Metalorganic Chemical Vapor Deposition Process Research Articles

Numerical Analysis of an Inline Metal-Organic Chemical Vapour Deposition Process Based on Sliding-Mesh Modelling

The flow behaviour under the influence of susceptor moving speed is a key factor for the fabrication of high-quality cadmium telluride (CdTe) thin films during the inline metal-organic chemical vapour deposition (MOCVD) process. The main purpose of this paper is to find a method to study the real-time dynamics of transport phenomena inside the reactor. The sliding mesh method is thus proposed and its feasibility is evaluated using computational fluid dynamics (CFD) modelling. A computational grid with 173,400 hexahedral cells is adopted through a grid sensitivity test validation. The simulations show that comparing to 2D modelling, the results of 3D modelling are found to be in good agreement with the experimental data for the temperature range of 628–728 K. Based on the velocity field, the temperature field and distribution of species concentration under different sampling time intervals of 60, 180 and 300 s, the thin film uniformity on both edges of the substrate is found to be influenced by the side effect of the baffle plate. The mass deposited on the substrate is further investigated under different susceptor moving speeds from 0.75 to 2.25 cm/min, and a moving speed between 0.75 to 1.13 cm/min is found to be effectively beneficial to the deposition process.

Invisible Surface Oxygen Vacancies in a Thin MgO Film: Impacts on the Chemical Activity and Secondary Electron Emission.

Today, Fs defects in MgO as isolated surface neutral oxygen vacancies are in the focus of surface science, catalysis research, and emission coating of microchannel plates. With the 10-4 atom % content at 750 K and under pO2 = 10-9 Torr, estimated by us from the known equilibrium T-x and p-T-x diagrams of MgO, Fs defects remain invisible or difficult-to-detect objects. The MgO(100) → MgO(100) + Fs + 1/2O2 phase transition was studied in MgO films deposited by the metal-organic chemical vapor deposition (MOCVD) procedure from the mixed-ligand Mg precursor on Si substrates at 725 K in the O2 flow where the nonstoichiometric phase (MgO/Fs) is formed in the gas medium containing simultaneous H2, CO, H2O, CO, and O2 species in unbalanced concentrations. Realization of the above transition was proven theoretically and experimentally through kinetic-thermodynamic analysis of the nonequilibrium system with revealing thermodynamic motive forces, i.e., the positive enthalpy and entropy, as well as through a new combination of diagnostic methods including the original differential dissolution method, due to which separate determination of the point and morphological defects was achieved. It was found that Fs defects occur when oxygen in the immediate vicinity to the substrate surface is replaced practically completely by the oxidized products of the precursor and the resulting oxygen pressure becomes enough for this process. The 90 mass % of the as-deposited MgO-film-involved (MgO/Fs) phase; its chemical activity is demonstrated through dissolution in hot water, while the electron donor activity is through 9 at 750 eV secondary electron yield. A good understanding of gas-phase reactions between the precursors and oxygen provides the fundamental basis of the MOCVD process to deposit MgO films that are dense, free from carbon, and of homogeneous texture. This makes the MOCVD process suitable also for use as coatings of microchannel plates.

Microstructural Investigation and On-Site Repair of Thin Pd-Ag Alloy Membranes.

Pd membranes act in an important role in H2 purification and H2 production in membrane reactors. Pd-Ag alloy membranes fabricated by consecutive electroless- and electroplating process on alumina tubes exhibited good stability under stringent heating/cooling cycles at a ramp rate of 10 K/min, imitating practical fast initiation or emergency shutdown conditions. Bilayer Pd-Ag membranes can form dense and uniform alloy after thermal treatment for 24 h at 823 K under H2 atmosphere, despite a porous structure due to the development of liquid-like properties above Tamman temperature to enforce the migrativity. On the contrary, alloying under N2 atmosphere resulted in a Pd-enriched layer. This led to a lower H2 flux but superior thermal stability compared to that alloying under H2 atmosphere. The trilayer approach of electroless-plated Pd, electro-polated Ag and electroless-plated Pd is not suitable to achieve homogeneous Pd-Ag alloys, which, on the other hand, presented the occurrence of a small gap between top Pd layer and middle Ag layer, probably due to insufficient wetting during plating process. An on-site repair treatment in analogous to MOCVD (Metal-organic Chemical Vapor Deposition) process was first proposed to extend the lifetime of Pd-Ag membrane, i.e., by vaporizing, and subsequent decomposition of Ag(OOCC2F5) powders to “preferentially” block the pinholes under vacuum and at working temperature of ca. 473–673 K, which effectively reduced the N2 flux by 57.4% compared to the initial value. The H2 flux, however, declined by 16.7% due to carbon deposition on the membrane surface, which requires further investigation. This approach shows some potential for on-site repair without disassembly or cooling to room temperature.

High-Throughput Growth of Wafer-Scale Monolayer Transition Metal Dichalcogenide via Vertical Ostwald Ripening.

For practical device applications, monolayer transition metal dichalcogenide (TMD) films must meet key industry needs for batch processing, including the high-throughput, large-scale production of high-quality, spatially uniform materials, and reliable integration into devices. Here, high-throughput growth, completed in 12 min, of 6-inch wafer-scale monolayer MoS2 and WS2 is reported, which is directly compatible with scalable batch processing and device integration. Specifically, a pulsed metal-organic chemical vapor deposition process is developed, where periodic interruption of the precursor supply drives vertical Ostwald ripening, which prevents secondary nucleation despite high precursor concentrations. The as-grown TMD films show excellent spatial homogeneity and well-stitched grain boundaries, enabling facile transfer to various target substrates without degradation. Using these films, batch fabrication of high-performance field-effect transistor (FET) arrays in wafer-scale is demonstrated, and the FETs show remarkable uniformity. The high-throughput production and wafer-scale automatable transfer will facilitate the integration of TMDs into Si-complementary metal-oxide-semiconductor platforms.

Vapor phase epitaxy of antimonene-like nanocrystals on germanium by an MOCVD process

Synthetic two-dimensional (2D) mono-elemental crystals, namely X-enes, have recently emerged as a new frontier for atomically thin nanomaterials with on-demand properties. Among X-enes, antimonene, the β-phase allotrope of antimony, is formed by atoms arranged in buckled hexagonal rings bearing a comparatively higher environmental stability with respect to other players of this kind. However, the exploitation of monolayer or few-layer antimonene and other 2D materials in novel opto-electronic devices is still hurdled by the lack of scalable processes. Here, we demonstrated the viability of a bottom-up process for the epitaxial growth of antimonene-like nanocrystals (ANCs), based on a Metal-Organic Chemical Vapor Deposition (MOCVD) process, assisted by gold nanoparticles (Au NPs) on commensurate (111)-terminated Ge surfaces. The growth mechanism was investigated by large- and local-area microstructural analysis, revealing that the etching of germanium, catalyzed by the Au NPs, led to the ANCs growth on the exposed Ge (111) planes. As a supportive picture, ab-initio calculations rationalized this epitaxial relationship in terms of compressively strained β-phase ANCs. Our process could pave the way to the realization of large-area antimonene layers by a deposition process compatible with the current semiconductor manufacturing technology.

Point Defect‐Induced UV‐C Absorption in Aluminum Nitride Epitaxial Layers Grown on Sapphire Substrates by Metal‐Organic Chemical Vapor Deposition

Herein, the optical properties of aluminum nitride (AlN) epitaxial layers grown on sapphire substrates by metal‐organic chemical vapor deposition (MOCVD) are reported. The structures investigated in this study are grown at highly different degrees of supersaturation in the MOCVD process. In addition, both pulsed and continuous growth conditions are employed and AlN is deposited on nucleation layers favoring different polarities. The samples are investigated by photoluminescence (PL), photoluminescence excitation (PLE), and absorption spectroscopy and are found to vary significantly in absorption and emission characteristics. Two distinct absorption bands in the UV‐C spectral range are observed and examined in greater detail, with either giving rise to a significant absorption coefficient of around 1000 cm−1. The corresponding defect transitions are identified by PL spectroscopy. Combined with secondary‐ion mass spectrometry (SIMS) measurements, these absorption bands are allocated to the incorporation of carbon and oxygen impurities, depending on the applied growth conditions. Furthermore, similarities with other epitaxial growth techniques serving as basis for UV‐C applications are highlighted. These results are highly relevant for a better understanding of absorption issues in AlN templates grown by various deposition techniques. In addition, consequences for the growth of efficient UV‐C devices by MOCVD on sapphire substrates are outlined.

Thin CdTe Layers Deposited by a Chamberless Inline Process using MOCVD, Simulation and Experiment

The deposition of thin Cadmium Telluride (CdTe) layers was performed by a chamberless metalorganic chemical vapour deposition process, and trends in growth rates were compared with computational fluid dynamics numerical modelling. Dimethylcadmium and diisopropyltelluride were used as the reactants, released from a recently developed coating head orientated above the glass substrate (of area 15 × 15 cm2). Depositions were performed in static mode and dynamic mode (i.e., over a moving substrate). The deposited CdTe film weights were compared against the calculated theoretical value of the molar supply of the precursors, in order to estimate material utilisation. The numerical simulation gave insight into the effect that the exhaust’s restricted flow orifice configuration had on the deposition uniformity observed in the static experiments. It was shown that > 59% of material utilisation could be achieved under favourable deposition conditions. The activation energy determined from the Arrhenius plot of growth rate was ~ 60 kJ/mol and was in good agreement with previously reported CdTe growth using metalorganic chemical vapour deposition (MOCVD). Process requirements for using a chamberless environment for the inline deposition of compound semiconductor layers were presented.

Tin(II) Aminothiolate and Tin(IV) Aminothiolate Selenide Compounds as Single-Source Precursors for Tin Chalcogenide Materials.

Tin aminothiolate compounds SnII(dmampS)2 (1) and SnIV(dmampS)2Se (2), where dmampS = 1-(dimethylamino)-2-methylpropane-2-thiolate, were synthesized. The molecular structures of 1 and 2 reveal a seesaw and distorted trigonal-bipyramidal geometry, respectively. The 1H NMR spectrum of 1 shows two types of resonances for the methyl groups of the α-carbon, methyl groups of the amino groups, and methylene groups at room temperature. On the other hand, the 1H NMR spectrum of 2 exhibits a single resonance for each of these groups. According to variable-temperature 1H NMR analysis, each of these two types of resonances occurring at relatively low temperatures (under 223 K for 1 and under 333 K for 2) are merged as a single resonance with increasing temperature. By using thermogravimetric and thermal decomposition analyses, the residual materials of compounds 1 and 2 are confirmed to be SnS and SnSSe, respectively. Compound 1 was subjected to a metal-organic chemical vapor deposition process, which allowed for the deposition of a dense and well-faceted orthorhombic phase SnS thin film on a SiO2/Si substrate with ∼200 nm thickness.

The Influence of AlN Nucleation Layer on Radio Frequency Transmission Loss of AlN‐on‐Si Heterostructure

Reducing radio frequency (RF) transmission loss is a key requirement when fabricating GaN‐on‐Si RF devices. To get a better insight into the RF loss mechanism in the GaN‐on‐Si structure, the RF loss of an AlN/Si template is investigated by varying the growth temperature of AlN during a metalorganic chemical vapor deposition process. The results show that the RF loss of the AlN/Si template is dominated by the interface loss due to the p‐type conductive channel at the AlN/Si interface, which is induced by the thermal diffusion of Al during the high‐temperature growth. Although a low growth temperature of the AlN nucleation layer can suppress the RF loss in the AlN/Si template, it results in a low crystalline quality of AlN for practical use. Optimizing the growth temperature of the AlN nucleation layer is essential to obtain a good balance between the crystalline quality, morphological quality, and RF loss such that the AlN/Si template is suitable for epitaxial growth of the complete GaN‐on‐Si RF device structure.

Violet Light-Emitting Diodes Based on p-CuI Thin Film/n-MgZnO Quantum Dot Heterojunction.

As the lighting technology evolves, the need for violet light-emitting diodes (LEDs) is growing for high color rendering index lighting. The present technology for violet LEDs is based on the high-cost GaN materials and metal-organic chemical vapor deposition process; therefore, there have recently been intensive studies on developing low-cost alternative materials and processes. In this study, for the first time, we demonstrated violet LEDs based on low-cost materials and processes using a p-CuI thin film/n-MgZnO quantum dot (QD) heterojunction. The p-CuI thin film layer was prepared by an iodination process of Cu films, and the n-MgZnO layer was deposited by spin-coating presynthesized n-MgZnO QDs. To maximize the performance of the violet LED, an optimizing process was performed for each layer of p- and n-type materials. The optimized LED with 1 × 1 mm2-area pixel fabricated using the p-CuI thin film at the iodination temperature of 15 °C and the n-MgZnO QDs at the Mg alloying concentration of 2.7 at. % exhibited the strongest violet emissions at 6 V.

Fabrication of ordered Sb–Te and In–Ge–Te nanostructures by selective MOCVD

The controlled growth of chalcogenide nanoscaled phase change material structures can be important to facilitate integration and to enable complex architectures for phase change memory and other microelectronic applications. Here, the growth of Sb–Te and In–Ge–Te alloys by metal–organic chemical vapour deposition (MOCVD) on patterned substrates featured with an array of recesses (~130 nm features width) was investigated. High selectivity, with preferential growth on a CoSi2 metallic layer at the recess bottom with respect to the surrounding SiO2 masking layer, was obtained, leading to a single-step fabrication of arrays of high-aspect-ratio chalcogenide nanostructures. The growth selectivity, as well as the morphology, composition and microstructure of the grown nanostructures, as a function of the different MOCVD process parameters, were investigated by scanning electron microscopy, transmission electron microscopy, energy dispersive x-ray spectroscopy, Raman spectroscopy and Fourier transformed infrared spectroscopy. Thanks to the chosen substrates, the synthesized nanostructures were also directly electrically accessible, as proved by conductive-atomic force microscopy.

A new metalorganic chemical vapor deposition process for MoS2 with a 1,4-diazabutadienyl stabilized molybdenum precursor and elemental sulfur.

Molybdenum disulfide (MoS2) is known for its versatile properties and hence is promising for a wide range of applications. The fabrication of high quality MoS2 either as homogeneous films or as two-dimensional layers on large areas is thus the objective of intense research. Since industry requirements on MoS2 thin films can hardly be matched by established exfoliation fabrication methods, there is an enhanced need for developing new chemical vapor deposition (CVD) and atomic layer deposition (ALD) processes where a rational precursor selection is a crucial step. In this study, a new molybdenum precursor, namely 1,4-di-tert-butyl-1,4-diazabutadienyl-bis(tert-butylimido)molybdenum(vi) [Mo(NtBu)2(tBu2DAD)], is identified as a potential candidate. The combination of imido and chelating 1,4-diazadieneyl ligand moieties around the molybdenum metal center results in a monomeric compound possessing adequate thermal characteristics relevant for vapor phase deposition applications. Hexagonal MoS2 layers are fabricated in a metalorganic CVD (MOCVD) process with elemental sulfur as the co-reactant at temperatures between 600 °C and 800 °C. The structure and composition of the films are investigated by X-ray diffraction, high resolution transmission electron microscopy, synchrotron X-ray photoelectron spectroscopy and Raman spectroscopy revealing crystalline and stoichiometric MoS2 films. The new MOCVD process developed for MoS2 is highly promising due to its moderate process conditions, scalability and controlled targeted composition.

Formation of Erbia-Yttria double layer fabricated by metal organic chemical vapor deposition process with changing oxygen flow rates

Er2O3 and Y2O3 are promising materials for advanced breeding blanket system of nuclear fusion reactor because they have high electrical resistivity and effective tritium permeation suppression. In this report, Er2O3 thin films were fabricated by metal organic chemical vapor deposition (MO-CVD) process with changing oxygen flow rates on the stainless steel 316 (SUS316) substrate with Y2O3 layer fabricated via radio frequency (RF)-sputtering. Samples were prepared with four conditions of oxygen rate, 0.08, 0.13, 0.25, 0.42 Pa∙m3/s (50, 75, 150 and 250 sccm, respectively) and only on Er2O3 / Y2O3–0.42 Pa∙m3/s sample was added thermal cycles. Four samples were observed with using X-ray diffraction (XRD), atomic force microscopy (AFM) and transmission electron microscopy (TEM). Increasing oxygen flow rate during MO-CVD process increased the thickness of Er2O3 thin film and decreased columnar width and succeeded in fabricating Er2O3 thin film and dense microstructure on the SUS 316 substrate with Y2O3 layer.

Optimization of MOCVD Hardware Configuration and Process for Growth of High Quality (Gd,Y)BCO Superconducting Tapes Based on CFD Modeling

A systematic computational fluid dynamic (CFD) study was performed to investigate the effects of hardware configuration and process parameters on flow field and temperature profile above the film growth surface for (Gd,Y)BCO superconducting tapes in a metalorganic chemical vapor deposition (MOCVD) reactor. Significant improvement in the uniformity of flow field and temperature profile was achieved by optimizing the gap between showerhead and susceptor, showerhead length, gas flow rate, and chamber pressure. As results of the improvement in hardware configuration based on CFD modeling, high quality (Gd,Y)BCO superconducting films were achieved and the limit on growth rate was increased. The improvement was not only in the surface morphology (achieving more clean and smooth surface with less outgrowth grains and impurity phase particles), but also in the cross sectional microstructure view (more uniform from the bottom to the top) for thick films processed by the reel-to-reel MOCVD. A 1.76-μm-thick (Gd,Y)BCO film in a 284-m-long tape yielded a self-field critical current of 769 A/12 mm width at 77 K.

Epitaxial growth optimization of AlGaN/GaN high electron mobility transistor structures on 3C-SiC/Si

The excellent characteristics of high electron mobility transistors based on AlGaN/GaN heterostructures rely on the properties of the substrate used for their epitaxial growth. In this work, we evaluate 3C-SiC as an alternative to the commonly used 4H-SiC. Up to 2 μm thick 3C-SiC layers on Si templates have been used as substrates to develop an epitaxial growth process for high-quality AlGaN/GaN heterostructures. We demonstrate the deposition of up to 5 μm crack-free heterostructures on 2 μm thick 3C-SiC on Si by using a metalorganic chemical vapor deposition process. Several characteristics of these structures, such as crystal quality, morphology, and electrical properties, are close to what can be achieved when using 4H-SiC substrates. The results of this work motivate further development in order to obtain thicker and semi-insulating 3C-SiC layers to be used instead of the expensive and size-limited 4H-SiC substrates.

Study on the uniformity of ZnO films grown by MOCVD

Abstract This study reports the use of CFD simulation software to simulate the growth process in a ZnO-MOCVD reaction chamber. The results of the rate of ZnO deposition in the simulation were in good agreement with experimental results and the correlation coefficient in all cases indicates medium and high correlation, which verified the correctness of the theoretical model of the numerical simulation. A streamline diagram of the reaction chamber and the technicians’ observations of this growth show that the adjustment of the entrance of the source of MO is key to obtaining a substrate film of uniform thickness. In order to obtain a good film deposition rate, we created a neural network model combined with a genetic algorithm to optimize the entrance flow of the MO source and determined the optimal input process parameters for film uniformity. The optimization results and experiments were compared and analyzed to obtain satisfactory consistency. Following the optimization, the coefficient of variation decreased from 3.6% to 1.28%, which significantly improved the uniformity of film thickness of ZnO film. These results will provide a solution to process parameter adjustment and high-quality epitaxial growth in the metal-organic chemical vapor deposition process.

Co-MOCVD processed seed layer for through silicon via copper metallization

A novel metallization for vertical integration in microsystems technology using through-silicon-via (TSV) was investigated. Cobalt metal-organic chemical vapor deposition (Co-MOCVD) process is capable of forming an excellent conformal ultra-thin film with good adhesion to the copper conductive and diffusion barrier layers. Co layer as a seed layer provides a direct copper electrochemical deposition (Cu-ECD). The main challenge of this metallization module is to reduce Co corrosion under the influence of Cu electrolyte. Based on the experimental results, the optimized deposition recipes have been obtained and discussed by varying the ECD parameters, and characterizing the deposited films. Thereby, the Co corrosion was minimized even for the ultra-thin film of 5 nm.Metallization processes were performed on blank and structured samples (on both coupons and 300 mm wafers). Barrier films stack deposition and in-vacuo annealing were carried out without breaking the vacuum in the 300 mm cluster tool. Afterwards, ECD processes were accomplished on coupon level in a lab-scale plating cell. Moreover, different metrology, ex-situ characterizations and measurements were performed by time-of-flight secondary ion mass spectroscopy (ToF-SIMS), transmission electron microscopy (TEM), cross sectional scanning electron microscopy (XSEM) and x-ray reflectometry (XRR), for revealing thickness loss, corrosion percentage and elemental depth profile.

Stability Analysis of Multi Process Parameters for Metal-Organic Chemical Vapor Deposition Reaction Cavity.

The parameters for metal-organic chemical vapor deposition (MOCVD) processes significantly influence the properties of ZnO films, especially the flow stability of the chamber, which is caused by process parameters such as the shape of reaction chamber, the working pressure, the growth temperature, the susceptor rotational speed, the gas flow rate, and the nature of the carrier gas at inlet temperature. These parameters are the preconditions for the formation of high-quality film. Therefore, this study uses Ar as a carrier gas, diethylzinc (DEZn) as a Zn source, and H2O as an oxygen source and adopts the reaction mechanism calculated by quantum chemistry, which includes ten gas reactions and eight surface reactions. The process parameters of a specific reaction chamber model were analyzed based on the computational fluid dynamics method. This study also presents an accurate prediction of the flow regime in the reactor chamber under any operating conditions, without additional experiments, based on an analysis of a great quantity of simulation data. Such research is also significant for selecting the growth parameters relevant to production, providing a specific process growth window, narrowing the debugging scope, and providing a theoretical basis for the development of MOCVD equipment and process debugging.

Validation of a Terminally Amino Functionalized Tetra‐Alkyl Sn(IV) Precursor in Metal–Organic Chemical Vapor Deposition of SnO2 Thin Films: Study of Film Growth Characteristics, Optical, and Electrical Properties

AbstractTin(IV) oxide is a promising semiconductor material with leading‐edge properties toward chemical sensing and other applications. For the growth of its thin films, metal–organic chemical vapor deposition (MOCVD) routes are advantageous due to their excellent scalability and potential to tune processing temperatures by careful choice of the reactants. Herein, a new and highly efficient MOCVD process for the deposition of tin(IV) oxide thin films employing a terminally amino alkyl substituted tin(IV) tetra‐alkyl compound is reported for the first time. The liquid precursor, tetrakis‐[3‐(N,N‐dimethylamino)propyl] tin(IV), [Sn(DMP)4], is thermally characterized in terms of stability and vapor pressure, yielding highly pure, polycrystalline tin(IV) oxide thin films with tunable structural and morphological features in the presence of oxygen. Detailed X‐ray photoelectron spectroscopy (XPS) analysis reveals the presence of oxygen vacancies and high amounts of chemisorbed oxygen species. Based on these promising features, the MOCVD process is optimized toward downscaling the thickness of tin(IV) oxide films from 25 to 50 nm to study the impact of incipient surface morphological changes occurring after initial thin‐film formation on the electrical properties as investigated by van der Pauw (vdP) resistivity measurements. Optical bandgaps of thin films with varying thicknesses are estimated using ultraviolet–visible (UV–vis) spectroscopy.

High Rate Growth of MOCVD-Derived GdYBCO Films Based on a Simple Self-Heating Method

The home-designed metal organic chemical vapor deposition (MOCVD) system was applied to prepare the Gd0.5Y0.5Ba2Cu3O7-δ (GdYBCO) films at a high deposition rate in order to improve the production efficiency and reduce the preparation cost of high temperature superconducting tapes. Based on a simple self-heating method, the distance between the shower head and the substrate surface can be reduced effectively to increase the concentration of metal organic sources on the substrate surface, which can commendably improve the deposition rate of GdYBCO films and the utilization ratio of metal organic sources. At last, the GdYBCO films were successfully prepared on the LaMnO3 template at the high deposition rate of 1 μm/min by the MOCVD process based on the simple self-heating method and the critical current (Ic) was more than 220 A/cm-width (77 K, 0 T), corresponding to the critical current density (Jc) more than 4.4 MA/cm2 (77 K, 0 T).