Sophisticated thin film growth techniques increasingly rely on the addition of a plasma component to open or widen a processing window, particularly at low temperatures. Taking advantage of continued increases in accelerator-based X-ray source brilliance, this real-time study uses X-ray Photon Correlation Spectroscopy (XPCS) to elucidate the nanoscale surface dynamics during Plasma-Enhanced Atomic Layer Deposition (PE-ALD) of an epitaxial indium nitride film. Ultrathin films are synthesized from repeated cycles of alternating self-limited surface reactions induced by temporally separated pulses of the material precursor and plasma reactant, allowing the influence of each on the evolving morphology to be examined. During the heteroepitaxial 3D growth examined here, sudden changes in the surface structure during initial film growth, consistent with numerous overlapping stress-relief events, are observed. When the film becomes continuous, the nanoscale surface morphology abruptly becomes long-lived with a correlation time spanning the period of the experiment. Throughout the growth experiment, there is a consistent repeating pattern of correlations associated with the cyclic growth process, which is modeled as transitions between different surface states. The plasma exposure does not simply freeze in a structure that is then built upon in subsequent cycles, but rather, there is considerable surface evolution during all phases of the growth cycle.

Indium nitride (InN) is a low-band-gap semiconductor with unusually high electron mobility, making it suitable for IR-range optoelectronics and high-frequency transistors. However, the development of InN-based electronics is hampered by the metastable nature of InN. The decomposition temperature of InN is lower than the required growth temperature for most crystal growth techniques. Here, we discuss growth of InN films and epitaxial layers by atomic layer deposition (ALD), a growth technique based on self-limiting surface chemical reactions and, thus, inherently a low-temperature technique. We describe the current state of the art in ALD of InN and InN-based ternary alloys with GaN and AlN, and we contrast this to other growth technologies for these materials. We believe that ALD will be the enabling technology for realizing the promise of InN-based electronics.

Plasma enhanced atomic layer deposition (PEALD) is a cyclic atomic layer deposition process that incorporates plasma-generated species into one of the cycle substeps. The addition of plasma is advantageous as it generally provides unique gas-phase chemistries and a substantially reduced growth temperature compared to thermal approaches. However, the inclusion of plasma, coupled with the increasing variety of plasma sources used in PEALD, can make these systems challenging to understand and control. This work focuses on the use of plasma diagnostics to examine the plasma characteristics of a hollow cathode enhanced capacitively coupled plasma (HC-CCP) source, a type of plasma source that has seen increasing attention in recent years for PEALD. Ultraviolet to near-infrared spectroscopy as well as spatially resolved Langmuir probe and emissive probe measurements are employed to characterize an HC-CCP plasma source using nitrogen based gas chemistries typical of nitride PEALD processes. Spectroscopy is used to characterize the relative concentrations of important reactive and energetic neutral species generated in HC-CCP systems as a function of applied RF power, gas chemistry, and pressure. In addition, the electron energy distribution function, electron temperature, plasma potential, and plasma density for the same process parameters are examined using an RF compensated Langmuir probe and emissive probe. These measurements indicated that electron temperature ( Te), electron density ( ne), and plasma potential ( Vp) varied significantly over the operating conditions examined with Te varying from 1.5 to 8 eV, Vp varying from 30 to 90 V, and ne varying between 1015 and low 1016 m−3. This wide range of plasma conditions is mediated by a mode transition from a low Te, high ne mode of operation at low pressure (<100 mTorr) to a high Te, low ne mode at higher pressures (>100 mTorr). These operational modes appear analogous to the classical γ and α modes of traditional capacitively coupled plasmas. Atomic N and H densities also vary significantly over the operating conditions examined.

Plasma-enhanced atomic layer deposition (PEALD) enables the epitaxial growth of ultrathin indium nitride (InN) films at significantly reduced process temperatures and with greater control of layer thickness compared to other growth methods. However, the reliance on plasma-surface interactions increases the complexity of the growth process. A detailed understanding of the relationship between the plasma properties and the growth kinetics is therefore required to guide the tuning of growth parameters. We present an in situ investigation of the early-stage PEALD growth kinetics of epitaxial InN within three different plasma regimes using grazing incidence small-angle x-ray scattering (GISAXS). The GISAXS data are supported by diagnostic studies of the plasma species generation in the inductively coupled plasma source as a function of the relative concentrations of the nitrogen/argon gas mixture used in the growth process. The growth mode is found to be correlated to the production of nitrogen species in the plasma, with high concentrations of the atomic N species promoting Volmer–Weber growth (i.e., island growth) and low concentrations promoting Stranski–Krastanov growth (i.e., layer-plus-island growth). The critical thickness for island formation, island center-to-center distance, and island radius are found to increase with ion flux. Furthermore, the island center-to-center distance and areal density are observed to change only during plasma exposure and to continue changing with exposure even after the methylindium adlayer is believed to have fully reacted with the plasma. Our results demonstrate the potential to control the growth kinetics during PEALD of epitaxial films by intentionally accessing specific regimes of plasma species generation.

improvement was observed at high annealing temperatures. At lower annealing temperatures, increased blueshifts were observed for samples grown with a higher proportion of atomic N; however, there was no noticeable influence of ions on blueshift regardless of whether atomic N or metastable N{sub 2}* was the dominant species present in the plasma. The key implication of this work is that it helps to elucidate a possible reason for some of the contradictory reports in the literature. The ions are not solely responsible for the commonly reported ''plasma damage.'' Furthermore, we demonstrate herein that atomic N and metastable N{sub 2}* each have different effects on the optical properties of dilute nitride materials grown by plasma-assisted molecular-beam epitaxy.

Ga2O3 is the only ultra-wide bandgap semiconductor with melt-growth substrate technology similar to that of Si, heterostructure device technology similar to that of the III-Nitride family, and high growth rate (GR) epitaxial technologies such as MOCVD and HVPE to support the development of ultra-high-breakdown voltage devices competitive with SiC technology. We have demonstrated for the first time a β-Ga2O3 MOSFET grown by high-GR MOCVD (Agnitron Technology’s Agilis 100 reactor) with record high mobility of 170 cm2/Vs, despite increased carrier scattering rate in the doped channel, facilitated by a significant improvement in epilayer quality. The high GR demonstrated via this method paves the road for demonstration of high breakdown voltage devices on a thick Ga2O3 buffer layer. [1] M.J. Tadjer et al., J. Phys. D: Appl. Phys. 54 (2021) 034005.

The ultra-wide bandgap semiconductor gallium oxide (Ga 2 O 3 ) offers substantial promise to significantly advance power electronic devices as a result of its high breakdown electric field and maturing substrate technology. A key remaining challenge is the ability to grow electronic-grade epitaxial layers at rates consistent with 20–40 μ m thick drift regions needed for 20 kV and above technologies. This work reports on extensive characterization of epitaxial layers grown in a novel metalorganic chemical vapor deposition tool that permits growth rates of 1.0–4.0 μ m h −1 . Specifically, optical, structural and electrical properties of epilayers grown at ∼1 μ m h −1 are reported, including employment in an operating MOSFET. The films demonstrate relatively smooth surfaces with a high degree of structural order, limited point defectivity (N d − N a ≈ 5 × 10 15 cm −3 ) and an optical bandgap of 4.50 eV. Further, when employed in a MOSFET test structure with an n + doped channel, a record high mobility for a transistor structure with a doped channel of 170 cm 2 V −1 s −1 was measured via the Hall technique at room temperature. This work reports for the first time a β-Ga 2 O 3 MOSFET grown using Agnitron Technology’s high growth rate MOCVD homoepitaxial process. These results clearly establish a significant improvement in epilayer quality at growth rates that can support future high voltage power device technologies.

Recent breakthroughs in bulk crystal growth of the thermodynamically stable beta phase of gallium oxide (β-Ga2O3) have led to the commercialization of large-area β-Ga2O3 substrates with subsequent epitaxy on (010) substrates producing high-quality films. Still, metalorganic chemical vapor deposition, molecular beam epitaxy, and processing of the (010) β-Ga2O3 surface are known to form subnanometer-scale facets along the [001] direction as well as larger ridges with features perpendicular to the [001] direction. A density function theory calculation of the (010) surface shows an ordering of the surface as a subnanometer-scale feature along the [001] direction. Additionally, the general crystal structure of β-Ga2O3 is presented, and recommendations are presented for standardizing (010) substrates to account for and control the larger-scale ridge formation.

We demonstrate the growth of ultra-thin AlN films on Si (111) and on a GaN/sapphire (0001) substrate using atomic layer epitaxy in the temperature range of 360 to 420 °C. Transmission electron microscopy and X-ray diffraction were used to characterize the interfaces, fine scale microstructure, and the crystalline quality of thin films. Films were deposited epitaxily on Si (111) with a hexagonal structure, while on the GaN/sapphire (0001) substrate, the AlN film is epitaxial and has been deposited in a metastable zinc-blende cubic phase. Transmission electron microscopy reveals that the interface is not sharp, containing an intermixing layer with cubic AlN. We show that the substrate, particularly the strain, plays a major role in dictating the crystal structure of AlN. The strain, estimated in the observed orientation relation, is significantly lower for cubic AlN on hexagonal GaN as compared to the hexagonal AlN on hexagonal GaN. On the Si (111) substrate, on the other hand, the strain in the observed orientation relation is 0.8% for hexagonal AlN, which is substantially lower than the strain estimated for the cubic AlN on Si(111).

Due to their superior breakdown fields compared with GaN and SiC and high thermal conductivity, AlxGa1−xN (x > 0.4) channel high‐electron‐mobility transistors (HEMTs) will find applications in extreme environments such as power electronics. Herein, the high‐temperature operation of ultrawide‐bandgap (UWBG) Al0.65Ga0.35N/Al0.4Ga0.6N metal oxide semiconductor heterostructure field effect transistors (MOSHFETs) with atomic layer‐deposited (ALD) high‐k gate dielectrics TiO2, Al2O3, and ZrO2 is reported. As compared with similar geometry HFETs, these devices exhibit a simultaneous reduction in gate‐leakage current by ≈104 and a positive shift of the threshold voltage as much as 4 V. This positive threshold shift indicates the introduction of negative charges at the oxide/barrier interface and within the thin oxide, attributed to the pre‐ALD plasma treatment. The gate leakage increases weakly with temperature up to 250 °C, whereas the peak drain currents decrease from ≈0.5 to 0.3 A mm−1. An analysis of the C–V and I–V characteristics reveals that this drain current decrease is due to a reduction in channel electron mobility. The potential mechanisms responsible for this are discussed. Up to the measured temperature of 250 °C, the devices withstand repeated temperature cycles without catastrophic degradation or breakdown, underscoring the promise of these materials.

Valence and conduction band offsets of atomic layer deposition (ALD) Al2O3 deposited on bulk AlN crystals were determined using x-ray photoelectron spectroscopy to be ΔEV = 0.75 eV and ΔEC = −1.45 eV, with a measured energy gap of the Al2O3 film of 6.9 eV. In addition, crystalline AlN deposited by atomic layer epitaxy on sapphire was evaluated, resulting in a valence band offset of ΔEV = −0.75 eV and a conduction band offset of ΔEC = 3.25 eV due to the wider bandgap of the crystalline Al2O3 substrate compared to amorphous ALD Al2O3. Both heterojunctions exhibited type-II behavior and similar valence band offsets.

Ga2O3 has emerged as a promising material for next-generation power electronics. Beyond the most stable and studied beta phase, metastable alpha-, epsilon-, and kappa-Ga2O3 have unique characteristics such as larger bandgaps, potential alloying for dopant and band engineering, and polarization, all of which can be leveraged in electronic device applications. Plasma-enhanced atomic layer deposition (PEALD) is a conformal, energy-enhanced synthesis method with many advantages including reduced growth temperatures, access to metastable phases, and improved crystallinity. In this study, PEALD was employed to deposit highly resistive, crystalline Ga2O3 films from 265 to 475 degrees C on c-plane sapphire substrates. Crystallinity, atypical at these low growth temperatures, was presumably due to the high flux of energetic ions to the growth surface independent of other growth parameters. Phase selectivity of beta, alpha, epsilon(kappa)-Ga2O3 was demonstrated as a function of plasma gas composition, gas flow and pressure during the plasma pulse, as well as growth temperature. Factors such as atomic oxygen generation and the flux of energetic ions were found to have a significant impact on the ability to attain metastable phases. Optimum films of each phase were fully characterized to determine the feasibility of PEALD Ga2O3 films. While both high-quality, single-phase beta- and alpha-Ga2O3 films were achieved, epsilon-Ga2O3 films were not able to be completely isolated and even under the best conditions contained components of beta- and kappa-Ga2O3 as identified by transmission electron microscopy. Trends suggest that this could be a limitation of the underlying substrate or reactor configuration.

The inclusion of plasma in atomic layer deposition processes generally offers the benefit of substantially reduced growth temperatures and greater flexibility in tailoring the gas-phase chemistry to produce specific film characteristics. The benefits plasmas provide, however, come at the cost of a complex array of process variables that often challenge the ability to predict, a priori, the influence of any one input parameter. In this work, the authors attempt to provide some clarity as to how plasmas are formed and controlled and how they can most optimally be employed within the framework of atomic layer deposition. To begin, the authors cover some of the fundamentals of plasma generation along with the production of energetic and reactive species and their transport within the plasma. They then focus on how different plasma generation schemes and geometries, often employed in plasma-enhanced atomic layer deposition (PEALD), differ in their production of energetic and reactive species. They also address the plasma-surface interactions that are critical for film growth and control of crystallinity. Throughout this work, the authors use both current experimental data and a review of previously published works to describe how variations in the approach to plasma generation and the interactions between plasma-produced species and the growth surface influence the plasma reactant step in PEALD processes. The authors highlight two case studies to demonstrate how these relationships can be used to control the phase purity of crystalline titanium dioxide (TiO2) films and grow crystalline growth of semiconducting indium nitride (InN).

Ga2O3 has emerged as a promising material for next generation power electronics. While β-Ga2O3 (monoclinic) is the most stable and studied of six Ga2O3 polymorphs, the slightly less energetically favorable α-, ε-, and κ-Ga2O3 phases have unique characteristics that can be exploited such as larger bandgaps, alloying for dopant control, or polarization beneficial to the formation of two-dimensional electron gas (2DEG) channels. Specifically, α-Ga2O3 (rhombohedral, corundum) has the largest bandgap of ~5.3 eV and can be alloyed with α-Al2O3 (8.8 eV) and α-In2O3 (3.7 eV) for bandgap engineering. Both ε-Ga2O3 (hexagonal, P63mc) and κ-Ga2O3 (orthorhombic, Pna21 ) phases are polar, with a predicted spontaneous polarization strength up to 10 times larger than GaN and 3 times larger than AlN. Like the III-N system, polarization induced charges can lead to higher charge densities and mobilities in 2DEGs formed at heterojunctions, which would improve the viability of Ga2O3 electronic devices. Plasma-enhanced atomic layer deposition (PEALD) is a popular, conformal, energy-enhanced synthesis method for thin films due to its many advantages, including: deposition at reduced growth temperatures, access to metastable phases, improved crystallinity, and increased growth rates. In this work, we use PEALD to produce high-quality heteroepitaxial Ga2O3 and (AlxGa1-x)2O3 (AlGO) films and investigate materials properties such as phase selectivity, ternary solubility limits, and electrical and optical performance. All Ga2O3 films were deposited in a Veeco Fiji G2 reactor equipped with a load lock and turbo pump using trimethygallium, trimethylaluminum, and O2 plasma. Initial studies on c-plane sapphire substrates at 350°C and 8 mTorr show the phase could be altered from β to α by a varying the pure O2 flow during plasma pulse from 5-40 sccm [1]. Optical emission spectroscopy indicate that the changes in the relative concentration of atomic oxygen is crucial for phase selectivity while the high ion flux to the surface can contribute to the crystallinity at low Tg [2]. To grow ε(κ)-Ga2O3 on c-plane sapphire required going to a much higher temperature (500°C), pressure (100’s mTorr), and O2 flow (100sccm) [1]. Without modifications to the current ALD system, pure ε(κ)-Ga2O3 on sapphire was not achieved under any conditions. Using optimum growth conditions for the three phases on sapphire, films were deposited on GaN and diamond to determine the effect of substrate structure. Transmission electron microscopy was conducted to determine the specific phases (β, ε, and κ) present in each case, and showed the amount of each phase varied with PEALD parameters. While films on diamond resulted in mixed β/ε(κ) phases, pure ε(κ)-phase films were attained on GaN and the strain varied with pressure and Tg. Vertical breakdown measurements were taken for both β- and ε(κ)-Ga2O3/n+ GaN substrates. Breakdown fields varied between 3.8-7.0 MV/cm dependent on the phase and strained state of the Ga2O3 films. β-Ga2O3 films showed less variability in breakdown field from device to device than ε(κ)-Ga2O3 films, but neither showed a dependence on device size. While PEALD is beneficial for depositing thin films of metastable phases, practical devices often require much thicker barrier and active layers. For this reason, we investigated integrating PEALD metastable Ga2O3 films with traditional semiconductor deposition techniques, such as molecular beam epitaxy (MBE), capable of extending these layers beyond 100 nm in thickness. The same MBE conditions were used to deposit Ga2O3 films on GaN substrates with and without PEALD ε(κ)-Ga2O3 nucleation layers. Those deposited without the PEALD metastable nucleation layer resulted in stable β-phase films, while those with nucleation layers resulted in pure ε(κ)-phase films. This shows importance of PEALD for realizing practical device structures using metastable phases. Finally, to investigate heterojunctions for 2DEG formation, AlxGa1-xO films were developed. While the full stoichiometric range could be reached using a PEALD digital alloying method, crystallinity was lost above x = 0.2 for the β phase, x = 0.35 for the ε(κ) phase, and x=0.6 for the α phase. Initial device structures will be shown in order to establish the feasibility of these films in device applications. [1] Wheeler, et al. Chem. Mater. 2020, 32, 1140-1152 [2] Boris, et al. JVST A 2019, 37(6), 060909 Figure 1

Cu2O and CuO are promising p-type semiconductor materials, which show potential for a variety of applications from photovoltaics to high-Tc superconductors. Atomic layer deposition (ALD) presents an advantageous technique for the growth of copper oxide due to the ability to grow on a variety of substrate materials and geometries with atomic precision in thickness and high uniformity. The work presented here is a comprehensive study on the effect of boost and precursor delivery on the growth of copper oxide films using the same precursor and under the same reactor environment. This is critical to understanding the growth mechanism and properties of ALD grown copper oxide films using the same starting precursor while varying the coreactants. In this study, the deposition of copper oxide is performed using the precursor bis-(dimethylamino-2-propoxide) Cu(II) (Cudmap) and either water or ozone as a coreactant. Keeping the copper precursor pulse constant, CuO films were produced with ozone, while Cu2O films were obtained using water. Through conventional precursor delivery, a saturated growth rate of 0.19 and 0.045 Å/cycle is established using ozone and water as coreagents, respectively. In order to enable more efficient precursor delivery, a vapor boost modification was implemented, which doubled the film growth rate to 0.38 Å/cycle when using ozone, higher than previously reported. While there was no increased growth rate using the vapor boost with water, the growth rate could be doubled to 0.09 Å/cycle by tripling the water dosage. In both cases, the as-deposited films were smoother when implementing a vapor boost and polycrystalline as deposited, which has not been previously observed for Cu2O films grown with Cudmap. From the results here, growth of CuO using ozone is most improved by using a Cudmap vapor boost delivery, indicating Cudmap limited growth, while Cu2O growth is limited by the water dosage.

Vertical GaN power switch technology is expected to be utilized in next-generation medium to high voltage power converters due to the low ON-resistance and high breakdown voltage enabled by the improved critical electric field and mobility compared to Si and SiC-based devices. As large area substrates have become available by hydride vapor phase epitaxy (HVPE) and ammonothermal growth, the properties of nitrides are no longer dominated by defects introduced by heteroepitaxial growth, allowing recent realization of several fundamental vertical power devices, including diodes with edge termination, trench MOSFETs, and CAVETs. However, additional materials challenges are coming to the forefront that need to be understood and surmounted in order to allow vertical GaN power devices to achieve their full potential, notably the realization of repeatable thick drift layers with low background doping. To enable this, a deeper understanding of substrate preparation and the effects of the substrate and growth initiation on the characteristics of the epitaxial layers is required for MOCVD growth of homoepitaxial films. We investigate these effects on epi morphology, uniformity, and impurity incorporation by growing simultaneously on wafers from different vendors. The goal of this work is to detect and identify defects in GaN substrates with a series of quick, non-destructive, inexpensive techniques with capabilities of mapping whole wafers. Four different substrates - three grown by hydride vapor phase epitaxy and the fourth by ammonothermal technique were obtained from multiple vendors. All had nominally similar as-received specifications (resistivity, thickness, off-cut angle, bow, surface finish). The substrates were evaluated with a variety of techniques including Raman spectroscopy, photoluminescence, white light interferometry, and Nomarski imaging, enabling to detection of different concentrations of grain boundaries, sample impurities, point defects, v-shaped pits, polishing defects, crystal stress damage, and non-uniform insulating and conducive regions. Comparing these results to those from homoepitaxial growth on the same wafers, the effects are both subtle and overt. Macroscopic surface morphology, which has shown a direct correlation to leakage current, copies and exaggerates that of the underlying substrate. Donor incorporation in the epitaxy is relatively uniform, regardless of the substrate doping. However, homoepitaxy on substrates with inhomogeneous impurity incorporation did show some near band edge broadening by PL. Carbon incorporation varied with substrate offcut angle, which is supported by DFT calculations. All interfaces between epitaxy and substrate have a large Si peak, which requires further study. Following optical characterization, vertical Schottky diodes were fabricated to quickly evaluate device performance. While most of the films showed the ability to withstand high electric fields, those with more uniform properties in the substrate also showed more uniform electrical properties. These results show that the bulk substrates enable the path to high voltage vertical devices, but also show the significant influence that substrates can play in device performance.

Hexagonal boron nitride (hBN) thin films were grown by plasma-enhanced chemical beam epitaxy (PE-CBE) on epitaxial graphene (EG) on macrostepped 4°-offcut 4H-SiC(0001) substrates. The choice of growth conditions in this system allowed for two prominent in-plane hBN/EG rotational alignments: a direct alignment of the hBN and EG lattices or a 30° in-plane rotational twist such that the ⟨112¯0⟩hBN and ⟨101¯0⟩EG directions are parallel. The use of nitrogen plasma in conjunction with borazine at growth temperatures of 1450 °C increased the crystallinity of the few-monolayer-thick films relative to films grown by CBE without plasma exposure. In vacuo x-ray photoelectron spectroscopy showed that films grown with nitrogen plasma exposure were stoichiometric to nitrogen-rich, depending on growth conditions, and exhibited no bonding indicative of additional phase formation. This PE-CBE process was shown to produce films with atomically abrupt interfaces between the hBN and EG lattices, as determined by cross-sectional transmission electron microscopy (TEM). Annular dark field and bright field scanning TEM paired with energy dispersive x-ray spectroscopy confirmed that the EG persisted throughout this deposition and no intercalative growth of hBN under the EG was detected. Higher PE-CBE growth rates produced hBN domains that nucleated uniformly across the substrate with little preferred orientation of their edges. In comparison, lower growth rates appeared to cause preferential nucleation on the macrostep edges with a 30° in-plane rotation relative to the EG, as confirmed by cross-sectional TEM. By correlating the hBN nuclei shape in AFM to the atomic registry of the hBN to the substrate, it was found that the triangular, macrostep-edge nuclei were arm-chair edge terminated. The ability to select different rotational alignments by changing epitaxial growth conditions may be used in future wafer-scale growth of hBN/graphene heterostructures to achieve varying degrees of graphene band structure modulation.