Growth and optical properties of large-scale MoS2 films with different thickness

The synthesis of large-scale molybdenum disulfide (MoS₂) with high quality is highly desirable for the promising applications in flexible optoelectronic devices. Here, we report a feasible one-step chemical vapor deposition (CVD) synthesis of continuous MoS₂ films with different layer-number via adjusting the growth temperature in the range of 740–800 °C. Influences of the annealing treatments at diverse temperature ranging from 300 to 500 °C on Raman and PL spectra of the monolayer MoS₂ film grown at 780 °C are reported. PL characterization shows that the PL emission of film annealed at 400 °C exhibits highest intensity with a blue-shift in comparison to that of the pristine film grown at 780 °C. The PL fluctuation of the MoS₂ film annealed at 400 °C is mainly originated from the high crystalline quality and strain-release. This study sheds a light on growth and performance optimization of the large-area two-dimensional transition metal dichalcogenides films.     

Microstructure and dielectric properties of the Ti-rich BaO–TiO2 thin films for microwave devices

Ti-rich BaO–TiO₂ thin films were grown on a Pt/Ti/SiO₂/Si substrate using rf sputtering and the structural and dielectric properties of the films were investigated. For the film grown at room temperature and rapidly thermal annealed (RTA) at 900 °C for 3 min, an amorphous phase with a small BaTi₅O₁₃ crystalline phase was formed. As the growth temperature increased, the amount of the BaTi₅O₁₁ crystalline phase increased. For the film grown at 350 °C and RTA at 900 °C for 3 min, the homogeneous BaTi₅O₁₁ phase was formed. The BaTi₄O₉ phase was developed when the growth temperature exceeded 450 °C. The thin film with the homogeneous BaTi₄O₉ phase was obtained when the film was grown at 550 °C and RTA at 900 °C for 3 min. The dielectric properties of the films were measured at 1–6 GHz range. The dielectric constant (ϵ_r) of the BaTi₅O₁₁ film was about 33 and the dissipation factor was about 0.01. The ϵ_r and the dissipation factor of the BaTi₄O₉ film were about 37 and 0.005, respectively.     

Preparation and characterization of TiO2 thin films by PECVD on Si substrate

Titanium oxide thin films were prepared on p-Si(l00) substrate by plasma enhanced chemical vapor deposition using high purity titanium isopropoxide and oxygen. The deposition rate was little affected by oxygen flow rate, but significantly affected by RF power, substrate temperature, carrier gas flow rate, and chamber pressure. Morphology of the film became coarser with increasing deposition time and chamber pressure, and the film showed less uniformity at high deposition rates. It was also found that the overall deposition process is controlled by heterogeneous surface reaction below 200°C., but controlled by mass transfer of reactants at higher temperatures. TiO₂ films deposited at temperatures lower than 400°C was amorphous, but showed the anatase crystalline structure upon 400°C deposition. The dielectric constant was about 47 for the films post-treated by rapid-thermal annealing (RTA) at 800°C. The leakage current was about 2×10⁻⁵ A/cm² for the films deposited at 400°C and RTA-treated at 600°C. However, it was decreased to less than 3×10⁻⁷ A/cm² for the film RTA-treated at 800°C.     

Solvothermally grown WO3·H2O film and annealed WO3 film for wide-spectrum tunable electrochromic applications

Tungsten trioxide (WO₃) is a classical electrochromic (EC) material with advantages of abundant reserves, high coloration efficiency and cyclic stability. However, WO₃ films are often accompanied by a narrow spectrum of modulation due to a single-color change from transparent to blue. In this work, we report a wide-spectrum tunable WO₃·H₂O nanosheets EC film solvothermally grown on fluorine-doped tin oxide (FTO) glass. Interestingly, the crystalline WO₃·H₂O nanosheets film is transformed into amorphous WO₃ after annealing at 250 °C for 1 h. The amorphous film can be transformed into crystalline WO₃ film by increasing the annealing temperature to 450 °C. After annealing at 250 °C, the WO₃ film exhibits an optical modulation of 75.8% in a broad solar spectrum range of 380–1400 nm and blocks 88.9% of solar irradiance. Fast switching responses of 4.9 s for coloration and 6.0 s for bleaching, and a coloration efficiency of 86.4 cm² C⁻¹ are also achieved. Additionally, the WO₃ film annealed at 250 °C also demonstrates an excellent cyclic stability, where 99.6% of the initial optical modulation can be retained after 1500 cycles. This simple and mild solvothermal method used in this work provides a new idea for the preparation of wide-spectrum tunable WO₃ EC films.     

Structural and optical properties of diamond and nano-diamond films grown by microwave plasma chemical vapor deposition

We compare structural and optical properties of microcrystalline and nanocrystalline diamond (MCD and NCD, respectively) films grown on mirror polished Si(100) substrates by microwave plasma chemical vapor deposition. The films were characterized by SEM, Raman spectroscopy, XRD, and AFM. Optical properties were obtained from transmittance and reflectance measurements of the samples in the wavelength range of 200–2000 nm. Raman spectrum of the MCD film exhibits a strong and sharp peak near 1335 cm⁻¹, an unambiguous signature of cubic crystalline diamond with weak non-diamond carbon bands. Along with broad non-diamond carbon bands, Raman spectra of NCD films show features near 1140 cm⁻¹, the intensity of which is significantly higher in the film grown at 600°C compared to the NCD film grown at higher temperature. The Raman feature near 1140 cm⁻¹ is related to the calculated phonon density of states of diamond and has been assigned to nanocrystalline or amorphous phase of diamond. XRD patterns of the MCD film show sharp peaks and NCD films show broad features, corresponding to cubic diamond. The rms surface roughness of the films was observed to be approximately 60 nm for MCD film that reduced substantially to 17 and 34 nm in the NCD films grown at 600 and 700°C, respectively. Tauc's optical gap for the diamond film is found to be approximately 5.5 eV. NCD grown at 700°C has a high optical absorption coefficient in the whole spectral region and the NCD film grown at 600°C shows very high transmittance (∼78%) in the near IR region, which is close to that of diamond. This indicates that the NCD film grown at 600°C has the potential for applications as optical windows since its surface roughness is significantly low as compared to the MCD film.     

Phase development and crystallization of CuAlO2 thin films prepared by pulsed laser deposition

A polycrystalline CuAlO₂ single-phase target was fabricated by the conventional solid-state reaction route using Cu₂O and Al₂O₃. Thin films of CuAlO₂ were deposited by a pulsed laser deposition process on sapphire substrates at different temperatures. Then, post-annealing was followed at different conditions, and the phase development process of the films was examined. As grown thin films in the temperature range of 450–650 °C were amorphous. The c-axis oriented single phase of CuAlO₂ thin films were obtained when the films were post-annealed at 1100 °C in air after growing at 650 °C. Phi-scan of the film clearly showed 12 peaks, each of which are positioned at intervals of 30°. This is thought to be caused by the rhombohedral structured CuAlO₂ thin film growing in the states of 30° tilt during the annealing process. Hall effect analysis of the film was carried out.     

Fabrication and characterization of MOCVD (In1-xAlx)2O3 (0.1≤x≤0.6) ternary films

A series of (In_1-xAl_x)₂O₃ (0.1 ≤ x ≤ 0.6) films with tunable bandgap were grown on MgO (100) substrates by MOCVD. The influences of chemical compositions and growth temperatures on the film properties were studied systematically. XRD analyses indicated that the film quality degraded from crystalline to amorphous structure as Al concentration (x) increased. The (In_1-xAl_x)₂O₃ films prepared at 700 °C exhibited better film crystallinity than those of the ones grown at 600 °C. The films prepared at 700 °C with x = 0.1–0.3 showed an epitaxial In₂O₃ <111> orientation with the corresponding growth relationship of In₂O₃ (111)∥MgO (100). The film with x = 0.2 exhibited the best crystallinity and the largest grain size of 25.9 nm. The Hall mobilities and resistivities of the films were influenced evidently by Al concentrations. The Hall mobility showed a monotonous decrease from 12 to 1.1 cm²V^?1s^?1 as x increased from 0.1 to 0.6. The lowest resistivity of 9.2 × 10^?3 Ω cm was acquired for the film with x = 0.2. The average transmittances in the visible region for all the films were beyond 83%. The bandgap of the (In_1-xAl_x)₂O₃ films can be regulated in the range of 3.85–4.88 eV by changing Al concentrations from 0.1 to 0.6.     

Microwave dielectric properties of the BaTi5O11 thin film grown on the poly-Si substrate using rf magnetron sputtering

BaTi₅O₁₁ thin films were grown on the poly-Si/SiO₂/Si substrate using rf magnetron sputtering. The BaO-TiO₂ thin film deposited on the poly-Si substrate had an amorphous phase even though the growth temperature was high at 550 °C. The amorphous film was crystallized into the BaTi₅O₁₁ phase when the film was post annealed above 800 °C. The post annealing temperature is one of the most important factors for the formation of the crystalline BaTi₅O₁₁ thin film. The homogeneous BaTi₅O₁₁ thin film was obtained when the film was grown at 550 °C and rapid thermal annealed (RTA) at 900 °C for 3 min. The dielectric constant (ɛ_r) of the BaTi₅O₁₁ film measured at 100 kHz was about 35 and the dissipation factors of all the films were smaller than 4.0%. The dielectric properties of the BaTi₅O₁₁ thin film were also measured at microwave frequencies. For the BaTi₅O₁₁ thin film grown at 550 °C and RTA at 900 °C for 3 min, the ɛ_r of 34–30 and dielectric loss of 0.025 ± 0.005 were obtained at 1–6 GHz.     

Low temperature atomic layer deposition of SiO2 thin films using di-isopropylaminosilane and ozone

Silicon dioxide (SiO₂) films are deposited by atomic layer deposition (ALD) at low temperatures from 100 to 200 °C using di-isopropylaminosilane (SiH₃N(C₃H₇)₂, DIPAS) as the Si precursor and ozone as the reactant. The SiO₂ films exhibit saturated growth behavior confirming the ALD process, showing a growth rate of 1.2 Å/cycle at 150 °C, which increases to 2.3 Å/cycle at 250 °C. The activation energy of 0.24 eV, extracted from temperature range of 100–200 °C, corresponds to the reported energy barrier for reaction between DIPAS and surface –OH. The temperature dependence of the growth rate can be explained in terms of the coverage and chemical reactivity of the thermally activated precursor on the surface. The ALD-SiO₂ films deposited at 200 °C show properties such as refractive index, density, and roughness comparable to those of conventionally deposited SiO₂, as well as low leakage current and high breakdown field. The fraction of Si–O bond increases at the expense of Si–OH at higher deposition temperature.     

TaCx Thin Films Prepared by Atomic Layer Deposition as Diffusion Barriers for Cu Metallization

TaC_x films were deposited by atomic layer deposition (ALD) using tris (neopentyl) tantalum dichloride, (Ta[CH₂C(CH₃)₃]₃Cl₂) and H₂ plasma as the precursor and reactant, respectively, at substrate temperatures ranging from 200°C to 400°C. The ALD–TaC_x films with the formation of nanocrystalline structures and a rock‐salt phase were confirmed by X‐ray and electron diffraction. The ALD temperature window was found to be 225°C–300°C with a growth rate of ~0.11 nm per cycle. The resistivity of the ALD–TaC_x films was dependent on the microstructural features, such as the grain size and crystallinity, as well as their composition (C/Ta ratio), and the presence of impurities in the films, which could be controlled by varying the deposition parameters, such as the deposition temperature and reactant pulse conditions. With increasing deposition temperature and reactant pulse time, Ta‐rich films with a low Cl impurity concentration and larger grain size were obtained. The film with a resistivity less than 400 μΩ cm was obtained at 300°C, which was within the ALD temperature window, by optimizing the H₂ plasma pulse time. The step coverage of the film deposited at 300°C was approximately 100% over the trench structure (top opening width of 25 nm) with an aspect ratio of ~4.5. The performance of the ALD–TaC_x films deposited under the optimized conditions was evaluated as a diffusion barrier for the Cu interconnects. The structure of Cu (100 nm)/ALD–TaC_x (5 nm)/ Si was stable without the formation of copper silicide after annealing at 600°C for 30 min.     

Atomic layer deposition of pure In2O3 films for a temperature range of 200–300 °C using heteroleptic liquid In(DMAMP)2(OiPr) precursor

In₂O₃ films were deposited by atomic layer deposition (ALD) using a newly synthesized heteroleptic In precursor, In(DMAMP)₂(OⁱPr), and O₃ at 150–300 °C. Self-limiting growth characteristics were exhibited for a wide ALD temperature range of 200–300 °C and growth rate of 0.029–0.033 nm/cycle. At a low temperature of 150 °C, the amorphous In₂O₃ film was deposited, while polycrystalline In₂O₃ films were achieved at 200–300 °C. The In₂O₃ films grown in this ALD temperature range had high densities of 7.0–7.2 g/cm³, which are comparable to those of bulk In₂O₃. At all growth temperatures (150–300 °C), no carbon or nitrogen impurities were detected, suggesting high reactivity of the In(DMAMP)₂(OⁱPr) precursor. The ALD In₂O₃ films showed n-type electronic property with high electron concentrations of 1.6 × 10²⁰–3.6 × 10²⁰/cm³ and a Hall mobility of 31–39 cm²/V·s.     

Surface energy of the plasma treated Si incorporated diamond-like carbon films

Surface energy and surface chemical bonds of the plasma treated Si incorporated diamond-like carbon films (Si-DLC) were investigated. The Si-DLC films were prepared by r.f. plasma assisted chemical vapor deposition using benzene and diluted silane (SiH₄/H₂ = 10:90) as the precursor gases. The Si-DLC films were subjected to plasma treatment using various gases like N₂, O₂, H₂ and CF₄. The plasma treated Si-DLC films showed a wide range of water contact angles from 13.4° to 92.1°. The surface energies of the plasma treated Si-DLC films revealed a high polar component for O₂ plasma treated Si-DLC films and a low polar component for CF₄ plasma treated Si-DLC films. The CF₄ plasma treated Si-DLC films indicated the minimum surface energy. X-ray photoelectron spectroscopy (XPS) revealed that the polarizability of the bonds present on the surface explains the hydrophilicity and hydrophobicity of the plasma treated Si-DLC films. We also suggest that the O₂ plasma treated surface can provide an excellent hemocompatible surface from the estimated interfacial energy between the plasma treated Si-DLC surface and human blood.     

Preparation and characteristics of thin film with wear-resistant behavior on HDPE surface polymerized by C2H2–H2–SiH4 plasma

Plasma-polymerized deposition of an acetylene–hydrogen–silane mixture (C₂H₂–H₂–SiH₄) to obtain thin film with good wear behavior on a high-density polyethylene (HDPE) surface was present in this work. It was found that the bond between thin film and HDPE substrate was excellent and H₂ gas in system led the deposited thin film to better adhesive properties, but slower thin film deposition rate. Surface wear-resistant properties of modified HDPE were improved with the input of SiH₄. Infrared and X-ray photoelectron spectroscopy spectra suggested that there be large quantities of >CO, O H, C Si, and Si O groups in thin film and that the ratio of C to Si was increased due to the addition of SiH₄ and H₂, which inferred that the thin film structure and components lie between organic and inorganic materials. © 1998 John Wiley & Sons, Inc. J Appl Polym Sci 70: 1561–1566, 1998     

Temperature influence on the interlayer and surface morphology of diamond coating on 3D porous titanium substrates

Nanocrystalline (NCD) and/or microcrystalline (MCD) diamond films grown on three-dimensional porous titanium (Ti) substrate were obtained by hot filament chemical vapor deposition (HFCVD) technique. The morphology variation of diamond films grown on porous three-dimensional titanium substrate was studied at four different deposition temperatures to investigate their influence on nucleation density. Scanning electron microscopy images depicted the continuous change from microcrystalline diamond grains with a random crystallographic orientation, at 500 °C and 600 °C, to a cauliflower-like structure for deposits at 700 °C and 800 °C. Visible Raman spectroscopy confirmed the good quality of diamond films and revealed that the amount of amorphous carbon increased associated to the film morphology changes from MCD to NCD. X-ray diffraction analyses, performed both through θ–2θ scans and at grazing incidence angle, allowed the investigation of the crystallographic properties and structural evolution of the different film/substrate interface phases, such as TiC(111), TiC(200) and TiH₂. The results revealed that the temperature enhanced the nucleation sites for diamond growth.     

Hydrothermal preparation of BaTiO3 thin films

In preparing BaTiO₃ thin films under hydrothermal conditions, the effects of concentrations of nutrient and mineralizer, and reaction time on crystallinity, grain size, surface roughness, and film thickness were investigated. Experiments were performed in the ranges of 0.1-1.5M BaCl₂ · 2H₂O or Ba(OH)₂ · 8H₂O and 0-1.5 M KOH with varying reaction time from 0.16 to 8 hours at 140 °C. Bimodal dispersion of crystalline grains on the surface of BaTiO₃ thin films was predicted through nucleation and crystal growth reaction. As the concentrations of nutrient and/or mineralizer increased, grain size of the thin film became smaller, but more uniform and compact. When 0.4 M Ba(OH)₂ · 8H₂O was used with 1.0 M KOH, a reaction time longer than 4 hours was required in order to fabricate BaTiO₃ thin films.     

Atomic layer deposition of TiO2 from tetrakis-dimethylamido-titanium and ozone

Ozone (O₃) was employed as an oxygen source for the atomic layer deposition (ALD) of titanium dioxide (TiO₂) based on tetrakis-dimethyl-amido titanium (TDMAT). The effects of deposition temperature and O₃ feeding time on the film growth kinetics and physical/chemical properties of the TiO₂ films were investigated. Film growth was possible at as low as 75 °C, and the growth rate (thickness/cycles) of TiO₂ was minimally affected by varying the temperatures at 150–225 °C. Moreover, saturated growth behavior on the O₃ feeding time was observed at longer than 0.5 s. Higher temperatures tend to provide films with lower levels of carbon impurities. The film thickness increased linearly as the number of cycles increased. With thicker films and at higher deposition temperatures, surface roughening tended to increase. The as-deposited films were amorphous regardless of the substrate temperatures and there was no change of crystal phase even after annealing at temperatures of 400–600 °C. The films deposited in 0.5 mm holes with an aspect ratio of 3: 1 showed an excellent conformality.     

Seed layer mediated growth of high dielectric and low leakage BaTiO3 thin film using two-step sputtering process

In this study, we demonstrated the seed layer mediated growth of high-quality BaTiO₃ (BTO) thin films using a two-step radio frequency (RF) magnetron sputtering process. Since the as-grown BTO thin films obtained by RF magnetron sputtering at the deposition temperatures of 300–500 °C were amorphous with a low dielectric constant of 20, it is necessary to develop a fabrication process for obtaining crystalline high-k BTO thin films without sacrificing other film properties such as morphology and leakage current. First, it was revealed that ex-situ post-deposition annealing (PDA) at high temperatures in the 700–800 °C range led to the crystallization of BTO films and a high dielectric constant of 121. However, the film morphology deteriorated significantly during PDA, and consequently, a high leakage current was observed due to the rough and discontinuous surface containing voids and micro-cracks. To achieve an excellent leakage current characteristic as well as a high dielectric constant for a crystalline BTO thin film, in-situ crystallization was carried out through local epitaxial growth using a crystalline seed layer. The crystalline BTO seed layer was formed by annealing a 5-nm-thick amorphous BTO film at 700 °C on which the in-situ crystallized BTO main layer was deposited at 500 °C. The in-situ crystallization method resulted in a smooth and uniform surface and a high dielectric constant of 113. In addition, the in-situ crystallized BTO film exhibited a low leakage current density of 10⁻⁶ A/cm² (at 0.8 V) displaying an improvement by a factor of 10³ compared to the ex-situ crystallized BTO film.     

Formation of PbTiO<Subscript>3</Subscript> films from multilayered structures of primitive oxides

The possibility of the formation of PbTiO₃ from a multilayer structure of PbO and TiO₂ layers on Pt-coated Si substrates prepared by rapid thermal metal organic chemical vapor deposition (RTMOCVD) followed by an appropriate annealing process was examined. The metal organic precursors of PbO and TiO₂ were Pb(C₂H₅)₄ and Ti(Oi-C₃H₇)₄, respectively. The composition of the PbTiO₃ thin film was adjusted by control of the thickness of each binary oxide layer of PbO and TiO₂. The multilayer structure was converted into crystalline PbTiO₃ by rapid thermal annealing under O₂ ambient at temperature greater than 550 °C. As the annealing temperature was increased from 550 to 750 °C, the peaks related to perovskite PbTiO₃ in the XRD patterns became stronger and sharper. From this study, it was confirmed that the crystalline PbTiO₃ thin films could be prepared from the interdiffusion reaction of multilayer structure composed of primitive binary oxides through the appropriate post annealing process.     

Polymeric semiconducting carbon from fullerene by pulsed laser ablation

The polymeric semiconducting carbon films are grown on silicon and quartz substrates by excimer (XeCl) pulsed laser deposition (PLD) technique using fullerene C₆₀ precursor. The substrate temperature is varied up to 300 °C. The structure and optical properties of the films strongly depend on the substrate temperature. The grain size is increased and uniform polymeric film with improved morphology at higher temperature is observed. The Tauc gap is about 1.35 eV for the film deposited at 100°C and with temperature the gap is decreased upto 1.1 eV for the film deposited at 250 °C and increased to about 1.4 eV for the film deposited at 300 °C. The optical absorption properties are improved with substrate temperature. Raman spectra show the presence of both G peak and D peak and are peaked at about 1590 cm^− 1 and 1360 cm^− 1, respectively for the film deposited at 100 °C. The G peak position remains almost unchanged while D peak has changed only a little with temperature might be due to its better crystalline structure compared to the typical amorphous carbon films and might show interesting in device such as, optoelectronic applications.     

Model of morphology evolution in the growth of polycrystalline β-SiC films

The growth of β-SiC films via chemical vapor deposition (CVD) has been under intensive investigation because this is viewed to be an enabling material for a variety of new semiconductor devices in areas where silicon cannot effectively compete. However, the difficulty in achieving single-crystal or highly textured surface morphology in films with low bulk defect density has limited the use of β-SiC films in electronic devices. Although several researchers have reported results relating the morphology of β-SiC films to deposition parameters, including substrate temperature and gas composition, detailed knowledge of the effects of deposition parameters on film morphology and crystallographic texture is still lacking. If these relationships between deposition parameters and film morphology can be quantified, then it may be possible to obtain optimal β-SiC film morphologies via CVD for specific applications such as high-power electronic devices.The purpose of this study is to predict the dependence of the surface morphology of β-SiC films grown by CVD on substrate temperature and inlet atom ratio of Si:C, and to model the morphological evolution of the growing polycrystalline film. The Si:C ratio is determined by the composition of the reactant gases, propane (C₃H₈) and silane (SiH₄). A two-dimensional numerical model based on growth rate parameters has been developed to predict the evolution of the surface morphology. The model calculates the texture, surface roughness, and grain size of continuous polycrystalline β-SiC films resulting from growth competition between nucleated seed crystals of known orientation. Crystals with the fastest growth direction perpendicular to the substrate surface are allowed to overgrow all other crystal orientations. When a continuous polycrystalline film is formed, the facet orientations of crystals are represented on the surface. In the model, the growth parameter α_2D, the ratio of the growth rates of the {10} and {11} faces, determines the crystal shapes and, thus, the facet orientations of crystals. The growth rate parameter α_2D used in the model has been derived empirically from the textures of continuous β-SiC films reported in the literature.