Growth Of Thin Films Research Articles

Lead-free methyl ammonium tin iodide perovskite thin film growth in single step via plasma enhanced chemical vapour deposition technique and its optoelectronic properties

In the present work, lead free methyl ammonium tin iodide (CH3NH3SnI3 or MASnI3) perovskite thin films have been deposited via single step plasma enhanced chemical vapour deposition (PECVD) technique. In our earlier work, we reported lead based methyl ammonium lead iodide (CH3NH3PbI3 or MAPbI3) perovskite thin film deposition in 2-step, using sputtering technique for the PbI2 thin films and PECVD technique for CH3NH3I (MAI) thin films. Similarly, CH3NH3SnI3 perovskite thin films are deposited in this work using PECVD technique in single step. Lead is substituted with tin due to its toxic behaviour, environmental and health related issues. CH3NH3SnI3 perovskite is doped n-type via changing the molar ratio of SnI2 and CH3NH3I. SnI2/CH3NH3I ratio is changed from 0.33 to 2 to study the n-type doping of CH3NH3SnI3 perovskite. Deposited CH3NH3SnI3 perovskite thin films are deposited over p-type silicon wafer to make n-type doped n-CH3NH3SnI3/p-Si heterojunction photodiode.

MoS2-assisted growth of highly-oriented AlN thin films by low-temperature van der Waals epitaxy

Aluminum nitride (AlN) is a wide bandgap material used in acoustic devices, piezo- micro-electromechanical system and is promising for other electronic applications. However, for most applications, the AlN crystalline quality obtained by PVD or MOCVD is insufficient, and suitable growth substrates providing an adapted lattice match and coefficient of thermal expansion are limited. Alternatively, monocrystalline AlN wafers are not yet available in 200/300 mm sizes and suffer from high costs and quality issues. Here, we propose a novel approach involving a two-dimensional transition metal dichalcogenide (TMD) material as a seed layer, which displays an excellent lattice matching with AlN (>98%) allowing a strong enhancement in the c axis texture of sputtered AlN layers on Si(100)/SiO2 thermal oxide (500 nm) substrates. We have successfully demonstrated an eightfold improvement of the AlN (002) rocking curve compared to reference samples grown on thermal SiO2, thus providing a relevant and cost-effective process for the large-scale deployment of high-quality III-N materials on silicon-based substrates.

Studies on B-doping during low-temperature growth of nc-Ge thin films via PECVD to mitigate unwanted conduction characteristics from the post-deposition oxygen absorption

Post-deposition O absorption is a common issue in low-temperature grown nc-Ge films, that makes the material unstable and induces high n-type electrical conductivity ∼10−2 S cm−1. An attempt has been made to mitigate the oxygen absorption issue through B doping of the nc-Ge thin film network at a low deposition temperature of ∼220 °C, employing a conventional capacitively coupled PECVD. At a B2H6 flow rate of 3.0 sccm, the incorporation of a restricted quantity of B maintains a narrow band gap of ∼1.04 eV, significantly low conductivity of ∼6.76 ×10−7 S cm−1, activation energy ∼398 meV, and photosensitivity of 6.0. Spectroscopic studies indicated that B doping facilitated reduced O-intake in the nc-Ge matrix, possibly via passivating the grain boundary defects and dangling bonds in the amorphous matrix and inducing the preferential absorption of O atoms in the Ge–O2 configuration compared to its Ge–Ox (x < 2) counterpart. The diminished O-induced carriers and the supplied acceptor levels by the B dopants compensate for the inherent n-type carrier concentration. However, at higher B2H6 flow rates, significant B incorporation in the film matrix introduces numerous defects, degrading the crystallinity, despite increasing its p-type conductivity to 2.16 ×10−5 S cm−1 and maintaining a narrow band gap. Organized switching in the type of conductivity from the n-type to p-type ensues via gradually rising the B-dopants within the nc-Ge thin film network during its growth, which deserves attention for specific device applications.

In situ monitoring of industrial-scale chemical vapor deposition using residual gas analysis

The maintenance of industrial-scale equipment demands more effort and incurs higher costs compared to that of laboratory-scale equipment, necessitating the use of predictive maintenance techniques to mitigate unforeseen outcomes. This paper presents a demonstration of the in situ monitoring of industrial-scale low-pressure chemical vapor deposition equipment by using a residual gas analyzer (RGA). The RGA provides reactions of precursor gases by tracing the concentration and composition of residual gases within vacuum reactors. Furthermore, RGA analysis enables the prediction of the growth rate of the thin-film, providing insights into thin-film growth dynamics during the process. In situ monitoring using an RGA can be applied to diverse semiconductor fabrication processes, including thin-film growth, oxidation, reactive ion etching, and ion implantation, owing to its compatibility with vacuum processes. This study addresses the existing difficulties in the exploration of RGA monitoring techniques for industrial-scale equipment and bridges the disparity between laboratory-scale and industrial-scale processes.

Doped SnO2 thin films fabricated at low temperature by atomic layer deposition with a precise incorporation of niobium atoms

Nb-doped SnO2 (NTO) thin films were synthesized by atomic layer deposition technique at low temperature (100 °C). For an efficient incorporation of the Nb atoms, i.e. fine control of their amount and distribution, various supercycle ratios and precursor pulse sequences were explored. The thin film growth process studied by in-situ QCM revealed that the Nb incorporation is highly impacted by the surface nature as well as the amount of species available at the surface. This was confirmed by the actual concentration of the Nb atom incorporated inside the thin film as determined by XPS. Highly transparent thin films which transmit more than 95% of the AM1.5 global solar irradiance over a wide spectral range (300–1000 nm) were obtained. In addition, the Nb atoms influenced the optical band gap, conduction band, and valence band levels. While SnO2 thin film were too resistive, films tuned to conductive nature upon Nb incorporation with controlled concentration. Optimal incorporation level was found to be ⩽1 at.% of Nb, and carrier concentration reached up 2.5 × 1018 cm−3 for the as-deposited thin films. As a result, the high optical transparency accompanied with tuned electrical property of NTO thin films fabricated by ALD at low temperature paves the way for their integration into temperature-sensitive, nanostructured optoelectrical devices.

Harnessing ion beam erosion engineering for controlled self-assembly and tunable magnetic anisotropy in epitaxial films

The engineering of the surface morphology and the structure of the thin film is one of the essential technological assets for regulating the physical properties and functionalities of thin film-based devices. This study presents an easy and handy approach to tailor the surface structure of epitaxial thin films utilizing low-energy ion beam. Here, we investigate the evolution of the surface structure and magnetic anisotropy (MA) in epitaxial Fe/MgO (001) model systems subjected to multiple cycles of ion beam erosion (IBE) after thin film growth. The growth of Fe film occurs in the form of three–dimensional islands and exhibits intrinsic biaxial MA. Following a few cycles of IBE, an induced uniaxial magnetic anisotropy leads to a split in the hysteresis loop, and the film displays almost uniaxial magnetic switching behavior. More distinctly, we present a clear and conclusive evidence of (2 × 2) reconstruction of the Fe surface due to the atomic rearrangement by IBE. Furthermore, 57Fe isotope sensitive nuclear resonance scattering measurement provides insight into the depth-resolved magnetic information due to the modified surface topography. We also demonstrate that thermal annealing can reversibly tune the surface reconstruction and induced UMA. The feasibility of the IBE technique by adequately selecting IBE parameters for surface structure modification has been highlighted apart from conventional tailoring of the morphology for the tuning of UMA and introduces a new dimension to our understanding of self-assembled surface morphology evolution by IBE.

Epitaxy of Monoclinic VO2 on Large-Misfit 3m Template Enabled by a Metastable Interfacial Layer.

We report the epitaxial growth of a monoclinic VO2 thin film on the CoFe2O4(111) template, assisted by an interfacial layer of the metastable orthorhombic phase. The interface between orthorhombic VO2 and CoFe2O4 is atomically sharp without noticeable interfacial diffusion. The (010)-faceted orthorhombic VO2 layer is lattice-matched to both the CoFe2O4(111) template and the monoclinic phase, although they have different surface symmetries. The occurrence of an orthorhombic VO2 thin layer significantly lowers the in-plane misfit strains of the monoclinic VO2 epilayer, along both the [100] and [001] axes. Our first-principles calculations confirm that the low-misfit orthorhombic VO2 is preferred on CoFe2O4(111) over the large-misfit monoclinic phase, at the initial growth stage. Additionally, upon increasing the film thickness to ∼8 nm, the orthorhombic phase is no longer favored, and the bulk stable monoclinic VO2 appears to minimize the free energy of the system. Moreover, we show that the metal-to-insulator transition of our VO2 epilayer can be efficiently triggered by both the temperature and Joule self-heating effect.

High growth rate metal organic chemical vapor deposition grown Ga2O3 (010) Schottky diodes

We report on the growth of Si-doped homoepitaxial β-Ga2O3 thin films on (010) Ga2O3 substrates via metal-organic chemical vapor deposition (MOCVD) utilizing triethylgallium (TEGa) and trimethylgallium (TMGa) precursors. The epitaxial growth achieved an impressive 9.5 μm thickness at 3 μm/h using TMGa, a significant advance in material growth for electronic device fabrication. This paper systematically studies the Schottky barrier diodes fabricated on the three MOCVD-grown films, each exhibiting variations in the epilayer thickness, doping levels, and growth rates. The diode from the 2 μm thick Ga2O3 epilayer with TEGa precursor demonstrates promising forward current densities, the lowest specific on-resistance, and the lowest ideality factor, endorsing TEGa’s potential for MOCVD growth. Conversely, the diode from the 9.5 μm thick Ga2O3 layer with TMGa precursor exhibits excellent characteristics in terms of lowest leakage current, highest on-off ratio, and highest reverse breakdown voltage of −510 V without any electric field management, emphasizing TMGa’s suitability for achieving high growth rates in Ga2O3 epilayers for vertical power electronic devices.

Heteroepitaxial growth of Ga2O3 thin films on Al2O3(0001) by ion beam sputter deposition

Deposition of epitaxial oxide semiconductor films using physical vapor deposition methods requires a detailed understanding of the role of energetic particles to control and optimize the film properties. In the present study, Ga2O3 thin films are heteroepitaxially grown on Al2O3(0001) substrates using oxygen ion beam sputter deposition. The influence of the following relevant process parameters on the properties of the thin films is investigated: substrate temperature, oxygen background pressure, energy of primary ions, ion beam current, and sputtering geometry. The kinetic energy distributions of ions in the film-forming flux are measured using an energy-selective mass spectrometer, and the resulting films are characterized regarding crystalline structure, microstructure, surface roughness, mass density, and growth rate. The energetic impact of film-forming particles on the thin film structure is analyzed, and a noticeable decrease in crystalline quality is observed above the average energy of film-forming Ga+ ions around 40 eV for the films grown at a substrate temperature of 725 °C.

Monoclinic LaSb2 Superconducting Thin Films.

Rare-earth diantimondes exhibit coupling between structural and electronic orders, which are tunable under pressure and temperature. Here we present the discovery of a new polymorph of LaSb2 stabilized in thin films synthesized using molecular beam epitaxy. Using diffraction, electron microscopy, and first-principles calculations we identify a YbSb2-type monoclinic lattice as a yet-uncharacterized stacking configuration. The material hosts superconductivity with a Tc = 2 K, which is enhanced relative to the bulk ambient phase, and a long superconducting coherence length of 1730 Å. This result highlights the potential thin film growth has in stabilizing novel stacking configurations in quasi-two-dimensional compounds with competing layered structures.

Examining the influence of W thickness on the Si-on-W Interface: A comparative metrology analysis

W/Si thin-film multilayer structures are used in various applications such as X-ray, neutron, and extreme ultraviolet optics. The interfaces between the films play such a fundamental role in the performance of these structures that a sub-nanometer and non-destructive characterization of such interfaces is necessary, albeit challenging. In this study, we investigate the interface Si-on-W and the effect of W thickness on such an interface using low energy ion scattering (LEIS), X-ray reflectivity (XRR), and transmission electron microscopy (TEM). We extract the Si-to-W error-function-like compositional change to quantitatively compare the effective interface width measured by the different techniques. We demonstrate that, in the case of Si-on-W, the effective interface width measured by LEIS and XRR agrees with the values extracted from TEM analysis within a 0.1 nm error margin. Noting that TEM is a destructive method, these results exemplify the value of LEIS and XRR as analysis techniques for resolving thin film interfaces. Surprisingly, all techniques employed in the study show that a structure with 20 nm of W has a sharper Si-on-W interface compared to a structure with 4 nm of W, which we interpret as the effect of both the correlated roughness from the substrate − present in the case of 4 nm W − and the larger crystals − present in the W film in the case of 20 nm W- resulting in less intermixing. This directly shows the value of extracting exact interface widths for the analysis and understanding of thin film growth in multilayer systems.

Chemical Bonding and Crystal Structure Schemes in Atomic/Molecular Layer Deposited Fe-Terephthalate Thin Films.

Advanced deposition routes are vital for the growth of functional metal-organic thin films. The gas-phase atomic/molecular layer deposition (ALD/MLD) technique provides solvent-free and uniform nanoscale thin films with unprecedented thickness control and allows straightforward device integration. Most excitingly, the ALD/MLD technique can enable the in situ growth of novel crystalline metal-organic materials. An exquisite example is iron-terephthalate (Fe-BDC), which is one of the most appealing metal-organic framework (MOF) type materials and thus widely studied in bulk form owing to its attractive potential in photocatalysis, biomedicine, and beyond. Resolving the chemistry and structural features of new thin film materials requires an extended selection of characterization and modeling techniques. Here we demonstrate how the unique features of the ALD/MLD grown in situ crystalline Fe-BDC thin films, different from the bulk Fe-BDC MOFs, can be resolved through techniques such as synchrotron grazing-incidence X-ray diffraction (GIXRD), Mössbauer spectroscopy, and resonant inelastic X-ray scattering (RIXS) and crystal structure predictions. The investigations of the Fe-BDC thin films, containing both trivalent and divalent iron, converge toward a novel crystalline Fe(III)-BDC monoclinic phase with space group C2/c and an amorphous Fe(II)-BDC phase. Finally, we demonstrate the excellent thermal stability of our Fe-BDC thin films.

Engineering Oxide Epitaxy beyond Substrate Constraint.

Orientation engineering is a crucial aspect of thin film growth, and it is rather challenging to engineer film epitaxy beyond the substrate constraint. Guided by density functional theory calculations, we use SrRuO3 (SRO) as a buffer layer and successfully deposit [111]-oriented CoFe2O4 (CFO) on [001]-, [110]-, and [111]-oriented SrTiO3 (STO) substrates. This enables subsequent growth of [111]-oriented functional oxides, such as PbTiO3 (PTO), overcoming the constraint of the substrate. This strategy is quite general and applicable to lanthanum aluminate and yttria-stabilized zirconia substrates as well. X-ray Φ scans and atomic resolution aberration-corrected scanning transmission electron microscopy (AC-STEM) reveal detailed epitaxial relations in each of the cases, with four variants of [111]-CFO found on [001]-STO and two variants found on [110]-STO, formed to mitigate the large lattice misfit strain between the film and substrate. Our strategy thus provides a general pathway for orientation engineering of oxide epitaxy beyond substrate constraint.

On direct-current magnetron sputtering at industrial conditions with high ionization fraction of sputtered species

In the industry, there is a preference for robust and technologically straightforward solutions that can deliver desired products at reasonable costs. This study introduces a reliable, robust, and cost-effective ion-assisted thin film growth technique called moving focused magnetic field magnetron sputtering. At the core of this technology lies the generation of dense plasma within a small area of the target and the controlled movement of this plasma across the entire target surface. The deposition process, powered by a direct current generator, behaves similarly to high-power impulse magnetron sputtering and yields coatings with properties comparable to those produced by this method. Notably, this study marks the first application of an ion meter to measure the ionized metal flux fraction of sputtered titanium at industrial conditions, revealing values of up to 34% measured at the substrate position.

Machine-learning-empowered identification of initial growth modes for 2D transition metal dichalcogenide thin films

In situ reflection high-energy electron diffraction (RHEED) is a powerful technique for monitoring surface states and offers invaluable insights into thin film growth. However, extracting hidden features and subtle changes from its vast data remains as a challenge. This work bridges the gap by employing machine learning (ML)-empowered RHEED analysis to elucidate the growth dynamics of two-dimensional (2D) transition metal dichalcogenide (TMDC) thin films grown under two distinct growth modes. Principal component analysis (PCA) and its modified processes were used to separate contributions of the graphene substrate and the MoSe2 film in the RHEED video. The ML-empowered RHEED analysis allowed us to effectively filter out the strong substrate signal and reconstructing RHEED videos solely for the MoSe2 films. This approach enabled detailed monitoring of film growth with unique features, and clearly distinguishing between the layer-by-layer growth mode and the island one. This work demonstrates the potentials of ML-empowered RHEED analysis for revealing complex growth dynamics of 2D TMDC materials, paving the way for advanced thin film monitoring and autonomous control in wider scope of thin film technologies.

Growth of ZnO thin Films from Depleted Batteries for Water Remediation

AbstractZnO films were obtained by electrodeposition technique from commercial Zn2+ solutions and those obtained from spent alkaline batteries. The type of counterion and pH impact directly on the structural, morphological, and optical properties of the electrodeposited ZnO films. The morphological and crystallographic orientation differences observed by X‐ray diffraction (XRD) analysis and high‐resolution field emission scanning electron microscopy (HR‐FESEM), demonstrates the influence of the type and origin of precursors used in the ZnO synthesis process. Those samples grown from commercial nitrate solutions exhibit nanocolumns revealing a preferential growth in the (002) direction. On the other hand, random growth (hexagonal plates, agglomerations, clusters, etc.) is observed in samples obtained through recycled solutions. All deposited samples achieved a transparency close to 80 % and an optical band gap of around 3.30 eV. The as‐deposited films were evaluated toward the photodegradation capacity of methylene blue (MB) for potential technological applications. Results exhibit that samples prepared from recycled ZnCl2 solutions presented more than 80 % degradation per mass of ZnO. This work demonstrates a virtuous circle since ZnO films are deposited by a facile and scalable technique from discarded batteries and used for MB photodegradation. Furthermore, the simplicity of recovery of these substrates after application makes them an attractive and pragmatic option for a range of water treatment applications. Synopsis: Zinc from depleted alkaline batteries is reused to obtain ZnO thin films that remove contaminating dyes from water.

Comparative analysis of phase coherence length in polycrystalline CdO films on two distinct substrates

The role of substrates in thin film growth encompasses structural and morphological characteristics which, as a consequence, can also affect electronic properties. This article reports studies on the structural, morphological, and magnetotransport properties of Cadmium Oxide (CdO) films grown on two distinct substrates, amorphous glass, and crystalline silicon, by spray pyrolysis technique. The crystallinity of CdO grown on Silicon (CdO/Si) is higher as compared to the CdO grown on glass (CdO/glass), although CdO/Si morphology presents a dome-like surface. In both cases, samples showed exponential behavior in the electrical resistance curves in the temperature ranges between 1.9 K to 300 K and negative magnetoresistance, due to the weak localization effect, for temperatures lower than 110 K. The highest electronic mobility for CdO/Si is attributed to the better crystallinity of the domes. The weak localization effect is correlated by the 3D Kawabata model, fitting the magnetoresistance curves to determine the phase coherence length over a temperature range of 4.2 K to 100 K. Despite the huge differences in the morphological and electrical properties, the linear behavior of temperature-dependent phase coherence length, attributed to the electron-electron interaction in this temperature range, is found to be independent of the employed substrate. This remarkable result indicates the potential application of the low-cost spray pyrolysis technique for producing high-speed photodetectors.

Growth of high quality polycrystalline InGaO thin films by spray pyrolysis for coplanar thin-film transistors on polyimide substrate

The current mobile devices are moving towards flexible electronics. Introducing crystalline oxide semiconductors on flexible substrates is important to satisfy the requirements of high-resolution displays on flexible substrates. This study investigates the low-cost, as-grown polycrystalline (Poly) InGaO thin film transistor by spray pyrolysis on polyimide (PI) substrate. Grazing Incidence X-ray Diffraction (GI-XRD) measurements demonstrate that In0.8Ga0.2O, In0.7Ga0.3O, and In0.5Ga0.5O compositions exhibit crystallization on-set temperatures of ∼330, ∼350, and ∼415°C, respectively. Poly-In0.7Ga0.3O thin film with lower oxygen-vacancy (∼15 %) and less than 5 % O-H group could be achieved at the substrate temperature of 370°C. The hysteresis-free device performance with an average saturation mobility of 43.73 cm2V−1s−1 has been obtained using the poly-In0.7Ga0.3O with optimized N2O plasma treatment on the poly-oxide thin film. The TFTs show remarkable stability under humid environments and various stress conditions such as positive bias temperature, negative bias temperature, and mechanical stresses. In addition, the 96-stage gate shift register made of poly-In0.7Ga0.3O TFTs by spray pyrolysis exhibits the rising and falling times of less than 820 ns. Therefore, the poly-In0.7Ga0.3O TFTs by spray pyrolysis could be used for high-resolution, cost-effective, flexible active-matrix light-emitting displays.

In situ monitoring of thin alumina passive film growth by surface plasmon resonance (SPR) during an electrochemical process

This article presents a sensing technique to characterize the growth of an alumina passive film on an aluminum micro structured layer in situ. The technique uses surface plasmon resonance (SPR) on aluminum coated gratings with spectroscopic measurements during electrochemical polarization in 0.02M Na2SO4. The structure of the sensor was first simulated and then fabricated by photolithography. The grating was then replicated by nanoimprint (NIL) in Sol–Gel before pure aluminum layer was deposited by RF magnetron sputtering to produce the samples used in this study. Coupled plasmonic and electrochemical measurements confirmed the feasibility of in situ characterization (thickness) of alumina passive film on aluminum-based gratings in neutral aqueous media. Combining both measurements with an appropriated SPR spectrum fitting lead to alumina thickness monitoring within a few nanometers’ accuracy. The objectives and challenges of this study are to better characterize the alumina growth during electrochemical process combining in situ electrochemical process and SPR spectra in order to determine thin passive layer characteristics.

Magnetic compensation in sputtered ferrimagnetic Mn 4−x Ga x N thin films

Fully compensated ferrimagnets are attracting increasing attention for spintronics. Here we report a series of Mn 4−x Ga x N ferrimagnetic thin films grown on (100)-oriented MgO by magnetron sputtering. A small tetragonal distortion with c/a = 0.99 leads to perpendicular magnetic anisotropy with a [001] easy axis. The magnetisation decreases with increasing Ga content up to x = 0.18, where the magnetic moment is close to zero at room temperature. It increases with further increase of x, indicating the magnetic compensation composition has been crossed and the dominant sublattice has switched from Mn on the corner sites, where it is progressively replaced by nonmagnetic Ga, to noncollinear Mn on the face-centered sites. Compensation found at 235 K in a remanent scan of the x = 0.18 film is confirmed by measurements of the anomalous Hall effect and interpolation of the inverse coercivity. This work establishes the conditions for thin film growth of Mn 4−x Ga x N that could be used for room-temperature ferrimagnetic spintronics. The behaviour of thin films is compared with that of bulk material.