Phase transformation and paired-plate precipitate formation in Pb0.91La0.09Zr0.65Ti0.35O3 films grown on sapphire substrates

We report on the phase transformation behavior of Pb_0.91La_0.09Zr_0.65Ti_0.35O₃ (9/65/35) PLZT films grown on r-sapphire substrates via rf-magnetron sputtering. A complex microstructure results in these films depending on deposition and annealing conditions. A random equiaxed polycrystalline grain morphology was observed after rapid thermal annealing or furnace annealing when the as-deposited films were predominantly pyrochlore. Precipitate formation (100–150 nm) was observed in PLZT films that were deposited at temperatures in excess of 490°C with a perovskite structure, after furnace annealing at 700°C. We believe that this is related to internal stresses in the films due to both the lattice mismatch and the thermal expansion mismatch between the PLZT film and the sapphire substrate.     

Optical and electrical properties of crystalline indium tin oxide thin film deposited by vacuum evaporation technique

Indium tin oxide (ITO) thin film was deposited on glass substrate by means of vacuum evaporation technique and annealed at 200 °C, 300 °C and 400 °C in air for 1 h. The characterization and properties of the deposited film samples were analyzed by X-ray diffraction (XRD), scanning electron microscopy (SEM), and UV-VIS-NIR spectroscopy techniques. From the XRD patterns, it was found that the deposited thin film was of crystalline at an annealing temperature of 400 °C. The crystalline phase was indexed as cubic structure with lattice constant and crystallite size of 0.511 nm and 40 nm, respectively. The SEM images showed that the films exhibited uniform surface morphology with well-defined spherical grains. The optical transmittance of ITO thin film annealed at 400 °C was improved from 44% to 84% in the wavelength range from 250 nm to 2 100 nm and an optical band gap was measured as 3.86 eV. Hall effect measurement was used to measure the resistivity and conductivity of the prepared film.     

Progress in flexible perovskite solar cells with improved efficiency

Perovskite solar cell has emerged as a promising candidate in flexible electronics due to its high mechanical flexibil-ity,excellent optoelectronic properties,light weight and low cost.With the rapid development of the device structure and mater-ials processing,the flexible perovskite solar cells (FPSCs) deliver 21.1％ power conversion efficiency.This review introduces the latest developments in the efficiency and stability of FPSCs,including flexible substrates,carrier transport layers,perovskite films and electrodes.Some suggestions on how to further improve the efficiency,environmental and mechanical stability of FPSCs are provided.Specifically,we considered that to elevate the performance of FPSCs,it is crucial to substantially improve film quality of each functional layer,develop more boost encapsulation approach and explore flexible transparent electrodes with high conductivity,transmittance,low cost and expandable processability.     

Spraying Perovskite Intermediate Enabling Inch-Scale Microwire Film Fabrication for Integration Compatible Efficient-Photodetectors Array

Metal halide perovskite microwires (MWs) have emerged as promising photoactive materials for highly efficient photodetectors (PDs). However, large-scale MWs film fabrication is still a formidable challenge for achieving integration compatible perovskite PDs arrays, owing to precipitation and structure crushing of MWs during deposition and annealing. Herein, a strategy of fabrication of inch-scale perovskite MWs films is presented by depositing perovskite intermediate suspension through spray-coating, which addresses the trade-off present between the high flatness of MWs film and its large-scale fabrication. The single crystalline perovskite MWs weave a film with high enough flatness rendering narrow performance distribution of high efficiency on the 7 × 7 PDs arrays. The formamidinium lead iodide (FAPbI₃) PDs arrays show average responsivity and detectivity of (1.60 ± 0.46) A W⁻¹ and (1.49 ± 0.50) × 10¹² Jones. The methanaminium lead iodide (MAPbI₃) PDs arrays show average responsivity and detectivity of (0.065 ± 0.046) A W⁻¹ and (2.54 ± 0.77) × 10¹¹ Jones. The champion PDs based on FAPbI₃ MWs film and MAPbI₃ MWs film show detectivity of 1.26 × 10¹³ and 9.67 × 10¹¹ Jones, which are much higher than that of corresponding polycrystalline films and located on the top ranking of similar devices.     

Transformation process of laser ablated PZT thin films

Transformation behavior of piezoelectric lead zirconate titanate (PZT) thin films prepared by laser ablation on unheated Al₂O₃ substrates was investigated within a broad temperature region. As-deposited films were mainly amorphous containing some microcrystalline perovskite and pyrochlore phases. The rhombohedral perovskite was the main phase in the films annealed between 500 and 800°C. These films also contained some pyrochIore, PbTiO₃, PbO, and ZrO₂. The PbO and ZrO₂ disappeared in the optimal annealing temperature interval of 700 to 800°C. Decomposition reactions took place above 800°C due to evaporation of lead and diffusion reactions occurred between substrate and film so that the films annealed at 1100°C consisted of ZrO₂, TiO₂, and PbO.     

Effect of post deposition heat treatment on microstructure parameters,optical constants and composition of thermally evaporated CdTe thin films

Thin film microstructure and its properties can be effectively altered with post deposition heat treatments. In this respect, CdTe thin films were deposited on glass substrates at a substrate temperature of 200 °C using thermal evaporation technique, followed by air annealing at different temperatures from 200 to 500 °C. Structural analysis reveals that CdTe thin films have a cubic zincblend structure with two oxide phases related to CdTe₂O₅ and CdTeO₃ at annealing temperature of 400 and 500 °C respectively. Regardless of the annealing temperature, the plane (111) was found to be the preferred orientation for all films. The crystallite size was observed to increase with annealing temperature. All films were found to display higher lattice parameters than the standard, and hence found to carry a compressive stress. Optical measurements suggest high uniformity of films both before and after post deposition heat treatment. Films annealed at 400 °C displayed superior optical properties due to its high refractive index, optical conductivity, relative density and low disorder. Furthermore, according to the compositional measurements, CdTe thin films were found to exhibit Te rich and Cd rich nature at regions near the substrate and center of the film respectively, for all annealing temperatures. However, composition of the regions near the substrate was found to become more Te rich with increasing annealing temperature. The study suggests that changing the annealing temperature as a post deposition treatment affects structural and optical properties of CdTe thin film as well as its composition. According to the observations, films annealed at 400 °C can be concluded to be the best films for photovoltaic applications due to its superior optical and structural properties.     

Tuning the Properties of CZTS Films by Controlling the Process Parameters in Cost-Effective Non-vacuum Technique

Highly dispersive Cu₂ZnSnS₄ (CZTS) nanoparticles were successfully synthesized by a simple solvothermal route. A low cost, non-vacuum method was used to deposit CZTS nanoparticle ink on glass substrates by a doctor blade process followed by selenization in a tube furnace to form Cu₂ZnSn (S,Se)₄ (CZTSSe) layers. Different selenization conditions and particle concentrations were considered in order to improve the crystallinity and surface morphology; the annealing temperature was varied between 400°C and 550°C and the annealing time was varied between 5 min and 20 min in a selenium-nitrogen atmosphere. The influence of annealing conditions on structural, compositional, optical and electrical properties of CZTSSe thin films was studied. An improvement in the structural and surface morphology was observed with increasing of annealing temperature (up to 500°C). An enhancement in the crystallinity and surface morphology were observed for thin films annealed for 10–15 min. Absorption study revealed that the band gap energy of as-deposited CZTS thin film was approximately 1.43 eV, while for CZTSSe thin films it ranged from 1.15 eV to 1.34 eV at different annealing temperatures, and from 1.33 eV to 1.38 eV for different annealing times.     

Quantum confinement and size effects in Cu2ZnSnS4 thin films produced using solution processed ultrafine nanoparticles

Copper–zinc–tin-sulfide (Cu₂ZnSnS₄, abbreviated as CZTS) is a direct band gap p-type semiconductor material with high absorption coefficient. Using oleylamine as solvent/stabilizing agent and metal chlorides and sulfur particles as chemical precursors, CZTS based nanoparticles were produced and subsequently deposited as thin films on glass substrates via spin coating of the nanoinks. The effect of temperature on crystallite size and phase composition was assessed after the solution mixture was undercooled by 30, 70 or 90 °C. Upon cooling the solution from 230 to 140 °C i.e. by 90 °C, maximum refinement in the nanoparticles size was noticed with average size on the order of few nanometers. The morphological and compositional studies of the nanoparticles were performed by means of scanning electron microscope, X-ray diffraction and Fourier transform infrared spectroscopy techniques. Phase-pure CZTS formation was confirmed from fast Fourier transform (FFT) patterns and lattice fringes observed during HR-TEM examination. Characterization of the annealed spin coated films, made from nanoink containing ultrafine nanoparticles, indicated morphological changes in the film surface during air annealing at 350°C that can be attributed to depression of CZTS phase decomposition temperature. Spectrophotometric studies of the annealed films suggested quantum confinement effect through an associated increase in the band gap value from 1.34 to 2.04 eV upon reduction in the nanoparticle size caused by increasing the degree of undercooling to 90 °C.     

Structural and optoelectronic properties of nanostructured TiO2 thin films with annealing

About 480 nm thick titanium oxide (TiO₂) thin films have been deposited by electron beam evaporation followed by annealing in air at 300–600 °C with a step of 100 °C for a period of 2 h. Optical, electrical and structural properties are studied as a function of annealing temperature. All the films are crystalline (having tetragonal anatase structure) with small amount of amorphous phase. Crystallinity of the films improves with annealing at elevated temperatures. XRD and FESEM results suggest that the films are composed of nanoparticles of 25–35 nm. Raman analysis and optical measurements suggest quantum confinement effects since Raman peaks of the as-deposited films are blue-shifted as compared to those for bulk TiO₂ Optical band gap energy of the as-deposited TiO₂ film is 3.24 eV, which decreases to about 3.09 eV after annealing at 600 °C. Refractive index of the as-deposited TiO₂ film is 2.26, which increases to about 2.32 after annealing at 600 °C. However the films annealed at 500 °C present peculiar behavior as their band gap increases to the highest value of 3.27 eV whereas refractive index, RMS roughness and dc-resistance illustrate a drop as compared to all other films. Illumination to sunlight decreases the dc-resistance of the as-deposited and annealed films as compared to dark measurements possibly due to charge carrier enhancement by photon absorption.     

Influence of the Thermal Conditions of Fabrication and Treatment on the Optical Properties of In<Subscript>2</Subscript>O<Subscript>3</Subscript> Films

In₂O₃ films on Al₂O₃ (012) substrates are fabricated by dc magnetron sputtering at various temperatures (20–600°C). The effect of annealing and the substrate temperature on the film properties are studied by the ellipsometric method and the optical transmission method. Refractive-index profiles are constructed and band gaps for direct and indirect transitions are found. It is established that annealing leads to densification of the film material and unifies the refractive index. Annealing also decreases and unifies the energies of band-to-band transitions, which can be explained by lowering the influence of barriers in annealed films. However, the band gap for direct transitions varies greater than for indirect transitions. This fact can be associated with the mechanism of indirect transitions, notably, the participation of phonons facilitates interband transitions even if they are hindered by extra barriers caused by grain boundaries. The latter can be indirect evidence of the actuality of indirect transitions in indium oxide.     

Monitoring the Formation of a CH3NH3PbI3–xClx Perovskite during Thermal Annealing Using X‐Ray Scattering

Grazing incidence wide and small angle X‐ray scattering (GIWAXS and GISAXS) measurements have been used to study the crystallization kinetics of the organolead halide perovskite CH₃NH₃PbI_3–xCl_x during thermal annealing. In situ GIWAXS measurements recorded during annealing are used to characterize and quantify the transition from a crystalline precursor to the perovskite structure. In situ GISAXS measurements indicate an evolution of crystallite sizes during annealing, with the number of crystallites having sizes between 30 and 400 nm increasing through the annealing process. Using ex situ scanning electron microscopy, this evolution in length scales is confirmed and a concurrent increase in film surface coverage is observed, a parameter crucial for efficient solar cell performance. A series of photovoltaic devices are then fabricated in which perovskite films have been annealed for different times, and variations in device performance are explained on the basis of X‐ray scattering measurements.     

Substrate‐Dependent Spin–Orbit Coupling in Hybrid Perovskite Thin Films

Solution‐processing hybrid metal halide perovskites are promising materials for developing flexible thin‐film devices. This work reports the substrate effects on the spin–orbit coupling (SOC) in perovskite films through thermal expansion under thermal annealing. X‐ray diffraction (XRD) measurements show that using a flexible polyethylene naphthalate (PEN) substrate introduces a smaller mechanical strain in perovskite MAPbI_3?xCl_x films, as compared to conventional glass substrates. Interestingly, the linear/circular photoexcitation‐modulated photocurrent studies find that decreasing mechanical strain gives rise to a weaker orbit–orbit interaction toward decreasing the SOC in the MAPbI_3?xCl_x films prepared on flexible PEN substrates relative to rigid glass substrates. Simultaneously, decreasing the mechanical strain causes a reduction in the internal magnetic parameter inside the MAPbI_3?xCl_x films, providing further evidence to show that introducing mechanical strain can affect the SOC in hybrid perovskite films upon using flexible substrates toward developing flexible perovskite thin‐film devices. Furthermore, thermal admittance spectroscopy indicates that the trap states are increased in the perovskite films prepared on flexible PEN substrates as compared to glass substrates. Consequently, PEN and rigid glass substrates lead to shorter and longer photoluminescence lifetimes, respectively. Clearly, these findings provide an insightful understanding on substrate effects on optoelectronic properties in flexible perovskite thin‐film devices.     

Copper-Silver Alloy for Advanced Barrierless Metallization

In this study we observed significantly improved properties, over a pure copper (Cu) film, for a copper-silver alloy film made with a pure copper film co-sputtered with a minute amount of either Ag_0.3N_0.4 or Ag_1.2N_0.7 on a barrierless Si substrate. In either case, no noticeable interaction between the film␣and the Si substrate was found after annealing at 600°C for 1 h. The Cu(Ag_0.3,N_0.4) film was thermally stable after annealing at 400°C for 240 h. The film’s resistivity was ∼2.2 μΩ cm after annealing at 600°C, while its leakage current was found to be lower than that of a pure Cu film by three orders of magnitude. The adhesion of the Cu(Ag_1.2,N_0.7) film to the Si substrate was approximately seven times that of a pure Cu film to a silicon substrate. Hence, a Cu film doped with Ag and N seems to be a better candidate for both barrierless metallization and the making of superior interconnects.     

Modification of the structural lattice parameters and electron spectra of <Emphasis Type="Italic">n</Emphasis>-GaAs films on sapphire on irradiation with reactor neutrons

Changes in the structural parameters of epitaxial GaN films on sapphire (n-GaN/Al₂O₃(0001)) induced by irradiation with reactor neutrons with integrated fluences up to 7.25 × 10¹⁹ fn cm⁻² (φ_fn/φ_tn ≈ 1) and subsequent isochronal annealing at temperatures up to 1000°C are studied. Measurements of the lattice parameters a and c of the irradiated n-GaN films show that the parameter c increases by 0.38% and the parameter a remains almost unchanged. From theoretical estimations, it follows that, in the irradiated n-GaN film, the elastic tensile stress along the c axis is as high as ∼1.5 GPa, whereas the compression stress in the basal plane of the unit cell is about −0.5 GPa. The tension of the irradiated GaN film along the hexagonal axis induces a decrease in the band gap E _g by 37 meV and a lowering of the charge neutrality level by 22 meV with respect to the corresponding parameters in the initial GaN film on sapphire. The parameter c changed by irradiation with reactor neutrons by Δc can be recovered by annealing in the temperature range 100–1000°C, with the basic stage of annealing at about 400°C.     

SrHfO3 as gate dielectric for future CMOS technology

Thin epitaxial films of the high-κ perovskite SrHfO₃ were grown by molecular beam epitaxy on Si(100) and investigated by ellipsometry and X-ray photoelectron spectroscopy to determine its band gap and valence band offset. Conducting AFM shows a good correlation between topography and current mapping, pointing to direct tunneling conduction. Long channels MOSFETs with low equivalent oxide thickness (EOT) were fabricated and their channel mobility measured. Mobility enhancement can be achieved by post processing annealing in various gases but at the cost of interfacial regrowth. An alternative approach is to increase mobility without changing EOT is by electrically stressing the gate dielectric at ∼150 °C.     

Effect of annealing temperature on structural,electrical and optical properties of spray pyrolytic nanocrystalline CdO thin films

Nanocrystalline CdO thin films were prepared onto a glass substrate at substrate temperature of 300 °C by a spray pyrolysis technique. Grown films were annealed at 250, 350, 450 and 550 °C for 2.5 h and studied by the X-ray diffraction, Hall voltage measurement, UV-spectroscopy, and scanning electron microscope. The X-ray diffraction study confirms the cubic structure of as-deposited and annealed films. The grain size increases whereas the dislocation density decreases with increasing annealing temperature. The Hall measurement confirms that CdO is an n-type semiconductor. The carrier density and mobility increase with increasing annealing temperature up to 450 °C. The temperature dependent dc resistivity of as-deposited film shows metallic behavior from room temperature to 370 K after which it is semiconducting in nature. The metallic behavior completely washed out by annealing the samples at different temperatures. Optical transmittance and band gap energy of the films are found to decrease with increasing annealing temperature and the highest transmittance is found in near infrared region. The refractive index and optical conductivity of the CdO thin films enhanced by annealing. Scanning electron microscopy confirms formation of nano-structured CdO thin films with clear grain boundary.     

Metalorganic vapor phase epitaxial growth of GaInAsP/GaAs

Ga_xAs_yP_1−y lattice matched to GaAs has been grown by low pressure metalorganic phase vapor epitaxy over the entire compositional range. At T_G = 670°C broad peaks of low intensity are observed in the 10K photoluminescence for y = 0.2–0.4 due to the predicted miscibility gap in this compositional region. An increase in growth temperature leads to a smaller miscibility gap. The band gap as well as the morphology show a strong dependence on substrate misorientation. The smoothest GalnAsP surfaces are obtained on exact oriented substrates. For the ternary GalnP the surface roughness is correlated to the degree of ordering in the temperature range of 600 to 750°C. The smallest band gap together with the smoothest surface is obtained on (100) 2° off to (111)B. Ordering effects are also observed in the quaternary GalnAsP. Broad-area lasers processed from the grown layers show high slope efficiency (0.9 W/A) and low internal losses (<3 cm⁻¹).     

High resistivity LT-In0.47Ga0.53P grown by gas source molecular beam epitaxy

Low-temperature (LT) growth of In_0.47Ga_0.53P was carried out in the temperature range from 200 to 260°C by gas source molecular beam epitaxy using solid Ga and In and precracked PH₃. The Hall measurements of the as-grown film showed a resistivity of ∼10⁶ Ω-cm at room temperature whereas the annealed film (at 600°C for 1 h) had at least three orders of magnitude higher resistivity. The Hall measurements, also, indicated activation energies of ∼0.5 and 0.8 eV for the asgrown and annealed samples, respectively. Double-crystal x-ray diffraction showed that the LT-InGaP films had ∼47% In composition. The angular separation, Δθ, between the GaAs substrate and the as-grown LT-InGaP film on (004) reflection was increased by 20 arc-s after annealing. In order to better understand the annealing effect, a LT-InGaP film was grown on an InGaP film grown at 480°C. While annealing did not have any effect on the HT-InGaP peak position, the LT-InGaP peak was shifted toward the HT-InGaP peak, indicating a decrease in the LT-InGaP lattice parameter. Cross-sectional transmission electron microscopy indicates the presence of phase separation in LT-InGaP films, manifested in the form of a “precipitate-like” microstructure. The analytical scanning transmission electron microscopy analysis of the LT-InGaP film revealed a group-V nonstoichiometric deviation of ∼0.5 at.% P. To our knowledge, this is the first report about the growth and characterization of LT-InGaP films.     

High-quality conformal silicon oxide films prepared by multi-step sputtering PECVD and chemical mechanical polishing

High-quality conformal oxide films were obtained by using multi-step sputtering (MSSP) plasma enhanced chemical vapor deposition (PECVD) process with argon ion sputtering and chemical mechanical polishing (CMP). The repeated deposition by plasma enhanced chemical vapor deposition (PECVD) and anisotropic etching of oxide films by multi-step sputtering PECVD improve the step coverage and gap filling capability significantly. The argon plasma treatment enhances the binding energy of Si-O in the SiO₂ network, and the temperature dependence of stress for MSSP oxide film showed no hysteresis after the heating cycle up to 440 °C. The stress-temperature slope of MSSP oxide film was found to be much less than that of conventional PECVD oxide film. The slope for 1.1 μm thick film is about 5.8×10⁵ dynes/cm²/°C which is smaller than that of thermally grown oxide film. It seems that MSSP oxide film reduces stress-temperature hysteresis and becomes more dense and void-free in the narrow gaps with inter-metal spacing of 0.5 μm. After filling of the narrow gap, we adopted the CMP process for global planarization and obtained good planarization performance. The uniformity of the film thickness was about 4% and the degree of the planarization was over 95% after CMP process.     

Low-Temperature Crystallized and Flexible 1D/3D Perovskite Heterostructure with Robust Flexibility and High EQE-Bandwidth Product

All-inorganic perovskite cesium lead triiodide (CsPbI₃) has attracted much attention among the perovskite family due to its excellent optoelectronic properties and chemical stability. However, the high-temperature crystallization process makes CsPbI₃ less compatible with commercially flexible substrates, limiting its application into flexible optoelectronics. Here, a cation of 1-(3-aminopropyl)-2pyrrolidinone (APP) is reported that can form 1D (APP)PbI₃ perovskite as templates, and significantly reduce the CsPbI₃ black-phase transition energy with a low annealing temperature of 75 °C, which further enables a flexible (APP)PbI₃/γ-CsPbI₃ (1D/3D) heterostructure photodetector on ITO/PET substrate. A high external quantum efficiency (EQE) greater than 2377% is observed along the orientated 1D/3D heterostructure. The high gain and low noise result in a high specific detectivity (D*) over 10¹² Jones under −0.6 V low bias. The optimized device structure brings a high EQE × bandwidth product of 119 kHz under a low driving bias. Due to the high toughness of orientated APP⁺ ions and the face-connected [PbI₃]⁻ chains structure as a strong energy absorber, the flexible photodetector also shows excellent phase stability and impressive flexibility, remaining >90% initial responsivity after over 20 000 times bending with potential flexible imaging application in harsh environments.