm thick Ni_1-xFe_x (x=0.6–0.8) films, prepared on MgO(0 0 1) covered with a buffer layer of Fe or Ni as well as on naked MgO(0 0 1). The 100 nm thick buffer layers of Fe and Ni were pre-grown on MgO(0 0 1). All of Ni_0.20Fe_0.80, Ni_0.40Fe_0.60, Fe and Ni films could be epitaxially grown at 250°C by dc-biased plasma sputtering at 2.9 kV in pure Ar gas.The films of Ni_0.20Fe_0.80 and Ni_0.40Fe_0.60 were grown in their own stable phase, bcc and fcc on MgO(0 0 1), respectively. However, Ni_0.20Fe_0.80 film could be grown in fcc phase pseudomorphic with Ni(0 0 1) up to 20 nm thick on Ni/MgO(0 0 1), while Ni_0.40Fe_0.60 film in bcc phase pseudomorphic with Fe(0 0 1) up to 10 nm thick on Fe/MgO(0 0 1). With increasing thickness, their growth phases transformed into their own stable phases. Whether or not the pseudomorphic phase may be induced and what its critical thickness may be should depend primarily on the lattice misfit between the crystal planes in contact. The growth mode of Ni_0.40Fe_0.60 film was investigated more in details to be compared with the simulations of the average strain energy versus thickness and with those of the critical thickness of the pseudomorphic films versus the lattice misfit between the contacted crystal planes.     

Quick response PZT/P(VDF-TrFE) composite film pyroelectric infrared sensor with patterned polyimide thermal isolation layer

The fabrication method and the pyroelectric response of a single element infrared sensor based lead zirconate titanate (PZT) particles and polyvinylidene fluoride P(VDF-TrFE) copolymer composite thick film is reported in this paper. A special thermal insulation structure, including polyimide (PI) thermal insulation layer and thermal insulation tanks, was used in this device. The thermal insulation tanks were fabricated by laser micro-etching technique. Voltage responsivity (R_V), noise voltage (V_noise), noise equivalent power (NEP), and detectivity (D^*) of the PZT/P(VDF-TrFE) based infrared sensor are 1.2 × 10³ V/W, 1.25 × 10⁻⁶ V Hz^1/2, 1.1 × 10⁻⁹ W and 1.9 × 10⁸ cm Hz^1/2 W⁻¹ at 137.3 Hz modulation frequency, respectively. The thermal time constant of the infrared sensor τ_T was about 15 ms. The results demonstrate that the composite infrared sensor show a high detectivity at high chopper frequency, which is an essential advantage in infrared detectors and some other devices.     

Modified Lanthanum Zirconium Oxide buffer layers for low-cost,high performance YBCO coated conductors

The pyrochlore Lanthanum Zirconium Oxide, La₂Zr₂O₇ (LZO), has been developed as a potential replacement barrier layer in the standard RABiTS three-layer architecture of physical vapor deposited CeO₂ cap/YSZ barrier/Y₂O₃ seed on Ni–5%W metal tape. The main focus of this research is to ascertain whether: (i) we can further improve the barrier properties of LZO; (ii) we can modify the LZO cation ratio and still achieve a high level of performance; and (iii) it is possible to reduce the number of buffer layers. We report a systematic investigation of the LZO film growth with varying compositions of La:Zr ratio in the La₂O₃–ZrO₂ system. Using a metal–organic deposition (MOD) process, we have grown smooth, crack-free, epitaxial thin films of La_xZr_1?xO_y (x = 0.2–0.6) on standard Y₂O₃ buffered Ni–5W substrates in short lengths. Detailed XRD studies indicate that a single epitaxial LZO phase with only (0 0 1) texture can be achieved in a broad compositional range of x = 0.2–0.6 in La_xZr_1?xO_y. Both CeO₂ cap layers and MOD–YBCO films were grown epitaxially on these modified LZO barriers. High critical currents per unit width, I_c of 274–292 A/cm at 77 K and self-field were achieved for MOD–YBCO films grown on La_xZr_1?xO_y (x = 0.4–0.6) films. These results indicate that LZO films can be grown with a broad compositional range and still support high performance YBCO coated conductors. In addition, epitaxial MOD La_xZr_1?xO_y (x = 0.25) films were grown directly on biaxially textured Ni–3W substrates. About 3 μm thick YBCO films grown on a single MOD–LZO buffered Ni–3W substrates using pulsed laser deposition show a critical current density, J_c, of 0.55 MA/cm² (I_c of 169 A/cm) at 77 K and 0.01 T. This work holds promise for a route for producing simplified buffer architecture for RABiTS based YBCO coated conductors.     

Current transport mechanism and photovoltaic properties of photoelectrochemical cells of ITO/TiO2/PVC–LiClO4/graphite

This paper deals with the current transport mechanism of solid state photoelectrochemical cells of ITO/TiO₂/PVC–LiClO₄/graphite as well as the physical properties of a component of a device affecting its performance. The principle of operation and a schematic energy level diagram for the materials used in the photoelectrochemical cells are presented. The device makes use of ITO films, TiO₂ films, PVC–LiClO₄ and graphite films as photoanode, photovoltaic material, solid electrolyte and counter electrode, respectively. The device shows rectification. The J_sc and V_oc obtained at 100 mW cm⁻² were 0.95 μAcm⁻² and 180 mV, respectively.     

Photoelectrochromic properties of NiO film deposited on an N-doped TiO2 photocatalytical layer

N-doped TiO₂ film was synthesized on indium–tin oxide (ITO) conducting glass substrate by the hydrolysis method and characterized by X-ray diffraction (XRD), X-ray photoelectron spectroscopy (XPS) and scanning electron microscopy (SEM). Then high porous NiO was deposited onto the TiO_2?xN_x layer by chemical bath deposition (CBD) to prepare a double-layer TiO_2?xN_x/NiO electrode. The photoelectrochromic properties of the TiO_2?xN_x/NiO electrode were discussed through the results of UV–vis transmittance spectra, cyclic voltammogram and photocurrent transient measurements. It was found that the TiO_2?xN_x/NiO electrode was sensitive to light and exhibited a noticeable photoelectrochromism. The NiO film changed its color from colorless to brown, and the transmittance varied from 86.8% to 14.5% at 500 nm after 1 h irradiation.     

Influence of growth morphology on the Néel temperature of CrRu thin films and heterostructures

Dimensionality effects on epitaxial and polycrystalline Cr_1?xRu_x alloy thin films and in Cr/Cr–Ru heterostructures are reported. X-ray analysis on Cr_0.9965Ru_0.0035 epitaxial films indicates an increase in the coherence length in growth directions (1 0 0) and (1 1 0) with increasing thickness (d), in the range 20≤d≤300 nm. Atomic force microscopy studies on these films shows pronounced vertical growth for d>50 nm, resulting in the formation of columnar structures. The Néel temperatures (T_N) of the Cr_0.9965Ru_0.0035 films show anomalous behaviour as a function of d at thickness d≈50 nm. It is interesting to note that this thickness corresponds to that for which a change in film morphology occurs. Experiments on epitaxial Cr_1?xRu_x thin films, with 0≤x≤0.013 and d=50 nm, give T_N–x curves that correspond well with that of bulk Cr_1?xRu_x alloys. Studies on Cr/Cr_0.9965Ru_0.0035 superlattices prepared on MgO(1 0 0), with the Cr layer thickness varied between 10 and 50 nm, keeping the Cr_0.9965Ru_0.0035 thickness constant at 10 nm, indicate a sharp decrease in T_N as the Cr separation layers reaches a thickness of 30 nm; ascribed to spin density wave pinning in the Cr layers for d<30 nm by the adjacent CrRu layers.     

Thermal stabilities of metal bottom electrodes for Ta2O5 metal-oxide-metal capacitor structure

Thermal stabilities of various metal bottom electrodes were examined by using a Ta₂O₅ metal-oxide-metal (MOM) capacitor structure. After depositing 10-nm thick Ta₂O₅ on metal-electrode/poly-Si, we performed rapid thermal oxidation (RTO) at 850 °C for 60 s in an O₂ ambient. A chemical-vapor-deposition (CVD) WSi₂ electrode showed satisfactory thermal stability after the RTO, while other examined electrode materials exhibited thermal degradation caused by oxidation failure or interfacial reaction between the substrate poly-Si and the Ta₂O₅. After post-annealing at 650 °C for 30 min (in N₂ condition) with CVD TiN top electrode, an effective oxide thickness (T_ox) of ∼32 Å and a leakage current density of ∼10⁷ A/cm² at 1.25 V were obtained from the MOM capacitor with the WSi₂ bottom electrode. Other electrode materials, such as TiN, TiSi_x, WN_x, W, and Ta, were severely oxidized during the RTO in the MOM structures, and very poor capacitor properties were obtained in terms of T_ox and leakage current.     

Electrode reaction of Sr1−xLaxCo0.8Fe0.2O3−δ with x = 0.1 and 0.6 on Ce0.9Gd0.1O1.95 at 600 ≤ T ≤ 800 °C

The electrode reaction of the perovskite phases Sr_1−xLa_xCo_0.8Fe_0.2O_3−δ (x = 0.1 and 0.6) on Ce_0.9Gd_0.1O_1.95 has been investigated by impedance spectroscopy in the temperature range 600 ≤ T ≤ 800 °C. Thick porous electrodes (t ∼ 20 μm) were sprayed on Ce_0.9Gd_0.1O_1.95 and ac impedance spectra were recorded on symmetrical cells at the equilibrium. The analysis of the complex impedance diagrams clearly indicates the presence of two contributions. The low frequency one was assigned to the gas phase oxygen diffusion through the porous electrode and a finite length diffusion (Warburg) impedance was used to describe the high frequency (HF) data. The polarization resistance of the HF impedance contribution (R_w) is higher for x = 0.1 while the activation energy of R_w is higher for x = 0.6. The variations of R_w versus the La content, temperature and thickness indicate that the Warburg-type impedance contains information of both bulk oxygen diffusion and surface processes.     

Influence of thickness and band structure of insulating barriers on resistance and tunneling magnetoresistance properties of magnetic tunnel junctions with Al-oxide and Ti-alloyed Al-oxide barriers

We investigated the influence of insulating barrier thickness and the Ti composition dependence of the band structure of Al-oxide on the resistance and tunneling magnetoresistance (TMR) behavior of the magnetic tunnel junction (MTJ). Low resistance × area (RA) value (1.1 MΩ μm²) was achieved by decreasing the Al-oxide thickness down to 1.0 nm. However, this led to the partial oxidation of the bottom ferromagnetic (FM) electrode of the junction and non-continuous thin barriers by the occurrence of pinholes, with low TMR ratio of 8.3%. For an alternative for low RA value, we developed a new Ti-alloyed Al-oxide (TiAlO_x) that had lower band gap than Al-oxide as an insulating barrier of MTJ. As the Ti concentration increased up to 5.33 at.% Ti in Al, the RA value of the MTJs was reduced from 9.5 to 0.69 MΩ μm², owing to the band-gap reduction of TiAlO_x caused by the formation of extra bands, mainly composed of Ti-3d orbitals, within the band gap. It was analyzed that TiAlO_x has localized d states in the band gap below the conduction band. In addition, the TMR ratio increased with the Ti concentration and reached a maximum of 49% at 5.33 at.% Ti owing to the microstructural evolution of Ti–Al alloy film in the pre-oxidation state.     

Electrical properties of yttrium doped strontium titanate with A-site deficiency as potential anode materials for solid oxide fuel cells

Yttrium doped strontium titanate with A-site deficiency ((Y_0.08Sr_0.92)_1 ? xTiO_3 ? δ) was synthesized by conventional solid state reaction. The deficiency limit of A-site in (Y_0.08Sr_0.92)_1 ? xTiO_3 ? δ is below 6 mol% in Ar/H₂ (5%) at 1500 °C. The sinterability of (Y_0.08Sr_0.92)_1 ? xTiO_3 ? δ samples decreases slightly with increasing A-site deficiency level (x). The ionic conductivity of (Y_0.08Sr_0.92)_1 ? xTiO_3 ? δ samples increases while the electronic conductivity decreases with increasing A-site deficient amount. The defect chemistry analysis indicates that the introduction of A-site deficiency results in not only the increase of oxygen vacancy concentration but also the decrease of Ti³⁺-ion concentration. The latter plays the main role in the electrical conduction. (Y_0.08Sr_0.92)_1 ? xTiO_3 ? δ shows good thermal-cyclic performance in electrical conductivity and has an excellent chemical compatibility with YSZ electrolyte below 1500 °C.     

The interaction of O2 with the surface of polycrystalline gadolinium at the temperature range 300–670 K

Auger-Electron-Spectroscopy (AES) and Direct-Recoils-Spectrometry (DRS) were applied to study the interaction of O₂ with a polycrystalline gadolinium surface, in the temperature range 300–670 K and oxygen pressure up to 2 × 10^? 6 Torr. It has been found that initial uptake of oxygen, at coverage measurable by the techniques used here, results in rapid oxide island formation. The subsurface is believed to be a mixture of oxide particles and oxygen dissolved in the Gd metal, the latter being the mobile species, even at relatively low temperatures.Enhanced inward diffusion of oxygen starts as early as 420 K and dictates the surface oxygen concentration and effective thickness of the forming oxide. The oxygen accumulation rate at the near-surface region, as measured by the O(KLL) AES signal intensity, goes through a maximum as a function of temperature at 420 K. This is a result of the combination of still efficient oxygen chemisorption that increases surface occupation and slow inward diffusion. The thickest oxide, ~ 1.7 nm, is formed at 300 K and its effective thickness was found to decrease with increasing temperature (due to oxygen dissolution into the metal bulk).Diffusion coefficients of the oxygen dissolution into the bulk were evaluated for various temperatures utilizing models for infinitely thin oxide layer and thick oxide layer, respectively. The best fit under our experimental procedure was obtained by the thick layer model, and the coefficients that were calculated are D₀ = 2.2 × 10^? 16m²s^? 1 and E_a = 46kJ/mol.     

A ceria layer as diffusion barrier between LAMOX and lanthanum strontium cobalt ferrite along with the impedance analysis

A thin interlayer of samarium doped ceria (SDC) is applied as diffusion barrier between La_1 ? xSr_xCo_yFe_1 ? yO₃ x = 0.1–0.4, y = 0.2–0.8 (LSCF) cathode and La_1.8Dy_0.2Mo_1.6W_0.4O₉ (LDMW82) electrolyte to obstruct Mo–Sr diffusion and solid state reaction in the intermediate temperature range of SOFC. We demonstrate the effectiveness of the diffusion barrier through contrasting the clearly defined interfaces of LSCF/SDC/LDMW82 against a rugged growing product layer of LSCF/LDMW82 in 800 °C thermal annealing, and analyze the product composition and the probable new phase. In addition, the measured polarization resistance is considerably lower for the half-cell with a diffusion barrier. Therefore, the electrochemical performance of the LSCF cathode is investigated on the SDC-protected LDMW82. The cell with LSCF (x = 0.4) persistently outperforms the one with x = 0.2 in polarization resistance because of its small low-frequency contribution. The activation energy of polarization resistance is also lower for La_0.6Sr_0.4Co_yFe_1 ? yO₃ (112–135 kJ/mol), than that for La_0.8Sr_0.2Co_yFe_1 ? yO₃ (156–164 kJ/mol). La_0.6Sr_0.4Co_yFe_1 ? yO₃ y = 0.4–0.8 is the proper composition for the cathode interfaced to SDC/LDMW82.     

The growth and field evaporation of Er and deuterated Er films

The morphological structure of clean and deuterated Er films deposited on W substrates and their removal by field evaporation have been investigated as part of a program directed toward the development of deuterium ion sources for neutron generators. Annealed Er films up to ~ 20 monolayers in thickness deposited on W < 110 > substrates appear pseudomorphic. Thicker annealed films form a hexagonal close-packed < 0001 > orientated over-layer with the Pitsch–Schrader orientation relation. The pseudomorphic and hexagonal close-packed character of the films is retained up to the last atomic layer that forms the film-substrate interface. Deuterated Er films appear polycrystalline. At 77 K in Ar, annealed Er films field evaporate at 2.5 V/Å primarily as Er^2 + and deuterated Er films evaporate at ~ 2.4 V/Å primarily as ErD_x^2 +. Field evaporation of both clean and deuterated Er films shows signs of space charge induced field lowering when film thicknesses exceeding ~ 10 layers were field evaporated using 20 ns duration voltage pulses.     

Lead free KNN/P(VDF-TrFE) 0–3 pyroelectric composite films and its infrared sensor

(K_0.5Na_0.5)NbO₃ (KNN)/[P(VDF-TrFE)70:30] composite thick films with different KNN weight ratios have been fabricated and the effect of KNN mass content on the material structure and properties have been studied in this paper. Properties of the infrared sensor based KNN/[P(VDF-TrFE)70:30] composite thick film were also systematically studied. It was found that the sample containing 30 wt.% KNN show optimal properties for pyroelectric appliance and the highest pyroelectric coefficient was 63 μCm⁻² K⁻¹. Infrared sensors using 30 wt.% KNN-70 wt.%[P(VDF-TrFE)70:30] show highest detectivity (D¹ = 3.21 × 10⁸ cm Hz^1/2 W⁻¹) at 137.3 Hz, indicating it is an promising candidate in lead-free quick response infrared detectors.     

Cation site environment in ultrathin TiOx films grown on Pt(1 1 1) probed by X-ray absorption spectroscopy at the Ti 2p edge

We present the results of a XAS experiment carried out at the Ti 2p edge on well-ordered TiO_x ultrathin films grown on the Pt(1 1 1) surface. XAS at the Ti 2p edge has been extensively applied to the study of Ti bulk compounds, particularly to the study of titania. According to the literature, the corresponding Ti 2p edge spectral shape is related to the stoichiometry and crystal field symmetry at the Ti sites. In the present study we aim at extending the potential of the XAS technique by discussing Ti 2p spectra obtained on several, dimensionally confined, TiO_x phases in the form of ultrathin films. One of the main features of these films is their high degree of structural order. Furthermore, the results of previous studies provide valuable information about the chemistry and structure of the films, so that we are able to analyse the current XAS data in detail and to compare them with the appropriate Ti 2p XAS data of bulk oxides. We find that in the case of ultrathin film with a fully oxidised Ti⁴⁺ stoichiometry, the Ti 2p XAS data display features that are very similar to the ones observed in related bulk systems. The XAS data of the reduced TiO_x films (with x < 2) show a rather different and specific shape. By comparing the experimental spectra with an atomic type of model calculation we show that the Ti 2p XAS profiles can be attributed mainly to stoichiometry-symmetry effects.