Remote N2 Plasma Research Articles

Characterization of remote N2 plasma by various techniques

The distribution of electron temperature (Te), electron density (Ne) in a remote N2 plasma was studied with the help of emission spectroscopy, Langmuir probe diagnostic techniques. The results show that the characteristic peaks were concentrated in the spectral range of 280–440 nm, whereas NIII spectral lines were dominant. The Te varies with RF power, gas pressure and axial distance. The electronic temperature decreases as the RF power rises from 20 to 100 W. When the pressure increases from 15 to 35 Pa, the Te increases at first and then decreases. For the given RF power and pressure, the Te in the discharge area increases and the Te in the remote area decreases with the increase of the axial distance. The Ne in the remote N2 plasma was of the order of 10E15cm−3. The Ne increases when the RF power increases and decreases with the increase of the pressure and axial distance.

Effect of Hydrogen Plasma Treatment on Atomic Layer Deposited Silicon Nitride Film

Changes in the thin film properties of SiNx deposited via atomic layer deposition using remote N2 plasma were investigated based on the frequency of adding a hydrogen (H2) plasma treatment step during the process. The deposition rate decreased from 0.36 to 0.32 A cycle−1 when compared to SiNx deposited through the conventional deposition process for a thin film that was subjected to H2 treatment processes every 10th cycle, every 5th cycle, and every single cycle of SiNx deposition compared to the deposition process without H2 plasma at a temperature of 400 °C. As the hydrogen treatment process increased beyond a 5:1 ratio, the hydrogen content in the thin film increased based on secondary ion mass spectroscopy analysis, and a change in binding energy state was shown via X-ray photoelectron spectroscopy. The thin film deposited using the hydrogen plasma treatment process at a ratio of 10:1 showed similar characteristics to the SiNx thin film deposited through the conventional atomic layer deposition process and showed excellent etch resistance without an increase in the etch rate. The step coverage characteristics were increased by 16% compared to the deposition process without a H2 plasma treatment process.

Photoluminescence Induced by Substitutional Nitrogen in Single-Layer Tungsten Disulfide.

The electronic and optical properties of two-dimensional materials can be strongly influenced by defects, some of which can find significant implementations, such as controllable doping, prolonged valley lifetime, and single-photon emissions. In this work, we demonstrate that defects created by remote N2 plasma exposure in single-layer WS2 can induce a distinct low-energy photoluminescence (PL) peak at 1.59 eV, which is in sharp contrast to that caused by remote Ar plasma. This PL peak has a critical requirement on the N2 plasma exposure dose, which is strongest for WS2 with about 2.0% sulfur deficiencies (including substitutions and vacancies) and vanishes at 5.6% or higher sulfur deficiencies. Both experiments and first-principles calculations suggest that this 1.59 eV PL peak is caused by defects related to the sulfur substitutions by nitrogen, even though low-temperature PL measurements also reveal that not all the sulfur vacancies are remedied by the substitutional nitrogen. The distinct low-energy PL peak suggests that the substitutional nitrogen defect in single-layer WS2 can potentially serve as an isolated artificial atom for creating single-photon emitters, and its intensity can also be used to monitor the doping concentrations of substitutional nitrogen.

Robust SiNx/GaN MIS-HEMTs With Crystalline Interfacial Layer Using Hollow Cathode PEALD

In this letter, we report gallium nitride-based metal-insulator-semiconductor high-electron-mobility transistors (GaN MIS-HEMTs) with a 16-nm-thick silicon nitride (SiN x ) gate insulator and surface passivation layer grown using low-temperature (300 °C) hollow cathode plasma-enhanced atomic layer deposition. Tris(dimethylamino) silane and a remote N2 plasma were used as the silicon precursor and the nitrogen co-reactant, respectively. Though the growth temperature was as low as 300 °C, we obtained excellent film properties such as a high refractive index (2.00), a high film density (2.9 g/cm3), and a low wet etch rate (0.8 nm/min) in 100:1 hydrofluoric acid. High-resolution transmission electron microscopy images of the gate stacks showed ~1.5 nm $\beta $ -phase Si3N4 crystalline interfacial layer on the GaN surface. The devices showed a negligible hysteresis of ~50 mV, a steep subthreshold slope of 76 mV/dec, and a high ON/OFF drain current ratio of ~109. In addition, the devices showed a small positive/negative bias temperature threshold voltage ( ${V}_{\text {th}}$ ) instability ( $\Delta {V}_{\text {th}}\le 0.2$ V at 25 °C and 150 °C) as well as a mitigated current collapse under an off-state quiescent ${V}_{\text {DS}}$ of 20 V.

Interface Engineering of Monolayer MoS2/GaN Hybrid Heterostructure: Modified Band Alignment for Photocatalytic Water Splitting Application by Nitridation Treatment.

Interface engineering is a key strategy to deal with the two-dimensional (2D)/three-dimensional (3D) hybrid heterostructure, since the properties of this atomic-layer-thick 2D material can easily be impacted by the substrate environment. In this work, the structural, electronic, and optical properties of the 2D/3D heterostructure of monolayer MoS2 on wurtzite GaN surface without and with nitridation interfacial layer are systematically investigated by first-principles calculation and experimental analysis. The nitridation interfacial layer can be introduced into the 2D/3D heterostructure by remote N2 plasma treatment to GaN sample surface prior to stacking monolayer MoS2 on top. The calculation results reveal that the 2D/3D integrated heterostructure is energetically favorable with a negative formation energy. Both interfaces demonstrate indirect band gap, which is a benefit for longer lifetime of the photoexcited carriers. Meanwhile, the conduction band edge and valence band edge of the MoS2 side increases after nitridation treatment. The modification to band alignment is then verified by X-ray photoelectron spectroscopy measurement on MoS2/GaN heterostructures constructed by a modified wet-transfer technique, which indicates that the MoS2/GaN heterostructure without nitridation shows a type-II alignment with a conduction band offset (CBO) of only 0.07 eV. However, by the deployment of interface nitridation, the band edges of MoS2 move upward for ∼0.5 eV as a result of the nitridized substrate property. The significantly increased CBO could lead to better electron accumulation capability at the GaN side. The nitridized 2D/3D heterostructure with effective interface treatment exhibits a clean band gap and substantial optical absorption ability and could be potentially used as practical photocatalyst for hydrogen generation by water splitting using solar energy.

Remote N2 plasma treatment to deposit ultrathin high-k dielectric as tunneling contact layer for single-layer MoS2 MOSFET

Remote N2 plasma treatment is explored as a surface functionalization technique to deposit ultrathin high-k dielectric on single-layer MoS2. The ultrathin dielectric is used as a tunneling contact layer, which also serves as an interfacial layer below the gate region for fabricating top-gate MoS2 metal–oxide–semiconductor field-effect transistors (MOSFETs). The fabricated devices exhibited small hysteresis and mobility as high as 14 cm2·V−1·s−1. The contact resistance was significantly reduced, which resulted in the increase of drain current from 20 to 56 µA/µm. The contact resistance reduction can be attributed to the alleviated metal–MoS2 interface reaction and the preserved conductivity of MoS2 below the source/drain metal contact.

Revealing the Nitridation Effects on GaN Surface by First-Principles Calculation and X-Ray/Ultraviolet Photoemission Spectroscopy

In this paper, we report a systematic study of the nitridation effects on GaN surface by first-principles calculations and X-ray/ultraviolet photoemission spectroscopy (XPS/UPS). According to the calculated electronic structures, two surface bands (i.e., the upper band and the lower band) can be seen within the bandgap for the typical surface configurations that may occur in the experimental condition as a result of surface reconstruction. By the deployment of sufficient nitridation, the energy positions of the lower band are modified toward the valence band by ~1 eV, resulting in the overlapping of the lower surface band with the valence band. Meanwhile, the upper surface band is also modified toward the valence band, but by a smaller amount. The modification to the positions of the surface bands is furthermore manifested by XPS/UPS spectra characterization performed on GaN sample that underwent surface treatment with low-energy remote N2 plasma. The theoretical and experimental results insightfully proclaim the nitridation effects on material properties at atomic level, and support a surface-state ionization model for the GaN band-edge (3.4 eV) emission in metal-AlGaN/GaN Schottky-on-heterojunction diode under forward bias.

Enhanced dielectric deposition on single-layer MoS2 with low damage using remote N2 plasma treatment

Using remote N2 plasma treatment to promote dielectric deposition on the dangling-bond free MoS2 is explored for the first time. The N2 plasma induced damages are systematically studied by the defect-sensitive acoustic-phonon Raman of single-layer MoS2, with samples undergoing O2 plasma treatment as a comparison. O2 plasma treatment causes defects in MoS2 mainly by oxidizing MoS2 along the already defective sites (most likely the flake edges), which results in the layer oxidation of MoS2. In contrast, N2 plasma causes defects in MoS2 mainly by straining and mechanically distorting the MoS2 layers first. Owing to the relatively strong MoS2–substrate interaction and chemical inertness of MoS2 in N2 plasma, single-layer MoS2 shows great stability in N2 plasma and only stable point defects are introduced after long-duration N2 plasma exposure. Considering the enormous vulnerability of single-layer MoS2 in O2 plasma and the excellent stability of single-layer MoS2 in N2 plasma, the remote N2 plasma treatment shows great advantage as surface functionalization to promote dielectric deposition on single-layer MoS2.

Covalent Nitrogen Doping and Compressive Strain in MoS2 by Remote N2 Plasma Exposure.

Controllable doping of two-dimensional materials is highly desired for ideal device performance in both hetero- and p-n homojunctions. Herein, we propose an effective strategy for doping of MoS2 with nitrogen through a remote N2 plasma surface treatment. By monitoring the surface chemistry of MoS2 upon N2 plasma exposure using in situ X-ray photoelectron spectroscopy, we identified the presence of covalently bonded nitrogen in MoS2, where substitution of the chalcogen sulfur by nitrogen is determined as the doping mechanism. Furthermore, the electrical characterization demonstrates that p-type doping of MoS2 is achieved by nitrogen doping, which is in agreement with theoretical predictions. Notably, we found that the presence of nitrogen can induce compressive strain in the MoS2 structure, which represents the first evidence of strain induced by substitutional doping in a transition metal dichalcogenide material. Finally, our first principle calculations support the experimental demonstration of such strain, and a correlation between nitrogen doping concentration and compressive strain in MoS2 is elucidated.

An improvement of HfO2/Ge interface by in situ remote N2 plasma pretreatment for Ge MOS devices

In situ remote N2 plasma pretreatment of Ge substrate before deposition of HfO2 is proved effective to reduce GeOx interlayer at the HfO2/Ge interface, resulting in a smaller capacitance equivalent oxide thickness, lower interface trap density and leakage current density for the metal/HfO2/n-Ge capacitors. However, it has no obvious impact on the metal/HfO2/p-Ge capacitors, showing a much higher interface trap density than that on n-Ge. The high equivalent permittivity of the HfO2 gate stacks (∼24.2) confirmed the removal of GeOx interlayer by N2 plasma pretreatment. In situ remote N2 plasma pretreatment is demonstrated perspective to make metal/HfO2/n-Ge MOSFET with scaling capacitance equivalent oxide thickness.

Double nitridation of crystalline ZrO2/Al2O3 buffer gate stack with high capacitance, low leakage and improved thermal stability

The gate dielectric stack composed of crystalline ZrO2 and Al2O3 buffer layer treated with double nitridation was developed to reduce the capacitance equivalent thickness (CET), leakage current density (Jg), interfacial state density (Dit), and enhance thermal stability as well. A high dielectric constant of the gate stack was provided by the crystalline ZrO2 with tetragonal/cubic phase. The Jg and Dit were suppressed by the insertion of the Al2O3 buffer layer treated with remote NH3 plasma nitridation because of the deactivation of the oxygen vacancies and the well passivation of the Si dangling bonds. A further nitridation using remote N2 plasma on ZrO2 was carried out to reduce the CET and Jg by the enhancement of the dielectric constant and the deactivation of the grain boundaries and oxygen vacancies. Accordingly, a low CET of 1.09nm, Jg of 3.43×10−5A/cm2, and Dit of 3.35×1011cm−2eV−1 were achieved in the crystalline ZrO2/Al2O3 buffer gate stack treated with the double nitridation. The hysteresis was also minimized significantly by the post-deposition annealing at 800°C, which is attributed to the enhanced thermal stability. The results indicate that the crystalline high-K dielectrics/buffer layer with double nitridation treatments is a promising gate stack structure beneficial to the sub-nanometer CET scaling in the future.

Effect of hydrogen participation on the improvement in electrical characteristics of HfO2 gate dielectrics by post-deposition remote N2, N2/H2, and NH3 plasma treatments

The structural and electrical characteristics of hafnium oxide (HfO2) gate dielectrics treated by a variety of post-deposition nitridation processes, including remote N2, N2/H2 and NH3 plasma, are presented by the x-ray photoelectron spectroscopy (XPS), high-resolution transmission electron microscopy and electrical measurements. The XPS measurement reveals that the nitrogen content in the HfO2 thin film treated by remote nitrogen and hydrogen plasma is higher than that treated only by remote nitrogen plasma, suggesting that the hydrogen has the capability to facilitate nitrogen dissociation. An ultra-thin interfacial layer (IL) thickness (∼0.3 nm), a high dielectric constant (20), an acceptable gate leakage current density (∼9 × 10−6 A cm−2), and a low capacitance equivalent thickness (1.9 nm) of the HfO2 gate dielectric were achieved by the post-deposition remote NH3 plasma nitridation treatment. However, an IL layer as thick as 1.5 nm was observed in the sample treated only by remote N2 plasma. The results indicate that the participation of hydrogen in the nitridation process is a promising way to improve the electrical properties of HfO2 gate dielectrics.

Study of the interaction of 4H–SiC and 6H–SiC(0001)Si surfaces with atomic nitrogen

The interaction of atomic nitrogen with 4H– and 6H–SiC(0001) Si-face surfaces is investigated. Clean and atomically smooth terraced surfaces obtained by in situ cleaning using atomic hydrogen have been exposed at 200°C and 750°C to atomic nitrogen produced by a rf remote N2 plasma. Spectroscopic ellipsometry is used for real-time monitoring of the kinetics of SiC surface modifications, and determining the thickness and properties of the nitrided layer. Surface potential measurements reveal the band bending of the nitrided SiC surface. An improvement in the heteroepitaxy of GaN on the low-temperature nitrided SiC surface is found.

Plasma cleaning and nitridation of sapphire (α-Al2O3) surfaces: New evidence from in situ real time ellipsometry

The interaction of α-Al2O3 (0001) surfaces with H atoms and N atoms from remote rf plasmas used for the cleaning and nitridation processes, respectively, is investigated at temperatures in the range of 200–600 °C. The chemistry and kinetics of the above processes are monitored in real time by in situ spectroscopic ellipsometry. Also, the chemistry of the nitrided sapphire surfaces is verified by x-ray photoelectron spectroscopy (XPS) analysis. Specifically, H atoms treatments are effective in removing carbon contaminants from the sapphire surface at temperatures of 200–400 °C. Real time ellipsometry is suitable to detect the cleaning end point and to verify the onset of the H-atom diffusion into the sapphire substrate. Remote N2 plasma nitridation at 200 °C is found to yield homogeneous and smooth AlN layers of about 5 Å, after approximately 25 min of nitridation, whereas high nitridation temperatures result in a damaged sapphire surface with AlN protrusions. Both ellipsometric and XPS data show that the sapphire nitridation can be interpreted in the framework of a chemical model, where the formation of NO competes with AlN formation. The chemisorption equilibrium of NO, which strongly depends on surface temperature, is the key factor controlling the nitridation chemistry and kinetics.

Treatment of poly(ether ether ketone) (PEEK) surfaces by remote plasma discharge. XPS investigation of the ageing of plasma‐treated PEEK

AbstractThe effect of a cold remote N2 plasma (CRNP) or N2 + O2 plasma (CRNOP) on poly(ether ether ketone) (PEEK) is studied. The amount of nitrogen or oxygen uptake and functionalities are determined by x‐ray photoelectron spectroscopy (XPS). After CRNP treatment, the N/C and O/C atomic ratios are 0.301 and 0.333, respectively. Nitrogen functional groups are not detected by CRNOP treatment, and the O/C atomic ratio is then 0.785. The ageing process of the treated PEEK surface in the open air is investigated in both cases. For CRNOP treatment the O/C atomic ratio decreases by carbonate function departure, whereas for CRNP treatment the total amount of nitrogen and oxygen graft atoms goes through a maximum after 1 h of air exposure.