Plasma Chemical Vapor Deposition Reactor Research Articles

Formation of Diamond Films with Different Grain Sizes on TiO2 Nanotubes and Its Field Emission Properties

Diamond films with different grain sizes are deposited on TiO2 nanotube (TNT) arrays prepared by anodic oxidation using a microwave plasma chemical vapor deposition reactor. The scanning electron microscope, X‐Ray diffractometer, and Raman results indicate that the diamond film is successfully deposited and that the substrate undergoes a phase transition due to the diamond deposition temperature, resulting in the rutile phase becoming dominant with lower energy bandgap and work function. Notably, after 5 h of deposition, a relatively continuous microcrystalline film is formed on the TNTs, and the diamond grains change from spherical to pyramidal and show excellent electron field emission behavior, with a low turn‐on field of 0.5 V μm−1 and a current density of 85.9 μA cm−2. In addition, the deposition environment of the nanocrystalline diamond has a large impact on the substrate morphology, resulting in a blocked electron transport path, which reduces the overall field emission performance. The enhanced performance is attributed to the synergistic effect between the highly efficient 1D electron path of the TNTs, the negative electron affinity of the diamond surface, and the lower work function of rutile TiO2.

Deposition of uniform diamond films on three dimensional Si spheres by using faraday cage in MPCVD reactor

Deposition of a consistent diamond coating on intricate surfaces has historically posed a difficulty. This article presents the advancement in research on depositing a uniform diamond coating on three-dimensional (3D) silicon spheres, utilizing a faraday cage within a microwave plasma chemical vapor deposition (MPCVD) reactor. A self-consistent three-dimensional multi-physics field model has been established for simulating the microwave electric field and plasma inside a reactor with or without a faraday cage. Results indicate the cage effectively reduces the discharge at the top of the silicon sphere and improves uniformity of the distribution of the microwave electric field and plasma electron density on the sphere's surface. MPCVD trials have demonstrated that a powerful discharge takes place at the apex of the silicon sphere resulting in an excessive thermal gradient if the cage is not added. The apex of the silicon sphere is covered with a blend of diamond and graphite phases. Due to the excessive internal stress of the coating, approximately 50 % of the samples experience coating detachment. After the addition of the cage, the strong discharge is transferred to the top of the cage, effectively suppressing the microwave electric field and plasma inside the cage. Improved quality, reduced internal stress, and enhanced uniformity of the polycrystalline diamond coating are achievable on the silicon spheres within the cage. Moreover, this technique offers a novel approach to coat diamond on complex 3D geometries.

Effect of boron doping levels on the microstructure and characteristics of high-quality boron-doped diamond electrodes prepared by MPCVD

In order to fully understand the relationship between boron doping level and material characteristics, a series of high-quality boron-doped diamond (BDD) electrodes with different boron doping levels (B/C ratios = 1000–5000 ppm) were prepared on a silicon substrate using a self-designed microwave plasma chemical vapor deposition (MPCVD) reactor in this study. The relationship between surface morphology, structural composition, chemical bonding state, electrical conductivity and electrochemical properties of BDD electrodes was investigated systematically. With the increase of boron doping level, the grain size of the BDD electrode tends to decrease, the crystal orientation tends to be dominated by (111) orientation, the conductivity increases sharply and then gradually stabilizes, while the width of the potential window tends to decrease (4.39 V to 3.95 V from 1000 ppm to 5000 ppm), and the reversibility and stability of the electrode improves significantly. In addition, such high-quality BDD electrodes also exhibit a higher sensitivity (0.1176 μAμM−1 cm−2) and lower limit of detection (0.276 μM) in the detection of dopamine. The boron doping level in BDD electrodes plays a prominent role in material characteristics such as surface morphology, structural composition, chemical bonding state, electrical conductivity and electrochemical properties. Despite the challenging synthesis of pure sp3 carbon materials at high boron doping levels, the BDD electrodes prepared in this study exhibit high quality without sp2 defects even with high boron doping levels, and possess extremely low resistivity (~10−3 Ω·cm) and a wide electrochemical potential window (~4 V), which has not been achieved in other previous research works and offer great potential in the electrochemical applications of BDD electrodes.

Practical finite-time command filtered backstepping control of MPCVD reactor systems with uncertainties

A practical finite-time command filtered backstepping control method is proposed in this paper for a microwave plasma chemical vapor deposition (MPCVD) reactor system. The MPCVD reactor system is modeled as a coupled nonlinear system with unknown control direction functions and unknown nonlinearities. To address the unknown nonlinearities, novel practical finite-time command filters are proposed to construct the estimations of such nonlinearities. On the other hand, an equivalent augmented system of the reactor system is proposed to address the design challenges that posed by the system unknown control direction functions. Additionally, it can be concluded that the proposed control method ensures practical finite-time stability of the reactor system tracking errors by using the practical finite-time Lyapunov stability criterion. Finally, the effectiveness of the approach is demonstrated through the simulation results.

Event-triggered adaptive NN practical finite-time control with its application to MPCVD reactors

The practical finite-time control problem of uncertain nonlinear systems is investigated in this paper. To address the uncertain nonlinearities of the system, neural networks are introduced to approximate the lumped nonlinearities containing the system unknown functions. On the other hand, to alleviate the signal transmission pressure of the system, an improved event-triggered mechanism is presented to reduce the controller update frequency without degrading the control performance of the system. By using practical finite-time stability, it is obtained that the system tracking errors are practical finite-time stable without Zeno behavior. Finally, the effectiveness of the proposed method is verified by the simulation results of its application to a microwave plasma chemical vapor deposition (MPCVD) reactor system.

Improved adaptive backstepping control of MPCVD reactor systems with non-parametric uncertainties

This paper presents an improved adaptive backstepping control strategy for a microwave plasma chemical vapor deposition (MPCVD) reactor system. To describe the dynamics of the reactor system, a non-parametric uncertain nonlinear system model with unknown control direction functions is built up. In order to deal with the non-parametric uncertainties of the system, direct adaptive laws are primarily proposed to estimate such uncertainties, which is superior to traditional adaptive backstepping that can only address parametric uncertainties. Moreover, an equivalence transformation of the system is given to address the system unknown control direction functions. By using Lyapunov stability criterion, it can be proved that the target signals (desired temperature, desired pressure, and desired gas flow rates) are tracked by the reactor system outputs with small errors. Finally, simulation results are given to demonstrate the effectiveness of the proposed control method.

Design and simulation of a novel MPCVD reactor with three-cylinder cavity

A novel microwave plasma chemical vapor deposition (MPCVD) reactor with three-cylinder cavity and outstanding tuning capability was proposed. The electric field and plasma in the reactor were simulated, and four geometric parameters were optimized. After optimization, the electric field intensity above the substrate exceeded 5×103V/m (input power of 1 W), which was 1.6 times that of the similar cylindrical reactors. Only one strong plasma formed above the substrate surface with an input power of 5 kW once the gas pressure exceeds 8 kPa. But the plasma coverage area was decreased with the increase of the gas pressure. The plasma coverage area could be restored by adjusting the height difference between the adjusting mechanism 1 and 2. The frequency detuning caused by the microwave frequency changes also could be returned by adjusting the adjusting mechanisms. The subsequent experimental results showed that uniform and high-quality diamond films could be deposited under the simulation condition (5 kW and 12 kPa). It could verify the accuracy of the simulation and the excellent performance of the new MPCVD reactor.

Preparation of single-crystal diamond for Small Angle X-ray Scattering in situ loading test

A 2.45 GHz/6 kW cylindrical cavity type microwave plasma chemical vapor deposition reactor was used for the growth of high optical quality single-crystal diamonds. The effects of growth temperature on the surface morphology and crystal quality and the optical properties of the synthesized diamond were studied using optical microscopy, XRD rocking curve, Raman spectroscopy, photoluminescence spectroscopy, Small Angle X-ray Scattering and X-ray topography. Diamond single crystal of the size of Φ7 × 0.5 mm3 were obtained at 1000 °C in a pocket holder with the average growth rate of 7.5 um/h. X-ray rocking curve of the sample was 32 arcsec, while the X-ray transmittance was over 80%. There were no evident NV defects peak in PL. After high pressure blasting test, the diamond windows prepared at 1000 °C can also withstand the pressure of 27 MPa. All these performances were suitable for the windows which was applied on Small Angle X-ray Scattering in situ loading test. Design of a device for Small Angle X-ray Scattering in situ loading test was demonstrated. The device was convenient for the research of material structural changes under high pressure.

Epitaxial lateral growth of single-crystal diamond under high pressure by a plate-to-plate MPCVD

The epitaxial lateral growth of single-crystal diamond (SCD) using a plate-to-plate microwave plasma chemical vapor deposition (MPCVD) reactor under high pressure is investigated. The radicals’ distribution in H2/CH4 plasma as a function of pressure was locally detected by optical emission spectroscopy (OES). Raman spectroscopy and optical microscope were employed to analyze the properties of SCD deposited in different pressure. The OES results show that radicals’ distribution along the substrate direction is symmetrical under 20 kPa pressure. The symmetrical distribution of radicals at 20 kPa is in favor of epitaxial lateral growth SCD around the seed and without polycrystalline diamond (PCD) rim. When the pressure is increased to 21.5 kPa, the optical emission spectra center of plasma shifts close to the microwave reflector where is far away from the microwave source. The contact state between the diamond seed and the plasma is deteriorated and the PCD rim occurs in the plasma uncovered area. While the epitaxial lateral growth pattern occurs in the plasma covered area and the lateral growth rate of this region improves with the increase of pressure. A higher growth rate does not result in good quality; meanwhile, the diamond growth step spacing and direction become inconsistent in the transition zone as a function of pressure increasing. Finally, the overall effective lateral expansion area does not increase with the improvement of pressure. Therefore, the uniform and symmetrical distributed plasma is more conducive to the epitaxial lateral growth of SCD, and the effective expansion growth SCD can be realized at 20 kPa.

Temperature stabilization of WC-Co cutting inserts with feedback to IR pyrometer upon growth of multilayer diamond coatings by microwave plasma chemical vapor deposition

We produced microcrystalline diamond coatings with nanocrystalline top diamond layer on WC-Co cutting inserts in a microwave plasma (2.45 GHz) chemical vapor deposition reactor. The coatings have a high uniformity of the substrate surface owing to elimination of the plasma edge effect by application of a moveable quartz ring above the substrate holder. Computer modeling showed how the positioning of the ring changes the electromagnetic field around the substrates. A new approach was used to stabilize the temperature of the cutting inserts during the coating process, which is based on in situ control of the quartz ring position by proportional-integral-differential (PID) regulation. The coatings have been characterized with microRaman spectroscopy in a mapping mode in cross section of the samples. Depth profiles of diamond Raman peak position and width are demonstrated and the stress in the films is estimated, the minimum stress being determined for the cutting insert apex.

Tetramethysilane-assisted enhancement of diamond nucleation on silicon substrate

This paper describes the effect of tetramethylsilane (TMS) on diamond nucleation on Si substrate under an applied bias voltage of 120 V, performed in a modified microwave plasma chemical vapor deposition (MPCVD) reactor. The introduction of TMS in the CH4/H2 plasma leads to a significant enhancement of nucleation density of diamond nuclei, namely from (3.7 ± 0.2) × 107/cm2 without the introduction of TMS to (4.7 ± 0.5) × 1010/cm2 at the TMS flow rate of 4 sccm. On the contrary, further increasing in the TMS flow rate to 8 sccm slightly reduces the nucleation density of diamond nuclei to (2.1 ± 0.3) × 1010/cm2, along with the increase in average size of diamond nuclei. High-resolution transmission electron microscopy (HRTEM) and X-ray photoelectron spectroscopy (XPS) allow us to study the microstructural and chemical composition evolution of Si/diamond interface. The obtained results suggest that bias-enhanced nucleation of diamond on Si substrate exhibits a direct relationship with the TMS flow rate.

Microstructural modification of diamond-graphite nanohybrid films via adjusting deposition temperatures for enhanced electron field emission

To achieve enhanced electron field emission, diamond-graphite nanohybrid films are deposited on Si substrates by means of a microwave plasma chemical vapor deposition (MPCVD) reactor. Liquid diethylamine is used as a sole reactive source. An increase of deposition temperature from 730 °C to 830 °C leads to remarkable changes of morphology and microstructure of diamond-graphite nanohybrid films, namely from a typical planar ultrananocrystalline diamond (UNCD) film at 730 °C to a novel nanocrystalline diamond/graphene nanowall (ND/GNW) film at 830 °C. The electrical conductivity of a ND/GNW film is measured to be 762.4 Ω−1·cm−1, while for a UNCD film it is 18.0 Ω−1·cm−1. Moreover, the electron field emission is significantly enhanced on a ND/GNW film. With an applied electrical field of 9.9 V μm−1 its emission current density is 1.6 mA cm−2, 8-time larger than that for a UNCD film. The possible electron emission mechanism is then discussed based on the Fowler-Nordheim theory. This work offers a simple way to alter effectively the microstructures of sp2/sp3 nanohybrid films that benefit greatly to develop carbon-based field emission cold cathodes featuring high performance.

A 915 MHz/75 kW cylindrical cavity type microwave plasma chemical vapor deposition reactor with a ladder-shaped circumferential antenna developed for growing large area diamond films

A 915MHz/75kW cylindrical cavity type microwave plasma chemical vapor deposition reactor was set up by scaling a 2.45GHz TM021 mode microwave resonant cavity. The new reactor retains a cylindrical geometry, which makes it possible to set up an adjustment mechanism for plasma distribution in the reactor during its operation. In addition, a ladder-shaped circumferential antenna was used as the microwave coupling mechanism, so that sealing reliability of the deposition chamber and high power capability of the reactor are ensured. Experimentally, 3–5inch diameter crack-free diamond films were prepared. The pressure was set at between 15 and 20kPa and input power used was between 40 and 60kW, respectively. Growth rate of diamond films ranged between 1.6 and 5.6μm/h for different size and quality materials, with deviations in thickness within a range of about ±4% and ±8% over 3 and 5inch areas. Morphology, crystalline quality as well as purity of the diamond films were characterized by using optical microscopy, Raman and photoluminescence spectra, and the results proved that the quality and the purity of the diamond films were excellent.

Novel Diamond Films Synthesis Strategy: Methanol and Argon Atmosphere by Microwave Plasma CVD Method Without Hydrogen.

Diamond thin films are grown on silicon substrates by only using methanol and argon mixtures in microwave plasma chemical vapor deposition (MPCVD) reactor. It is worth mentioning that the novel strategy makes the synthesis reaction works smoothly without hydrogen atmosphere, and the substrates temperature is only 500 °C. The evidence of surface morphology and thickness under different time is obtained by characterizing the samples using scanning electron microscopy (SEM). X-ray diffractometer (XRD) spectrum reveals that the preferential orientation of (111) plane sample is obtained. The Raman spectra indicate that the dominant component of all the samples is a diamond. Moreover, the diamond phase content of the targeted films was quantitatively analyzed by X-ray photoelectron spectroscopy (XPS) method, and the surface roughness of diamond films was investigated by atomic force microscope (AFM). Meanwhile, the possible synthesis mechanism of the diamond films in methanol- and argon-mixed atmosphere was discussed.

Influence of power density on high purity 63 mm diameter polycrystalline diamond deposition inside a 2.45 GHz MPCVD reactor

63 mm diameter polycrystalline diamond (PCD) films were synthesized via a microwave plasma chemical vapor deposition (MPCVD) reactor in 99% H2–1% CH4 atmosphere. Two different conditions, i.e. the typical condition (input power of 5 kW and gas pressure of 13 kPa) and the high power density condition (input power of 10 kW and gas pressure of 18 kPa), were employed for diamond depositions. The color changes of the plasma under the two proposed conditions with and without methane were observed by photographs. Likewise, the concentrations of hydrogen atoms and carbon active chemical species in plasma were analyzed by optical emission spectroscopy (OES). The morphologies and purity of the PCD films were investigated by scanning electron microscopy (SEM) and Raman spectroscopy, respectively. Finally, the transmission spectrum of the polished PCD plates was characterized by a UV–Vis–NIR spectrometer. Experimental results showed that both the concentrations of hydrogen atoms and carbon radicals increased obviously, with the boost input power and higher pressure. The films synthesized under the high power density condition displayed higher purity and more uniform thickness. The growth rates in 10 kW and 18 kPa reached ~7.7 µm h−1, approximately 6.5 times as much as that occurred in the typical process. Moreover, the polished plates synthesized under the high power density condition possessed a relatively high optical transmittance (~69%), approaching the theoretical values of approximately 71.4% in IR. These results indicate that the purity and growth rate of big-area PCD films could be simultaneously increased with power density.

Development of a plate-to-plate MPCVD reactor configuration for diamond synthesis

The design and performance of a microwave plasma chemical vapor deposition (MPCVD) reactor based on compressed microwave waveguides and plate-to-plate substrate holders are described. This reactor can be operated at pressures from 10 to 40kPa with microwave power of 0.4–1.2kW, and a high plasma power density up to 500W/cm3 can be obtained. The single-crystal diamond (lower substrate holder) and polycrystalline diamond (upper substrate holder) have been grown by the plate-to-plate MPCVD reactor using high pressure CH4-H2 mixture gases. Experimental results show that high quality single-crystal diamond and polycrystalline diamond were simultaneously synthesized at a growth rate of 25μm/h and 12μm/h, respectively. The results indicate that our MPCVD reactor is unique for the synthesis of diamond with high efficiency.

Analysis of hydrogen plasma in a microwave plasma chemical vapor deposition reactor

The aim of this work is to build a numerical model of hydrogen plasma inside a microwave plasma chemical vapor deposition system. This model will help in understanding and optimizing the conditions for the growth of carbon nanostructures. A 2D axisymmetric model of the system is implemented using the finite element high frequency Maxwell solver and the heat transfer solver in COMSOL Multiphysics. The system is modeled to study variation in parameters with reactor geometry, microwave power, and gas pressure. The results are compared with experimental measurements from the Q-branch of the H2 Fulcher band of hydrogen using an optical emission spectroscopy technique. The parameter γ in Füner's model is calibrated to match experimental observations at a power of 500 W and 30 Torr. Good agreement is found between the modeling and experimental results for a wide range of powers and pressures. The gas temperature exhibits a weak dependence on power and a strong dependence on gas pressure. The inclusion of a vertical dielectric pillar that concentrates the plasma increases the maximum electron temperature by 70%, the maximum gas temperature by 50%, and the maximum electron number density by 70% when compared to conditions without the pillar at 500 W and 30 Torr. Experimental observations also indicate intensified plasma with the inclusion of a pillar.

CVD 다이아몬드가 코팅된 알루미늄 방열판의 방열 특성

Nanocrystalline diamond(NCD) coated aluminium plates were prepared and applied as heat sinks for LED modules. NCD films were deposited on 1 mm thick Al plates for times of 2 - 10 h in a microwave plasma chemical vapor deposition reactor. Deposition parameters were the microwave power of 1.2 kW, the working pressure of 90 Torr, the CH4/Ar gas ratio of 2/200 sccm. In order to enhance diamond nucleation, DC bias voltage of �90 V was applied to the substrate during deposition without external heating. NCD film was identified by X-ray diffraction and Raman spectroscopy. The Al plates with about 300 nm thick NCD film were attached to LED modules and thermal analysis was carried out using Thermal Transient Tester (T3ster) in a still air box. Thermal resistance of the module with NCD/Al plate was 3.88 K/W while that with Al plate was 5.55 K/W. The smaller the thermal resistance, the better the heat emission. From structure function analysis, the differences between junction and ambient temperatures were 12.1 o C for NCD/Al plate and 15.5 o C for Al plate. The hot spot size of infrared images was larger on NCD/Al than Al plate for a given period of LED operation. In conclusion, NCD coated Al plate exhibited better thermal spreading performance than conventional Al heat sink.

H2 Mole Fraction Measurements in a Microwave Plasma Using Coherent Anti-Stokes Raman Scattering Spectroscopy

In an effort to provide insights into the thermochemical composition of a microwave plasma chemical vapor deposition (MPCVD) reactor, the mole fraction of H2 is measured at various positions in the plasma sheath, at pressures of 10 and 30 Torr, and at plasma powers ranging from 300 to 700 W. A technique is developed by comparing the Q(1)01 transition of experimental and theoretical spectra aided by the Sandia CARSFT fitting routine. Results reveal that the mole fraction of H2 does not vary significantly from its theoretical mixture at the parametric conditions examined. Furthermore, the ν″=1→ν′=2 vibrational hot band was searched, but no transitions were found. An analytical explanation for the increase in the temperature of H2 with the introduction of N2 and CH4 is also presented. Finally, because the mole fraction of H2 does not appear to deviate from the theoretical composition, the rotational and translational modes of H2 are shown to be approximately in equilibrium, and therefore, the rotational temperatures may be used to estimate the translational temperatures of H2.

Optical, electrical and microstructural properties of nanocomposite Ag/diamond by Ag ion implantation and subsequent annealing

An optical-grade, free-standing diamond (FSD) film is prepared by home-made microwave plasma chemical vapor deposition reactor at a condition of input power 8 kW and gas pressure18 kPa. Then, it is implanted with 80 keV Ag ions up to a fluence of 5.0 × 1016 ions/cm2. After implantation, a subsequent annealing in Ar ambient at 500 °C is carried out to fabricate Ag nanoparticles (NPs). Grazing incidence x-ray diffraction results clearly showed that Ag NPs with a (111) orientation are effectively formed after 500 °C annealing. Results from field emission scanning electron microscope and atomic force microscope observations indicated that Ag NPs could aggregate and grow on the surface of the diamond film during the annealing process. The Hall effects results showed that Ag-implanted FSD film exhibited an enhanced carrier mobility of 34.7 cm2 V−1 S−1 after 500 °C annealing. Moreover, Raman spectroscopy results show that the damages of the Ag-implanted FSD film are essentially a little and the crystallinity is almost recovered by annealing, it is implied that the enhancement in carrier mobility could be attributed to the conductive paths provided by Ag NPs.