Pulsed Laser Deposition Method Research Articles

Effect of Substrate Temperature on the Electrochemical and Supercapacitance Properties of Pulsed Laser-Deposited Titanium Oxynitride Thin Films

Abstract Electrocatalytically active titanium oxynitride (TiNO) thin films were fabricated on commercially available titanium metal plates using a pulsed laser deposition (PLD) method for energy storage applications. The elemental composition and nature of bonding were analyzed using x-ray photoelectron spectroscopy (XPS) to reveal the reacting species and active sites responsible for the enhanced electrochemical performance of the TiNO electrodes. Symmetric supercapacitor devices were fabricated using two TiNO working electrodes separated by an ion-transporting layer to analyze their real-time performance. The galvanostatic charge-discharge studies on the symmetric cell have indicated that TiNO films deposited on the polycrystalline titanium plates at lower temperatures are superior to TiNO films deposited at higher temperatures in terms of storage characteristics. For example, TiNO films deposited at 300°C exhibited the highest specific capacity of 69 mF/cm2 at 0.125 mA/cm2 with an energy density of 7.5 Wh/cm2. The performance of this supercapacitor (300°C TiNO) device is also found to be ∼ 22 % better compared to that of a 500°C TiNO supercapacitor with a capacitance retention ability of 90% after 1000 cycles. The difference in the electrochemical storage and capacitance properties is attributed to the reduced leaching away of oxygen from the TiNO films by the Ti plate at lower deposition temperatures, leading to higher oxygen content in the TiNO films and, consequently, a high redox activity at the electrode/electrolyte interface.

Electronic relaxation in PLD TiO2 films processed with femtosecond UV-laser

Modifications of shallow electron trap states near conduction band was analyzed after surface structuring of TiO2 thin films prepared via pulsed laser deposition method. Laser-induced periodic surface structures (LIPSS) were produced on the large-area films after irradiation with femtosecond KrF laser (λ = 248 nm). While spatial period of LIPSS Λ ≈ 190 ± 10 nm was not affected by laser fluence, coherence was increased with an increase of laser dose. Time-resolved microwave conductivity measurements accompanied by theoretical modelling revealed energetic positions of shallow electron trap states, connected to LIPSS. A possibility to alter the trap states energy via surface structuring of the material was shown.

High-performance solar-blind photodetectors based on Ta-doped ZnSnO3 single crystal thin films

High-quality Ta-doped ZnSnO3 single crystal thin films were grown on LiTaO3 substrates by pulsed laser deposition (PLD) method, and the effects of Ta doping on the lattice structure, surface morphology, electronic structure and photodetector performance of ZnSnO3 thin films are studied in detail. When the Ta doping content is 1%, the [0001]-oriented ZnSnO3 thin film present the highest quality, which the optical band gap (3.75eV), the smoothest surface roughness (0.83nm), and the biggest carrier concentration (4.03 × 1019cm-3). For the solar-blind photodetectors (PDs), based on these excellent characteristics, the 1% Ta-doped ZnSnO3 PD exhibits large light-to-dark current ratio (>103), responsivity (21.37A/W), detectivity ((3.63±0.71) ×1011 Jones) and external quantum efficiency (~1.04× 104%) under 254nm UV light at an applied bias of 5V. This study suggests that Ta doping can effectively improve the optoelectronic performance of ZnSnO3 PDs, laying the foundation for their application.

Polymer nanocomposite for protecting photovoltaic cells from solar ultraviolet in space

Abstract Polymer nanocomposite coatings of solar photovoltaic cells that absorb solar ultraviolet (UV) radiation and convert it into visible and near-infrared (NIR) light can increase the operational lifetime and the energy efficiency of the cells. We report a polymer nanocomposite spectrum converting layer (SCL) made of colorless polyimide CORIN impregnated with the nanoparticles (NPs) of fluoride NaYF4 doped with three-valent ions of Europium at a molar concentration of 60%. The NPs were the nanocrystals (179 ± 35 nm in size) in thermally stable hexagonal beta-phase. The visible-NIR photoluminescence quantum yield of the nano-powder was ∼69%. The SCLs were applied using the open-air multi-beam multi-target pulsed laser deposition method to silicon heterojunction (SHJ), copper-indium-gallium-selenide (CIGS), and inverted metamorphic multijunction (IMM) solar cells. The cells were exposed to UV radiation from a 365 nm light emitting diode. The I–V characteristics of the cells were measured with a solar simulator using AM0 filter. The proposed SCLs improved the UV stability of all three types of the cells: the power degradation of SHJs and IMMs cells was stopped or slightly reversed and the degradation rate of CIGSs decreased by ∼25%. The proposed SCLs have great commercial potential, especially for applications to space power.

I – V Characteristics of Hf0.5Zr0.5O2 films prepared via sol–gel and pulsed laser deposition methods

Stable [Formula: see text] (HZO) sols were obtained by adding acetylacetone (AcAc), and the mechanism through which AcAc improved the quality of the sol and the gel film was analyzed. Absorption spectroscopy results show that AcAc can chelate with [Formula: see text] and [Formula: see text], thus improving the hydrolysis resistance of the sol and the gel film, which optimizes their quality. Then, Pt/HZO/Pt structures were prepared via the sol–gel (SG) and pulsed laser deposition (PLD) methods, and their [Formula: see text] curves were studied. The Pt/HZO/Pt structure prepared via the SG (PLD) method shows a pronounced bipolar resistance switching (BRS) (unipolar resistance switching (URS)) effect. It was found that there are several defects on the surface of the HZO film prepared via the SG method, which permit oxygen ions to enter/exit HZO, thus resulting in the BRS effect. However, there are fewer defects on the surface of the HZO film prepared via the PLD method, which results in the URS effect.

Thermal Stability and Crystallization Processes of Pd78Au4Si18 Thin Films Visualized via In Situ TEM.

Amorphous alloys or metallic glasses (MGs) thin films have attracted extensive attention in various fields due to their unique functional properties. Here, we use in situ heating transmission electron microscopy (TEM) to investigate the thermal stability and crystallization behavior of Pd-Au-Si thin films prepared by a pulsed laser deposition (PLD) method. Upon heating treatment inside a TEM, we trace the structural changes in the Pd-Au-Si thin films through directly recording high-resolution images and diffraction patterns at different temperatures. TEM observations reveal that the Pd-Au-Si thin films started to nucleate with small crystalline embryos uniformly distributed in the glassy matrix upon approaching the glass transition temperature Tg=625K, and subsequently, the growth of crystalline nuclei into sub-10 nm Pd-Si nanocrystals commenced. Upon further increasing the temperature to 673K, the thin films transformed to micro-sized patches of stacking-faulty lamellae that further crystallized into Pd9Si2 and Pd3Si intermetallic compounds. Interestingly, with prolonged thermal heating at elevated temperatures, the Pd9Si2 transformed to Pd3Si. Simultaneously, the solute Au atoms initially dissolved in glassy alloys and eventually precipitated out of the Pd9Si2 and Pd3Si intermetallics, forming nearly spherical Au nanocrystals. Our TEM results reveal the unique thermal stability and crystallization processes of the PLD-prepared Pd-Au-Si thin films as well as demonstrate a possibility of producing a large quantity of pure nanocrystals out of amorphous solids for various applications.

High-performance orthorhombic correlated transparent conducting epilayer integrated on a flexible mica substrate: The case of CaMoO3

Recently, cubic perovskite SrTMO3 (TM = V, Nb, and Mo) compounds have attracted great interest as correlated transparent conducting oxides (CTCOs). However, in theory, none of these three oxides is capable of completely covering the entire visible (Vis) light wavelength range with transparency. Herein, epitaxial orthorhombic CaMoO3 thin films were grown on flexible mica substrates using a pulsed laser deposition (PLD) method. By exploiting the tilting of MoO6 octahedra, an optimal balance between plasma energy (ћωp) and electrical conductivity (σ) was realized in CaMoO3. Electronic transport characterizations indicated that the σ value of CaMoO3 is comparable to that of SrTMO3. The optical transmittance spectra demonstrated that the CaMoO3 film possesses superior Vis transparency compared to SrTMO3. From the ellipsometry analysis, it was found that the O 2p – V 3d interband transition occurs at around 4.16 eV while the screened plasma energy (ћωp) is approximately 1.37 eV. The favorable absorption edges for both the long and short wavelength regions ensure the high transparency of CaMoO3 across the entire Vis spectrum. Additionally, bending cyclic tests illustrated the excellent mechanical durability and endurance of the CaMoO3/mica films. The present work is instructive for exploring alternative CTCOs beyond SrTMO3, demonstrating that the optimal balance between ћωp and σ can be realized by manipulating the TMO6 octahedral tilting to improve the transparent conducting performance of correlated perovskite-type oxides.

Highly oriented epitaxial Cu2O (011) thin film grown on MgO (001) substrate by dynamic aurora PLD method

The epitaxial Cu2O films are grown on MgO (001) substrates by the dynamic aurora pulsed laser deposition (PLD) method. The structure and epitaxial growth of the as-prepared thin films at different substrate temperatures (25 °C to 600 °C) were investigated. The thin film prepared at room temperature (RT, 25 °C) exhibits (111) plane of monoclinic CuO phase with poor crystallinity. The thin films deposited at 200 °C to 600 °C show single-phase cubic Cu2O with good crystallinity. The highly oriented epitaxial Cu2O thin film on the MgO substrate is achieved at low temperatures of 200 °C by applying an induced electromagnetic field during thin film growth. The quality and crystallinity of epitaxial Cu2O thin films remarkably improved with increasing temperature from 200 °C to 600 °C and all these thin films exhibited an out-of-plane epitaxial relationship of Cu2O (011) ‖ MgO (001). The CuO thin film grown on MgO substrate at RT shows a single domain structure, as observed by RHEED. In constrast, Cu2O films grown at 200 °C to 600 °C exhibit two different kinds of domain structure with corresponding in-plane epitaxial relationship of Cu2O [100] ‖ MgO [110] and Cu2O [100] ‖ MgO [11¯0]. This report reveals, for the first time, the feasibility of epitaxial growth of highly oriented Cu2O (011) thin film achieved at the low temperature of 200 °C by the dynamic aurora PLD method. The quality of epitaxial Cu2O (011) is significantly enhanced with increasing substrate temperature from 200 °C to 600 °C.

Preparation of Ag-Cu nanoparticle film using a dual-beam pulsed laser deposition for power electronic packaging

Ag-Cu nanoparticles, integrating the advantages of Ag and Cu, are promising materials for power electronic packaging. In this work, a novel dual-beam pulsed laser deposition method was proposed to prepare an Ag-Cu nanoparticle film with various component ratios and used for die attach at low temperatures. The as-deposited Ag-Cu nanoparticle film was mainly composed of Ag-Cu solid solution, Ag element, and Cu element, and most of the nanoparticles were in the alloying state. The Ag-Cu sintered joint presented a dense microstructure with 10.8% porosity, and the shear strength of Ag-Cu sintered joints could reach 60 MPa at 250 °C. The sintered joint porosity increased as more Cu were added in the Ag-Cu nanoparticle film, resulting in a decrease in the interfacial connection ratio. The fracture mode of sintered joints gradually changed from the sintered layer to the mixed sintered layer and interface fracture. The dual-beam pulsed laser deposition method could guide in designing the component ratios of bimetallic nanoparticles.

Fabrication of ZnSnO3 single crystal films on sapphire substrates by pulsed laser deposition for solar-blind photodetectors

ZnSnO3 single crystal films were prepared on c-plane sapphire substrates using pulsed laser deposition and post-annealing methods. For the as-grown sample at 700 °C, post-annealing at 700 °C resulted in a significant improvement in the crystalline quality of the single crystal films, while post-annealing at 800 °C led to decomposition of ZnSnO3. Compared with the amorphous and mixed crystal ZnSnO3-based photodetectors (PDs), the single crystal ZnSnO3-based PD has a better light-to-dark current ratio (1.32 × 106) and higher responsivity (8.71 A/W) at 5 V under 254-nm UV (1.1 mW/cm2) illumination. Such a good performance serves as resounding validation of the remarkable potential of ZnSnO3 epitaxial films in the context of solar-blind PDs.

Fabrication of nanocrystalline SnO2 films by Nd:YAG pulsed laser deposition method for gas sensor applications

Fabrication of nanocrystalline SnO2 films by Nd:YAG pulsed laser deposition method for gas sensor applications

Role of substrate temperature on the performance of BaTiO3/Si photodetector prepared by pulsed laser deposition

In this study, the pulsed laser deposition (PLD) method was employed to fabricate nanostructured BaTiO3 films on glass and silicon substrates at varying temperatures. The structural analysis confirmed the formation of crystalline nanostructured BaTiO3 with mixed tetragonal and hexagonal phases, and the film deposited at 150 °C has the best crystallinity and largest particle size. The optical energy gap of the BaTiO3 nanostructure decreases from 3.94 to 3.84 eV, with increasing substrate temperature from 60 to 150 °C. Photoluminescence spectra of BaTiO3 films deposited at 25, 60, 100, and 150 °C exhibit emission peaks centered at 450, 512, 474, and 531 nm, respectively. Raman spectra of BaTiO3 films show E (LO), A (TO), E (LO) + TO, and B1 vibration modes. Hall measurements reveal that the mobility of the BaTiO3 film increases with temperature up to 100 °C and then decreases at 150 °C. The current–voltage characteristics of the BaTiO3/p-Si heterojunction, deposited over a temperature range of 25 to 150 °C, were investigated in the dark and under illumination. The heterojunctions exhibit rectifying properties, with the best rectification factor observed for the heterojunction prepared at 100 °C. The values of the ideality factor for the heterojunctions fabricated at 25, 60, 100, and 150 °C were 4.3, 3.8, 2.8, and 5, respectively. The study reveals an improvement in both the figures of merit and the photodetector performance with increased substrate temperature. The responsivity increases from 2.2 to 9.25 A/W as the deposition temperature rises from 25 to 100 °C. The detectivity (D*) and external quantum efficiency (EQE) of the photodetector prepared at the optimum substrate temperature of 100 °C, were found to be 4.62 × 1012 Jones and 114%, respectively, at 500 nm.

Effect of Nanoparticles on Reflectance Spectra of Cr/Cr2O3 Composites Synthesized by Pulsed Laser Deposition Method

Effect of Nanoparticles on Reflectance Spectra of Cr/Cr2O3 Composites Synthesized by Pulsed Laser Deposition Method

Photovoltaic and resistance switching properties of NiO/Pb0.92La0.08(Zr0.52Ti0.48)O3/LaNiO3

Due to its excellent ferroelectricity and photovoltaic effect (PE), Pb0.92La0.08(Zr0.52Ti0.48)O3 (PLZT) has considerable application potential in the field of multifunctional electronic devices. In this study, an Ag/NiO/PLZT/LaNiO3 structure is prepared on a Si substrate via a combination of sol–gel and pulsed laser deposition methods, and its ferroelectricity, PE and resistance switching (RS) properties are studied in detail. With decrease in temperature, coercive field of PLZT increases, and its residual polarization initially remains constant and then decreases. The results of ultraviolet-irradiation experiments show that the photogenerated open-circuit voltage (Vo) of PLZT first increases slightly and then decreases slightly as the temperature decreases. By changing the direction of PLZT polarization, the polarization field can be oriented in the same direction or opposite to the built-in electric field formed by p–n junction at NiO/PLZT interface. Thus, the total electric field required to drive the photogenerated carriers inside the structure can be tuned, which results in different Vo values. Furthermore, current–voltage characteristics of the structure are tested. It is found that as different polarization charges are generated at the NiO/PLZT interface for different PLZT polarization directions, the holes in NiO can be attracted or repelled by these polarization charges. Thereby, the interface barrier height of the p–n junction can be varied. Consequently, the structure exhibits a pronounced RS effect suitable for multilevel storage applications. These results represent an important experimental basis for the development and application of multifunctional electronic devices for optoelectronics and RS-based memories.

Photoelectric properties of two-dimensional electron gas at the (Ga0.5Al0.5)2O3/SrTiO3 heterointerfaces

We report a two-dimensional electron gas created at the (Ga0.5Al0.5)2O3/SrTiO3 heterointerfaces with different deposition temperatures and thicknesses by a pulsed laser deposition method. It is found that the critical deposition temperature for the metal-to-insulator transition is about 400 °C with a thickness of 43.2 nm. The carrier density and mobility of sample at the deposition temperature of 300 °C are 1012 cm−2 and 67.2 cm2 V−1 s−1 at 50 K, respectively. The thickness of the conductive layer is ∼4.0 nm estimated from the anisotropic magnetoresistance. The bandgaps of films deposited at different temperatures are in the range of 5.6–5.9 eV. Furthermore, the heterointerfaces have a strong response to 360 nm light with a relative resistance change of ∼70%. Our results are related to the charge transfer due to the oxygen defect at the interfaces, which provides a way for the development of third-generation semiconductor optoelectronic devices.

Investigating the interfacial charge transfer between electrodeposited BiVO4 and pulsed laser-deposited Co3O4 p-n junction photoanode in photoelectrocatalytic water splitting

The formation of a p-n junction consisting small-sized, and homogeneous material over the porous semiconductor is an effective strategy for improved photoelectrocatalytic (PEC) water oxidation. Here, the facile pulsed laser deposition (PLD) method was used to load small-sized Co3O4 on BiVO4. The BiVO4/Co3O4 (30 s) photoanode exhibits a higher photocurrent density of 4.66 mA cm−2 @ +1.23 VRHE which is ∼ 4-fold higher than pristine BiVO4. This improved PEC performance is due to the availability of more active sites, improved charge separation, rapid interfacial charge transfer process, higher injection ability, and higher water oxidation kinetics. The higher open circuit voltage (VOC) of BiVO4/Co3O4 offers the greater driving force for charge separation. On the other hand, the density functional theory (DFT) investigations were carried out for further understanding of the facile interfacial charge transfer process. The electrostatic plots from the DFT studies reveals that Co3O4 has a deeper potential than BiVO4 and this potential difference can induce a strong internal electric field across the junction which promotes facile charge transfer from BiVO4 to Co3O4 until equilibration. Under illumination, BiVO4 and Co3O4 act electron acceptor and hole acceptor, respectively. Hence, the hole accumulated water oxidation is taken place in the valence band maximum (VBM) of Co3O4 for an enhanced PEC performance of the p-n junction photoanode.

Optimizing deposition regimes to fabricate VO2/TiO2/c-Al2O3 thin films for active metasurfaces

Decreasing the scale of vanadium dioxide (VO2) structures is one of the ways to enhance the switching speed of the material. We study the properties of VO2 films of altered thicknesses in the range of 20–170[Formula: see text]nm prepared on c-sapphire substrates with a TiO2 sublayer by pulsed laser deposition (PLD) method. The synthesis regime to design a TiO2 film was preliminarily optimized based on XRD data. XRD patterns reveal an epitaxial growth of the VO2 films with distortion of the monoclinic cell to hexagonal symmetry. The positions of the lattice vibration modes in Raman spectra are similar to those in bulk VO2 when the film thickness is greater than [Formula: see text][Formula: see text]nm. For VO2 films thicker that [Formula: see text][Formula: see text]nm, a lattice strain results in the modes’ positions and intensity change. However, the electrically triggered transition in a [Formula: see text][Formula: see text]nm thick VO2 film reveals forward and reverse switching times as short as 20[Formula: see text]ns and 400[Formula: see text]ns, correspondingly.

High‐Quality NiFe Thin Films on Oxide/Non‐Oxide Platforms via Pulsed Laser Deposition at Room Temperature

AbstractSoft ferromagnetic permalloy (NiFe) thin films are promising for applications in spintronic devices because of their constituent electrical and magnetic properties. Electron beam evaporation and sputtering techniques have been used to deposit NiFe thin films. For in situ stacking of NiFe with functional complex oxides, the pulsed laser deposition (PLD) method is highly desirable. However, the growth of high‐quality NiFe (and non‐oxide thin films in general) by PLD remains a formidable task. Here, high‐quality NiFe thin films of various thicknesses on oxide/non‐oxide substrates with desirable magnetic properties by PLD at room temperature are reported. The magnetic properties are found to be strongly dependent on the laser fluence of the deposition process. The laser fluence of 4 J cm−2 produces the highest magnetization of ≈547 emu cc−1. The small coercivity (few Oersted) and sharp ferromagnetic switching behavior indicate uniaxial anisotropy with an easy axis along the in‐plane direction. In addition, thickness‐dependent magnetodynamics characterizations are studied via ferromagnetic resonance. These results offer significant insight into the PLD‐based development of thin metal magnetic films.

High Li-ion diffusion coefficient in LiMn1.5Ni0.5O4 thin films for all-solid Li-ion battery applications

Among various choices of high-performance cathode materials, Ni substituted LiMn2O4 spinel LiMn1.5Ni0.5O4 (LMNO) has proved to be one of the solutions to yield a high-performance and high-energy density material, which can operate at a higher potential window. This study explores the high diffusion coefficient and electrochemical performance at wide current rates of LMNO thin films with less than 50 nm thickness, fabricated on SrTiO3 and SS substrates by the pulsed laser deposition method. The LMNO film with less thickness and the performance without binder and conducting carbon widen the Li-ion path and decrease diffusion length, resulting a higher diffusion coefficient on the order of 10−5 to 10−6 cm2/s, which is several orders higher than the previously obtained reports for bulk counterpart. The cycling stability and rate capability at different current densities of LMNO thin film electrodes are further investigated. Charge–discharge profile at varying current rates of 5, 10, 15, 20, 25, 50, 75, 100, and 125 mA/cm2 is obtained for 500 cycles. The as fabricated film shows a stable profile for 500 cycles with 1.3 and 2.3 μA h/cm2 areal discharge capacity at 25 and 5 mA current rates, respectively. Electrode interfacial properties of LMNO film (before and after cycles) are analyzed using impedance technique. This study indicates that the LMNO thin films can be employed as a cathode layer for fabricating the all-solid thin film batteries for energy applications.

ZnO-Au Hybrid Metamaterial Thin Films with Tunable Optical Properties

ZnO-Au nanocomposite thin films have been previously reported as hybrid metamaterials with unique optical properties such as plasmonic resonance properties and hyperbolic behaviors. In this study, Au composition in the ZnO-Au nanocomposites has been effectively tuned by target composition variation and thus resulted in microstructure and optical property tuning. Specifically, all the ZnO-Au nanocomposite thin films grown through the pulsed laser deposition (PLD) method show obvious vertically aligned nanocomposite (VAN) structure with the Au nanopillars embedded in the ZnO matrix. Moreover, the average diameter of Au nanopillars increases as Au concentration increases, which also leads to the redshifts in the surface plasmon resonance (SPR) wavelength and changes in the hyperbolic behaviors of the films. As a whole, this work discusses how strain-driven tuning of optical properties and microstructure resulted through a novel Au concentration variation approach which has not been previously attempted in the ZnO-Au thin film system. These highly ordered films present great promise in the areas of sensing, waveguides, and nanophotonics to name a few.