Film Growth Process Research Articles

Multistage Regulation Strategy via Fluorine-Rich Small Molecules for Realizing High-Performance Perovskite Solar Cells.

Perovskite solar cells (PSCs) are an ideal candidate for next-generation photovoltaic applications but face many challenges for their wider application, including uncontrolled fast crystallization, trap-assisted nonradiative recombination, and inefficient charge transport. Herein, a multistage regulation (MSR) strategy for addressing these challenges is proposed via the introduction of fluorine-rich small molecules with multiple active points (i.e., 1-[Bis(trifluoromethanesulfonyl)methyl]- 2,3,4,5,6-pentafluorobenzene (TFSP)) into the precursor solution of the perovskite film. The addition of TFSP effectively delays and regulates the crystallization and growth process of the perovskite film for larger grains and fewer defects, and it effectively improves the coverage of self-assembled molecules for efficient charge transport. The multiple active points of TFSP induce a strong binding affinity with uncoordinated defects in the perovskite film. Moreover, the high fluorine content of TFSP induces strong electronegativity to establish a high binding strength between the perovskite film and electron transport layer. Finally, PSCs prepared by the MSR strategy demonstrated an optimal power conversion efficiency (PCE) of 25.46% and maintained 91.16% of the initial PCE under nonpackaged air conditions and at a relative humidity of 45% after 3000h.

Nucleation study of AlN crystal growth on 6H-SiC substrates using the MOCVD

This study delves into the nucleation process of AlN crystal growth on a 6H-SiC substrate using metal-organic chemical vapor deposition technology through molecular dynamics simulations and experimental research. It was found that AlN predominantly exhibits an island growth mode, with nucleation morphologies mainly being triangular and hexagonal. This paper provides a detailed analysis of the surface morphology and atomic structure of AlN thin films and compares the fusion processes of the crystals. Through simulations, this study reveals the formation energy and adsorption energy of different nucleation morphologies and their adsorption capacities for Al and N atoms. Additionally, the research observed various types of stacking faults that may occur during the AlN thin film growth process and explored the formation mechanisms of these faults and their impact on the quality of subsequent films. Ultimately, it concludes that hexagonal AlN with double-bonded Al atoms at the edges possesses more stable structural formation energy and stronger adsorption capacity, which contributes to the outward expansion of its edges but may also lead to a transition of the nucleation morphology to triangular.

Morphological and Composition Variations of Cu-Se Thick Films Electrodeposited on Au Substrate

The electrodeposition of copper selenide (Cu2Se) has been demonstrated to have various applications, such as in photovoltaics and thermoelectric devices1. The stoichiometry of electrodeposited CuxSe is found to be rather complex and sensitive to deposition conditions. Several studies have focused on the influence of the effect of bath temperature, electrolyte composition, the applied potential, and current density2–5. Although these parameters can control the thickness and the morphology of the deposited film, thick film fabrication research has not been frequently reported despite the necessity of thermo-device application6. The long length of the thermo-legs in a thermo-device is important, tenths to hundreds of microns. Thick thermo-legs minimize the interface thermal resistance and maximize the temperature drop, ∆T TEG . It is, however, noticed that the morphology and stoichiometry of thermos-leg often vary with film growth, posing many challenges in the fabrication of thick films7. Understanding the nucleation and growth mechanisms of Cu2Se during electrodeposition is essential for optimizing its properties.This work examines the growth process of thick Cu2Se films by electrodeposition on a gold substrate. Films were fabricated by potentiostatic and pulsed electrodeposition on a gold working electrode in an acidic electrolyte, H2SO4, containing 10 mM CuSO4 and 5 mM H2SeO3 at 55oC. A platinum mesh served as the counter electrode and all potentials were referred to Ag/AgCl/sat reference electrodes. Atomic composition and morphology were investigated as a function of applied potential and film thickness direction. About 12µm thick and dense Cu2Se films were grown by optimizing the deposition parameters. SEM observations showed that the deposits, obtained at potentials ranging between -130 mV and -450 mV, were non-uniform, accompanying many clusters of mossy morphology with composition variations. EDS analysis indicates that films are initially Se-rich films, possibly an admixture of Cu2Se and Cu3Se2 transitioning to a near stoichiometry composition of Cu2Se with increasing thickness of about 1µm, at potentials of -130mV and -250mV. Increasing the copper electrolyte concentration and employing pulsed electrodeposition did not significantly influence the film composition in the initial stages. These parameter changes may avoid the formation of mossy deposits to provide a smoother surface.References R. A. Hussain and I. Hussain, Solid State Sci, 100, 106101 (2020).D. Lippkow and H.-H. Strehblow, Electrochim Acta, 43, 2131–2140 (1998).A. Moysiadou, R. Koutsikou, and M. Bouroushian, Mater Lett, 139, 112–115 (2015).Z. Zainal, A. Kassim, M. Z. Hussein, and C. H. Ching, Mater Lett, 58, 2199–2202 (2004).A. Marlot and J. Vedel, J Electrochem Soc, 146, 177–183 (1999).S. Thanikaikarasan, D. Dhanasekaran, and K. Sankaranarayanan, Chinese Journal of Physics, 63, 138–148 (2020).K. Klosel, S. Pane, I. A. Mihailovic, and C. Hierold, Electrochim Acta, 403, 1139557 (2022).

Perovskite Film Passivation and Precursor Engineering for High Performance Devices

Perovskite films are attracting much attention due to their excellent optoelectronic properties. The corresponding photovoltaic devices have shown a record efficiency of 26.7% since 2009, which is very promising to surpass silicon solar cells. The defects of the perovskite films are the major negative factors in achieving high efficiency. The defects of the perovskite films are related to the polycrystal nature of the perovskite films, which is unavoided and caused by the solution-based method. Therefore, high-quality perovskite films with fewer defects are very critical to obtain high-efficiency devices. One strategy is to passivate defects of the films after the film fabrication. We passivate perovskite films with organic materials including polymers, organic small molecules as well as dye molecules. The organic molecules with the special organic functional groups interact with perovskite films to modify the defects of the films to improve the charge transport and reduce charge recombination, leading to improved device performance. The surface defects and the grain boundary defects of the perovskite films are passivated by the organic materials, which is confirmed by the electron/hole-only devices, electronic impedance spectroscopy (EIS) studies, photoluminescence, and time-resolved photoluminescence. The device efficiency increases significantly which is manifested by the J-V measurements. The passivation mechanism of the devices by organic materials is investigated and demonstrated. In addition, The other strategy is to incorporate some additives into the perovskite solutions to adjust the perovskite film growth toward fewer defects. We control the perovskite film growth process by precursor engineering via solvent and solute control. High-quality perovskite films can be obtained by our method for high-performance devices.

Enhanced the efficiency of carbon based perovskite solar cells via g-C3N4 as functional additives

The quality of perovskite layer plays an important role in the performance of perovskite solar cells. Various defects can arise during the crystal growth process of Perovskite thin film. However, by using additives. It is possible to effectively enhance crystallize and form high-quality perovskite films with improved morphology. g-C3N4, a carbon–nitrogen ring with delocalized π electrons and certain conductivity, facilitates the transport of charge carriers. When it is utilized as an additive in perovskite solar cells, g-C3N4 not only improves the quality and crystallinity of perovskite films, but also passivates defects. As a result of these improvements, the optimal efficiency for preparing carbon-based perovskite solar cells is 13.74 %. This represents a significant increase in photoelectric conversion efficiency from 10.39 % to 13.74 %, corresponding to a remarkable enhancement of 32.24 %. These findings provide valuable insights into the potential application of two-dimensional materials and carbon nitrogen ring for enhancing the performance of perovskite solar cells.

Insights into the growth of GaN thin films through liquid gallium sputtering: A plasma-film combined analysis.

This study presents the detailed characterization of a magnetron-based Ar-N2 plasma discharge used to sputter a liquid Ga target for the deposition of gallium nitride (GaN) thin films. By utilizing in situ diagnostic techniques including optical emission spectroscopy and microwave interferometry, we determine different temperatures (rotational and vibrational of N2 molecules, and electronic excitation of Ar atoms) and electron density, respectively. Beyond providing insights into fundamental plasma physics, our research establishes a significant correlation between gas-phase dynamics, particularly those of gallium atoms (flux and average energy at the substrate) and deposited GaN thin film properties (growth rate and crystalline fraction). These findings underscore the role of plasma conditions in enhancing thin film quality, highlighting the importance of plasma characterization in understanding and optimizing GaN thin film growth processes.

Lead iodide secondary growth and π-π stack regulation for sequential perovskite solar cells with 23.62% efficiency

The sequential deposited perovskite solar cells (PSCs) have received widespread attention due to its application potential in large-scale perovskite module and perovskite/silicon tandem solar cells. However, insufficient reaction between organic ammonium salts and PbI2 leads to residual PbI2 and low crystallinity of perovskite films, and the fragile Pb-I bonds easily creates iodine loss and reduces the stability of PbI6 framework. In this work, the 4-fluorobenzylamine (FBA) with C = O and –NH2 is employed in PbI2 precursor solution to regulate the secondary growth process of PbI2 film. Due to the low Gibbs free energy and high crystallinity of porous PbI2 film, sufficient reaction between organic ammonium salts and PbI2 is promoted, which results in large-grain, low-defect perovskite films. At the same time, through hydrogen bonding and π-π stacking interactions, the stability of the PbI6 skeleton is effectively improved, significantly suppressing non-radiative recombination and reducing defect state density. Finally, this strategy increases the power conversion efficiency (PCE) of PSCs from 22.06 % to 23.62 %, and the target PSCs maintain 96 % of their initial PCE after being placed in nitrogen for 1300 h.

Sputter-deposited TiOx thin film as a buried interface modification layer for efficient and stable perovskite solar cells

Despite perovskite solar cells (PSCs) based on a SnO2 hole-blocking layer (HBL) are achieving excellent performance, the non-perfect buried interface between the SnO2 HBL and the perovskite layer is still an obstacle in achieving further improvement in power conversion efficiency (PCE) and stability. The poor morphology with numerous defects and the energy level mismatch at the buried interface constrain the open circuit voltage and cause instability. Herein, a sputter-deposited TiOx thin film is used as a buried interface modification layer to address the aforementioned issues. Utilizing in situ grazing-incidence small-angle X-ray scattering (GISAXS) during the sputter deposition, we monitor and unveil the growth process of the TiOx thin film, identifying a 10 nm thickness optimum. The defects at the buried interface are passivated through tuning the growth, leading to a suppressed non-radiative recombination and improved PCE (from 22.19 % to 23.93 %). The evolution of the device performance and the degradation process of PSCs using operando grazing-incidence wide-angle X-ray scattering (GIWAXS) under the protocol ISOS-L-1I explains the enhanced stability introduced by the buried interface modification via a sputter-deposited TiOx thin layer. The perovskite decomposition process and the detrimental formation of PbI2 are both slowed down by the TiOx thin layer.

A novel photoelectrochemical based water splitting and uric acid biosensing using PLD grown In2Se3 thin films

By altering the deposition pressure during the film growth process using the pulsed laser deposition (PLD) technology, indium selenide (In2Se3) thin films have been optimized to produce their distinct phases. The phase purity, optical and morphological studies were carried out using XRD, Raman spectroscopy, XPS, UV–visible spectroscopy, AFM and FESEM measurements. A high absorption in the visible region is observed for In2Se3 thin films with suitable band edges for hydrogen evolution. Photoelectrochemical (PEC) activity for In2Se3 photoelectrodes having various phases was analyzed based on CV and I-t response. A good charge transport characteristics were observed using the EIS measurements on PLD grown In2Se3 thin films. The Mott–Schottky analysis for the charge carrier density, flat band potential, and depletion layer width was performed for the deposition pressure dependent phase formation and high performance for PEC water splitting conversion efficiency of 0.48 %, 0.57 % and 0.98 % corresponding to α-In2Se3, β-In2Se3 and γ-In2Se3 were observed, respectively. The as prepared In2Se3 thin films were employed for the detection of Uric Acid (UA) using the cyclic voltammetry (CV), differential pulse voltammetry (DPV) and chronoamperometry. The high sensitivity (0.38 mA/mM), selectivity and repeatability of the prepared biosensor demonstrates In2Se3 as potential candidate for the PEC based water splitting and biosensing application without the presence of an external mediator and can work in the self-powered mode.

Semantic segmentation in crystal growth process using fake micrograph machine learning

Microscopic evaluation is one of the most effective methods in materials research. High-quality images are essential to analyze microscopic images using artificial intelligence. To overcome this challenge, we propose the machine learning of “fake micrographs” in this study. To verify the effectiveness of this method, we chose to analyze the optical microscopic images of the crystal growth process of a Ge thin film, which is a material in which it is difficult to obtain a contrast between the crystal and amorphous states. By learning the automatically generated fake micrographs that mimic the crystal growth process, the machine learning model can now identify the low-resolution real micrographs as crystalline or amorphous. Comparing the three types of machine learning models, it was found that ResUNet ++ exhibited high accuracy, exceeding 90%. The technology developed in this study for the automatic and rapid analysis of low-resolution images is widely helpful in material research.

Beyond Structural Stabilization of Highly‐Textured AlN Thin Films: The Role of Chemical Effects

AbstractThe crystalline quality and degree of c‐axis orientation of hexagonal AlN thin films correlate directly with their functional properties. Therefore, achieving AlN thin films of high crystalline quality and texture is of extraordinary importance for many applications, but particularly in electronic devices. This systematic study reveals, that the growth of c‐axis‐orientated AlN thin films can be governed by a chemical stabilization effect in addition to the conventionally known structural, strain‐induced, stabilization mechanism. The promotion of in‐plane growth of AlN grains with c‐axis out‐of‐plane orientation is demonstrated on Y, W, or Al seed layers with different thicknesses and crystallinity preliminary exposed to N2 at room temperature. It is established that the stabilization mechanism is chemical in nature: the formation of an N‐rich surface layer on the metal seed layers upon exposure to N2 pre‐determines the polarity of AlN islands at the initial stages of thin film growth while the low energy barrier for the subsequent coalescence of islands of the same polarity contributes to grain growth. These results suggest that the growth of c‐axis oriented AlN thin films can be optimized and controlled chemically, thus opening more pathways for energy‐efficient and controllable AlN thin film growth 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.

Operando characterization of Cr-containing alloy passivation film by synchrotron radiation

Techniques of electrochemical-spectroscopic ellipsometry, electrochemical-Raman spectroscopy, and electrochemical-grazing incidence X-ray diffraction using the electrochemical synchrotron radiation source were combined to characterize the growth process of chromium-containing passivation film. The operando method can characterize passivation film in detail and monitor the growth process of these films, which can not be done sufficiently using uncombined traditional structural characterization techniques. For example, Fe-18 wt%Cr steel was used to monitor the passivation process, such as adsorbed species that transformed into stable species and the decrease in the dissolution of internal metals. This means that the operando method developed in this work could effectively monitor passivation.

Preparation and growth mechanism of nonpolar, semipolar and polar ZnO films: Correlation of preferred orientation, defects and optical properties

In the study, ZnO films with different preferred orientations were controllably prepared by using NH3·H2O to modulate the pH0 of chemical bath deposition. The samples were all characterised by field emission scanning electron microscopy (FESEM), atomic force microscopy (AFM), X-ray diffraction (XRD), ultraviolet-visible spectrophotometry (UV–VIS), X-ray photoemission spectroscopy (XPS) and photoluminescence (PL). The results show that ZnO films with polar, semipolar and nonpolar preferred orientations can be synthesised in a controlled manner by varying the pH0. Meanwhile, the influence of NH3·H2O concentration on the growth process of ZnO films is investigated in detail, and the relationship between the preferred orientation and optical properties is preliminarily discussed. At pH0= 7.32, the films exhibited semipolar (101) preferred orientation, the highest optical transmittance (89.15 %), and the highest concentration of Zni in the films. This study provides a method for the controlled synthesis of ZnO films with polar, semipolar and nonpolar preferred orientations and offers new possibilities for ZnO-based transparent semiconductor devices.

Resistive Memristors Using Robust Electropolymerized Porous Organic Polymer Films as Switchable Materials.

Porous organic polymers (POPs) with inherent porosity, tunable pore environment, and semiconductive property are ideally suitable for application in various advanced semiconductor-related devices. However, owing to the lack of processability, POPs are usually prepared in powder forms, which limits their application in advanced devices. Herein, we demonstrate an example of information storage application of POPs with film form prepared by an electrochemical method. The growth process of the electropolymerized films in accordance with the Volmer-Weber model was proposed by observation of atomic force microscopy. Given the mechanism of the electron transfer system, we verified and mainly emphasized the importance of porosity and interfacial properties of porous polymer films for memristor. As expected, the as-fabricated memristors exhibit good performance on low turn-on voltage (0.65 ± 0.10 V), reliable data storage, and high on/off current ratio (104). This work offers inspiration for applying POPs in the form of electropolymerized films in various advanced semiconductor-related devices.

Hardness Distribution and Growth Behavior of Micro-Arc Oxide Ceramic Film with Positive and Negative Pulse Coordination.

Micro-arc oxidation (MAO) is a promising technology for enhancing the wear resistance of engine cylinders by growing a high hardness alumina ceramic film on the surface of light aluminum engine cylinders. However, the positive and negative pulse coordination, voltage characteristic signal, hardness distribution characteristics of the ceramic film, and their internal mechanism during the growth process are still unclear. This paper investigates the synergistic effect mechanism of cathodic and anodic current on the growth behaviour of alumina, dynamic voltage signal, and hardness distribution of micro-arc oxidation film. Ceramic film samples were fabricated under various conditions, including current densities of 10, 12, 14, and 16 A/dm2, and current density ratios of cathode and anode of 1.1, 1.2, and 1.3, respectively. Based on the observed characteristics of the process voltage curve and the spark signal changes, the growth of the ceramic film can be divided into five stages. The influence of positive and negative current density parameters on the segmented growth process of the ceramic film is mainly reflected in the transition time, voltage variation rate, and the voltage value of different growth stages. Enhancing the cathode pulse effect or increasing the current density level can effectively shorten the transition time and accelerate the voltage drop rate. The microhardness of the ceramic film cross-section presents a discontinuous soft-hard-soft regional distribution. Multiple thermal cycles lead to a gradient differentiation of the Al2O3 crystal phase transition ratio along the thickness direction of the layer. The layer grown on the outer surface of the initial substrate exhibits the highest hardness, with a small gradient change in hardness, forming a high hardness zone approximately 20-30 μm wide. This high hardness zone extends to both sides, with hardness decreasing rapidly.

Cu thin film growth on stepped Si substrate: Effects of incident energy and thermal annealing

The existence of defects on the substrate surface is unavoidable and has a significant impact on the determination of surface properties. Among the prevalent types of defects, steps play an important role. In this study, molecular dynamics simulations are employed to explore the growth process of a thin film of Cu on a Si (001) substrate with a step. This research investigates how incident energy and thermal annealing affect the growth mode, surface roughness, film-substrate interface, and dislocation evolution. The results indicate that during the initial stage of the growth, the nucleation phenomenon was observed on terraces. The simulation indicates that the Cu atoms occur in an island growth mode on the stepped substrate. It is found that when the incident energy is increased and thermal annealing is performed, the surface curvature and roughness are reduced. Furthermore, the intermixing thickness at the interface increases due to the variation of the incidence energy. A dislocation analysis revealed that some dislocations disappeared before and after annealing, and a perfect dislocation appeared by increasing the incident energy.

A new method for characterizing the atomic composition distribution and interface structure of ultrathin multilayer films using molecular dynamics simulation assisted ARXPS

Characterizing ultrathin multilayer films' atom distribution and interface structure remains challenging. This paper innovatively characterized the chemical composition and distribution of Pt/Co/W ultrathin multilayer films by ARXPS. Molecular dynamics simulated the growth process of films to correspond to that in experiment. The results show that through ARXPS, the actual structure of Pt (2 nm)/Co (t = 0.5–3 nm)/W (2 nm) film could be obtained. For Pt (2 nm)/Co (2 nm)/W (2 nm) film, the actual structure was Pt/Co (1.73 nm)/W (0.78 nm)/WO3 + WO2 (1.48 nm). W at the top layer significantly diffused to the bottom layers, and oxidized W reduced from the surface to the interior of multilayer films. Molecular dynamics simulation confirmed that the interdiffusion degree of Co and W atoms was improved with the increase of Co atoms. The growth modes of Co and W layers were respectively layer-by-layer and island. As the number of Co atoms increased, the relative surface roughness of Co and W layers and the relative interface roughness of Co/W were increased. The in-plane magnetic anisotropy and coercivity were respectively enhanced and decreased due to the change in the surface/interface structure. This paper provides a new idea for analyzing ultrathin multilayer films' atom distribution and interface structure.

Effect of Al3+ on the surface microstructure and film formation mechanism of Zr-based conversion coatings with improved corrosion resistance performance on cold rolled steel

Most Zr conversion coatings are prepared on Al alloys, with Al3+ from the substrate contributing significantly to the film growth process. Thus, the effect of Al3+ on the electrochemical characteristics, surface microstructure and film-formation mechanism of Zr-based conversion coatings on old- rolled steel (CRS) substrates was investigated by growing the coatings with and without Al3+ as an additive. Electrochemical tests indicated that the anticorrosion performance of the Zr-Al coatings prepared in the presence of Al3+ was greatly superior to that of Zr conversion coatings obtained in the absence of Al3+. Field-emission scanning electron microscopy and X-ray photoelectron spectroscopy analysis indicated that adding of Al3+ in the conversion bath changed the surface microstructure of the Zr coating, greatly promoted the deposition of Zr and F on the CRS substrate and increased the film thickness and density. Both coatings were embedded into the etched CRS substrates. The presence of Al3+ additive induced the formation of different coating components. The Zr coating mainly consisted of ZrO2 and some FeFx, whereas the Zr-Al coatings comprised of ZrO2, ZrOxFy, Al2O3, AlFx and some FeFx. The present study results confirm the key role of Al3+ as an additive in the film formation and growth process of Zr coatings and its effect on enhancing the anticorrosion performance of CRS substrates in NaCl solutions.

Millisecond X-ray reflectometry and neural network analysis: unveiling fast processes in spin coating.

X-ray reflectometry (XRR) is a powerful tool for probing the structural characteristics of nanoscale films and layered structures, which is an important field of nanotechnology and is often used in semiconductor and optics manufacturing. This study introduces a novel approach for conducting quantitative high-resolution millisecond monochromatic XRR measurements. This is an order of magnitude faster than in previously published work. Quick XRR (qXRR) enables real time and in situ monitoring of nanoscale processes such as thin film formation during spin coating. A record qXRR acquisition time of 1.4 ms is demonstrated for a static gold thin film on a silicon sample. As a second example of this novel approach, dynamic in situ measurements are performed during PMMA spin coating onto silicon wafers and fast fitting of XRR curves using machine learning is demonstrated. This investigation primarily focuses on the evolution of film structure and surface morphology, resolving for the first time with qXRR the initial film thinning via mass transport and also shedding light on later thinning via solvent evaporation. This innovative millisecond qXRR technique is of significance for in situ studies of thin film deposition. It addresses the challenge of following intrinsically fast processes, such as thin film growth of high deposition rate or spin coating. Beyond thin film growth processes, millisecond XRR has implications for resolving fast structural changes such as photostriction or diffusion processes.