Hydrogen-terminated Diamond Surface Research Articles

Origin of two-dimensional hole gas at the hydrogen-terminated diamond surfaces: Negative interface valence-induced upward band bending

The surface transfer doping model has been extensively adopted as a mechanism to account for the generation of hole accumulation layers below hydrogen-terminated diamond (H-diamond) surfaces. To achieve effective surface transfer doping, surface electron acceptor materials with high electron affinity (EA) are required to produce a high density of two-dimensional hole gas (2DHG) on the H-diamond subsurface. We have established ingenious theoretical models to demonstrate that even if these solid materials do not have a high EA value, they remain capable of absorbing electrons from the H-diamond surface by forming a negatively charged interface to act as a surface electron acceptor in the surface transfer doping model. Our calculations, particularly for the local density of states, provide compelling evidence that the effect of an interface with negative charges induces an upward band bending on the H-diamond side. Furthermore, the valence band maximum of the diamond atoms at the interface crosses the Fermi level, giving rise to strong surface transfer p-type doping. These results give a strong theoretical interpretation of the origin of 2DHG on H-diamond surfaces. The proposed guidelines contribute to further improvements in the performance of 2DHG H-diamond field effect transistors.

Precision sub-monolayer manipulation of diamond surface chemistry using laser direct write oxidation in air

Manipulation and patterning of diamond surface chemistry is of interest for a wide range of diamond-based technologies. We report the patterned oxidation of hydrogen-terminated diamond surfaces with sub-monolayer (ML) precision by a deep-UV two-photon process performed in air. Using focused laser pulses of photon energy 4.66 eV (266 nm; below the diamond bandgap of 5.47 eV), hydrogen-terminated (001) surfaces were exposed with calibrated doses to remove carbon with a precision of 0.02 ML. The measurement of the electrical properties of the laser-exposed zone between ohmic electrodes enabled monitoring of the transition from a conducting H-terminated surface to insulating O-terminated. The surface resistance increases by more than 7 orders of magnitude for doses corresponding to 0.5 ML, and the I–V characteristics show a transition from linear to nonlinear for doses above 0.30 ML. We show that this behavior agrees well with a surface percolation model for carrier diffusion in which the laser etch rate for the H-terminated top layer is the same as for O-terminated. Hence, this work reveals an ultra-precise method for modifying the sub-monolayer surface chemistry with the practical advantages of a laser-induced mechanism compared to conventional plasma or chemical processing methods.

Temperature dependence of two-dimensional hole gas on hydrogen-terminated diamond surface

The two-dimensional hole gas (2DHG) at hydrogen-terminated diamond (H-diamond) surface has been widely used in the development of diamond-based electronics. However, the carrier transport behaviors of 2DHG are still poorly understood due to the difficulty in controlling surface adsorbates on H-diamond. In this work, the temperature dependence of the electrical properties of 2DHG on H-diamond was investigated through Hall effect measurements before and after thermal annealing. The results revealed that the establishment of 2DHG equilibrium state was closely related to surface adsorbates, and temperature-induced thermal desorption of adsorbates would lead to a decrease in carrier concentration and an enhancement of mobility on H-diamond. Based on this observation, the carrier mobility of 2DHG (at 300 K) was improved from 170 to 340 cm2 V−1 s−1 after thermal annealing to 400 K. Moreover, with thermal desorption of adsorbates, the activation energy of conductance exhibited an increasing tendency, and the carrier concentration became more dependent on temperature, which can be well explained by percolation theory. A dynamic equilibrium process was also proposed to illustrate the influence of surface adsorbate on carrier concentration and mobility of 2DHG, which provides a feasible method to regulate carrier mobility and concentration on H-diamond surface.

High mobility hydrogen-terminated diamond FET with h-BN gate dielectric using pickup method

Hydrogen-terminated diamond surfaces, emerging as a promising two-dimensional (2D) electron platform with great thermal and electronic properties, hold great potential for the next-generation high power and high frequency field effect transistor (FET). However, ideal gate dielectrics with high crystallinity and defect-free surfaces are still largely elusive. In this work, using the contamination-free pickup transfer method, hexagonal boron nitride (h-BN) flakes were fabricated on top of the hydrogen-terminated diamond surface to serve as a gate material and the passivation layer. The morphological and optical characterizations revealed the formation of homogeneous and intimate interface between h-BN and diamond. Benefiting from the h-BN gate dielectric layer, the maximum drain current density, subthreshold swing, and on/off ratio of diamond FET are measured to be −210.3 mA mm−1, 161 mV/dec, and 106, respectively. Especially, the transport measurement shows an almost constant Hall mobility of around 260 cm2 V−1 s−1 in the hole density range of 2 − 6 × 1012 cm−2, suggesting the excellent gate controllability of h-BN. Our results indicate that h-BN could form high-quality interface with hydrogen-terminated diamond, paving the way for the development of diamond-based electronic applications.

Normally-off operation in vertical diamond MOSFETs using an oxidized Si-terminated diamond channel

We fabricated (001) vertical diamond metal-oxide-semiconductor field-effect transistors (MOSFETs) with oxidized Si-terminated (C–Si–O) diamond channels on the surfaces and trench sidewalls. The C–Si–O diamond surface is approximately 1.0 eV weaker in negative electron affinity than the hydrogen-terminated (C–H) diamond surface, resulting in a smaller valence band bending between the interface of C–Si–O diamond surface and Al2O3, and larger the difference between the energy values of the fermi level and the valence band on the top (EF−EV), and the threshold voltage (Vth) shifts in the negative direction. As a result, the maximum drain current density was 108 mA/mm, the Vth was −9.0 V. Compared with conventional vertical diamond FETs using a C–H channel, the Vth was shifted more than 20 V in the negative direction to reach normally-off mode. The normally-off operation was achieved while maintaining high current density, which is the first case of normally-off operation that has been observed in vertical diamond FETs. In, addition, it was confirmed that the diode functions as a freewheeling diode by adding a reverse drain voltage and allowing current to flow, and the change of current-voltage characteristics was also investigated by swapping the source and drain positions and performing measurements.

Atomic Imaging of Interface Defects in an Insulating Film on Diamond.

The insulator/semiconductor interface structure is the key to electric device performance, and much interest has been focused on understanding the origin of interfacial defects. However, with conventional techniques, it is difficult to analyze the interfacial atomic structure buried in the insulating film. Here, we reveal the atomic structure at the interface between an amorphous aluminum oxide and diamond using a developed electron energy analyzer for photoelectron holography. We find that the three-dimensional atomic structure of a C-O-Al-O-C bridge between two dimer rows of the hydrogen-terminated diamond surface. Our results demonstrate that photoelectron holography can be used to reveal the three-dimensional atomic structure of the interface between a crystal and an amorphous film. We also find that the photoelectron intensity originating from the C-O bonds is strongly related to the interfacial defect density. We anticipate significant progress in the study of amorphous/crystalline interfaces based on their three-dimensional atomic structures analysis.

Radiation effect of X-ray with 100 kGy dose on the electrical properties of MESFET based on hydrogen-terminated diamond surface conductivity

The irradiation effect of X-ray on the electrical properties of Schottky-barrier diode (SBD) and metal-semiconductor field-effect transistors (MESFET) based on the surface conductivity of hydrogen-terminated single-crystal diamond (SCD) epilayers was investigated. The Ohmic contact was formed by a Pd/Ti/Au multilayer and the Schottky metal was Al thin film for the fabrication of the diamond SBDs and MESFETs. The X-ray irradiation was performed with a dose of 100 kGy. It was observed that both the forward current of the SBDs and the drain current of the MESFETs experienced a reduction after the X-ray irradiation. The type of the single-crystal diamond substrate had an obvious effect on the radiation properties. For the MESFETs on the type-Ib SCD substrate, the variation of the drain currents as the irradiation was inhomogeneous across the devices. For the MESFETs on the type-IIa SCD substrate, the reduction of the drain currents is more uniform and the threshold voltage changed little upon X-ray irradiation. The partial oxidation in the air of the exposure area in the device and the edge of the Al gate may be responsible for the degradation of the device performance under X-ray irradiation. The passivation technique with radiation-robustness is needed for diamond devices based on the surface conductivity of diamond.

Ab initio study of the effect of 2D layer rippling on the electronic properties of 2D/H-terminated diamond (100) heterostructures

We report an ab initio study of the effect of rippling on the structural and electronic properties of the hexagonal Boron Nitride (hBN) and graphene two-dimensional (2D) layers and heterostructures created by placing these layers on the Hydrogen-terminated (H-) diamond (100) surface. Surprisingly, in graphene, rippling does not open a band gap at the Dirac point but does cause the Dirac cone to be shifted and distorted. For the 2D/H-diamond (100) heterostructures, a combined sampling and a clustering approach were used to find the most favorable alignment of the 2D layers. Heterostructures with rippled layers were found to be the most stable. A larger charge transfer was observed in the heterostructures with rippled hBN (graphene) than their planner counterparts. Band offset analysis indicates a Type-II band alignment for both the wavy and planar heterostructures, with the corrugated structure having stronger hole confinement due to the larger valence band offset between the hBN layer and the H-diamond (100) surface.Graphic abstract

Hydrogen-Terminated Diamond Surface as a Gas Sensor: A Comparative Study of Its Sensitivities.

A nanocrystalline diamond (NCD) layer is used as an active (sensing) part of a conductivity gas sensor. The properties of the sensor with an NCD with H-termination (response and time characteristic of resistance change) are measured by the same equipment with a similar setup and compared with commercial sensors, a conductivity sensor with a metal oxide (MOX) active material (resistance change), and an infrared pyroelectric sensor (output voltage change) in this study. The deposited layer structure is characterized and analyzed by Scanning Electron Microscopy (SEM) and Raman spectroscopy. Electrical properties (resistance change for conductivity sensors and output voltage change for the IR pyroelectric sensor) are examined for two types of gases, oxidizing (NO2) and reducing (NH3). The parameters of the tested sensors are compared and critically evaluated. Subsequently, differences in the gas sensing principles of these conductivity sensors, namely H-terminated NCD and SnO2, are described.

Oxygenation of Diamond Surfaces via Hummer’s Method

Oxygen bonded with diamond surfaces impacts important properties such as electrical conductivity, Schottky barrier height, field emission, and chemical reactivity. Though processes such as thermal, hydrogen plasma, etc., are efficient in oxidizing the hydrogen-terminated diamond surfaces, the oxidation of pristine diamond surfaces through wet chemical treatments is still in its infancy. Herein, we investigated the efficacy of Hummer’s method, one of the most celebrated chemical oxidation procedures to convert graphite to graphene oxide, to oxidize the pristine diamond surfaces. We attempted to oxidize both microcrystalline diamond powders and polycrystalline diamond wafers. Due to the presence of an acidic oxidative environment and the formation of strong oxidizing agents such as Mn2O7 and MnO3+ during the course of the reaction, Hummer’s method is found to be very effective in oxidizing the pristine diamond surfaces. The degree of oxygen termination is validated through various spectroscopic and surface probe measurements. Microcrystalline diamond powder is more prone to oxidation to polycrystalline diamond wafers due to excess surface area, and many facets with different dangling bond densities are exposed to the oxidizing medium. The experimental observations are endorsed through molecular dynamics simulations.

Combined electrical resistivity-electron reflectivity measurements for evaluating the homogeneity of hydrogen-terminated diamond surfaces

The homogeneity of hydrogen termination on single-crystal CVD diamond surfaces exposed to air was studied with a new approach that encloses a combination of sheet resistance measurements, performed using four-point-probe method in Van Der Pauw configuration, and electron reflectivity measurements performed at intermediate kinetic energy to derive surface sensitive information on the chemical terminations (inelastic mean free path <0.8 nm). The coherence between the 2-dimensional spatial distributions of sheet resistance and electron reflectivity maps, as well as their similar dynamic range and consistency with an electron energy loss analysis, demonstrates that the proposed combined approach allows for a reliable and easy evaluation of both the effectiveness and homogeneity of the hydrogen-termination process of a diamond surface.

Electrochemical route to bio-compatible fluorine-terminated diamond surface

In this communication, we propose a novel method to electrochemically modify hydrogen-terminated diamond surface in MISFETs with LiF dielectric at room temperature. The chemical reaction is 2F- + C–H+2h+→C–F + HF. According to measurement results of X-ray photoelectron spectroscopy on diamond, C–F bonds were produced after electrochemistry modification. A model was proposed to explain the electrochemistry modification on MISFETs. In this model, the theoretical electrolysis voltage of F− was calculated to be −3.8V, which was consistent with the experimental value of -5V.

Surface transfer doping of diamond using solution-processed molybdenum trioxide

The surface of hydrogen-terminated diamond (H-terminated diamond) supports a p-type surface conductivity when interfaced with high electron-affinity surface acceptors through the surface transfer doping process. High electron-affinity transition metal oxides (TMOs), such as MoO3, have been regarded as superior candidates in surface transfer doping of diamond, holding great promise for enabling practical diamond electronic devices. In this work, a simple, solution-processed method is demonstrated to deposit a molybdenum trioxide (MoO3) layer on H-terminated diamond surface to achieve surface transfer doping of diamond. The surface of diamond following the deposition of solution-processed MoO3 (sp-MoO3) experienced significant reduction in sheet resistivity, corresponding to an increase in hole density, compared with the pristine air-doped diamond. This hole accumulation layer induced by sp-MoO3 is thermally stable up to 450 °C, and demonstrates metallic conductivity down to 250 mK with a strong spin-orbit interaction (SOI) in the induced two-dimensional (2D) surface conducting layer. Our study demonstrates that sp-MoO3 is comparable with thermally-evaporated MoO3 in doping performance but with great advantage as a simple, inexpensive and highly flexible fabrication method for developing diamond electronics.

Investigation of charge carrier trapping in H-terminated diamond devices

Surfaces and interfaces can dominate charge carrier transport dynamics in electronic devices, impeding realization of a material's full potential. Here, we investigate transport in a two-terminal diamond device comprising a conductive channel defined by a hydrogen-terminated diamond surface, bridging two TiC contacts. The surface charge distribution was imaged by monitoring the photoluminescence of nitrogen vacancy centers incorporated below the active device layer. A strong charge accumulation near the TiC contact/H-terminated channel interface is observed and is discussed in terms of deviation from Ohmic behavior evident in the DC electrical measurements. Small voltage steps applied to the device result in current transients due to carrier trapping at the contact/diamond interface. This gives rise to dynamic negative capacitance at low AC frequencies and is discussed in detail.

Annealing Temperature on Contact Properties between Nickel Film and Hydrogen-Terminated Single Crystal Diamond

Ohmic contact of nickel on hydrogen-terminated single-crystal diamond film was investigated with an annealing temperature ranging from room temperature to 750 °C in hydrogen atmosphere. Nickel film was deposited on a hydrogen-terminated single-crystal diamond surface with gold film in order to protect it from oxidation. Contact properties between nickel and hydrogen-terminated single crystal diamond were measured by a circular transmission line model. The lowest specific contact resistivity was 7.82 × 10−5 Ω cm2 at annealing temperature of 750 °C, indicating good ohmic contact, which reveals improved thermal stability by increasing temperature.

Analysis of mobility-limiting mechanisms of the two-dimensional hole gas on hydrogen-terminated diamond

Here we present an analysis of the mobility-limiting mechanisms of a two-dimensional hole gas on hydrogen-terminated diamond surfaces. The scattering rates of surface impurities, surface roughness, non-polar optical phonons, and acoustic phonons are included. Using a Schrodinger/Poisson solver, the heavy hole, light hole, and split-off bands are treated separately. To compare the calculations with experimental data, Hall-effect structures were fabricated and measured at temperatures ranging from 25 to 700 K, with hole sheet densities ranging from 2 to 6$\times10^{12}\;\text{cm}^{-2}$ and typical mobilities measured from 60 to 100 cm$^{2}$/(V$\cdot$s) at room temperature. Existing data from literature was also used, which spans sheet densities above 1$\times10^{13}\;\text{cm}^{-2}$. Our analysis indicates that for low sheet densities, surface impurity scattering by charged acceptors and surface roughness are not sufficient to account for the low mobility. Moreover, the experimental data suggests that long-range potential fluctuations exist at the diamond surface, and are particularly enhanced at lower sheet densities. Thus, we propose a second type of surface impurity scattering which is caused by disorder related to the C-H dipoles.

Activation of the Hydrogen-Terminated Diamond [100] by Hydrogen Atoms and Hydroxyl Groups

The process of producing active vacancies on a hydrogen-terminated diamond surface is the most important rate-limiting stage in CH4/H2 and CH4/H2/CO2 atmospheres. Hydrogen atom and the hydroxyl group can bone to the hydrogen atom on the diamond surface and create an active vacancy. Density functional theory (DFT) was used to study the extraction reaction by two reactants both hydrogen atom and the hydroxyl group. The result indicated that the hydroxyl group could reduce the energy required for diamond surface activation. What is more, the activation rate of the surface by the hydroxyl group was livelier at low temperature, while the activation rate of the hydrogen atom predicts on the contrary. The scanning electron microscope (SEM) and Raman spectra demonstrated that the introduction of CO2 in the CH4/H2 atmosphere could reduce the deposition temperature and raise the deposition rate at low temperature.

Strong spin-orbit interaction induced by transition metal oxides at the surface of hydrogen-terminated diamond

Hydrogen-terminated diamond possesses an intriguing p-type surface conductivity which is induced via thermodynamically driven electron transfer from the diamond surface into surface acceptors such as atmospheric adsorbates, a process called surface transfer doping. High electron affinity transition metal oxides (TMOs) including MoO3 and V2O5 have been shown to be highly effective solid-state surface acceptors for diamond, giving rise to a sub-surface two-dimensional (2D) hole layer with metallic conduction. In this work, low temperature magnetotransport is used as a tool to show the presence of a Rashba-type spin-orbit interaction with a high spin-orbit coupling of 19.9 meV for MoO3 doping and 22.9 meV for V2O5 doping, respectively, through the observation of a transition in the phase-coherent backscattering transport from weak localization to weak antilocalization at low temperature. Surface transfer doping of diamond with TMOs provides a 2D hole system with spin-orbit coupling that is over two times larger than that reported for diamond surfaces with atmospheric acceptors, opening up possibilities to study and engineer spin transport in a carbon material system.

Palladium forms Ohmic contact on hydrogen-terminated diamond down to 4 K

A hydrogen-terminated diamond (H-terminated diamond) surface supports a two-dimensional (2D) p-type surface conductivity when exposed to the atmosphere, as a result of the surface transfer doping process. The formation of reliable Ohmic contacts that persist to cryogenic temperature is essential for the exploration of quantum transport in the diamond 2D conducting channel. Herein, the contact properties of Pd on H-terminated diamond have been fully investigated down to 4 K using transmission line method measurements. Pd is shown to form an Ohmic contact on H-terminated diamond with linear I–V characteristics and low specific contact resistance in the range of (8.4 ± 1) ×10−4 Ω·cm2 to (1.3 ± 0.2) ×10−3 Ω·cm2 for the temperature range of 300 K–4 K. This is in stark contrast to reference devices with Au/Pt/Ti contacts, which exhibit a significant temperature dependence and non-Ohmic behavior at low temperature. Using 2D thermionic emission theory, a negative Schottky barrier height (SBH), − 23 ± 1 meV, between Pd and H-terminated diamond has been determined, in comparison to a positive SBH of 42 ± 1 meV for the Au/Pt/Ti/H-terminated diamond interface. These results show that Pd serves as an excellent candidate for forming reliable Ohmic contacts on H-terminated diamond for enabling precise electrical transport measurements at cryogenic temperature.

The Flexible Lubrication Performance of Graphene Used in Diamond Interface as a Solid Lubricant: First-Principles Calculations.

The interfacial friction performances of graphene covered and hydrogen-terminated diamond surfaces were investigated comparatively by first-principles calculations within density functional theory (DFT). Both systems exhibit similar excellent lubricating effects under small load, but the graphene covered interface presents small friction than that of hydrogenated system for the larger load. The calculated interfacial friction between two sheets of graphene covered diamond surface increases slowly than that of hydrogenated system in a wide range of pressure scale, and the friction difference between the two systems increases with increasing external pressure, indicating that graphene has flexible lubricating properties with high load-carrying capacity. This behavior can be attributed to the large interlayer space and a more uniform interlayer charge distribution of graphene covered diamond interface. Our investigations suggest that graphene is a promising candidate as solid lubricate used in diamond film, and are helpful for the understanding of interfacial friction properties of diamond film.