C. L. Hinkle

GaAs interfacial self-cleaning by atomic layer deposition

The reduction and removal of surface oxides from GaAs substrates by atomic layer deposition (ALD) of Al2O3 and HfO2 are studied using in situ monochromatic x-ray photoelectron spectroscopy. Using the combination of in situ deposition and analysis techniques, the interfacial “self-cleaning” is shown to be oxidation state dependent as well as metal organic precursor dependent. Thermodynamics, charge balance, and oxygen coordination drive the removal of certain species of surface oxides while allowing others to remain. These factors suggest proper selection of surface treatments and ALD precursors can result in selective interfacial bonding arrangements.

Defect-Dominated Doping and Contact Resistance in MoS2

Achieving low resistance contacts is vital for the realization of nanoelectronic devices based on transition metal dichalcogenides. We find that intrinsic defects in MoS2 dominate the metal/MoS2 contact resistance and provide a low Schottky barrier independent of metal contact work function. Furthermore, we show that MoS2 can exhibit both n-type and p-type conduction at different points on a same sample. We identify these regions independently by complementary characterization techniques and show how the Fermi level can shift by 1 eV over tens of nanometers in spatial resolution. We find that these variations in doping are defect-chemistry-related and are independent of contact metal. This raises questions on previous reports of metal-induced doping of MoS2 since the same metal in contact with MoS2 can exhibit both n- and p-type behavior. These results may provide a potential route for achieving low electron and hole Schottky barrier contacts with a single metal deposition.

Detection of Ga suboxides and their impact on III-V passivation and Fermi-level pinning

The passivation of interface states remains an important problem for III-V based semiconductor devices. The role of the most stable bound native oxides GaOx (0.5≤x≤1.5) is of particular interest. Using monochromatic x-ray photoelectron spectroscopy in conjunction with controlled GaAs(100) and InGaAs(100) surfaces, a stable suboxide (Ga2O) bond is detected at the interface but does not appear to be detrimental to device characteristics. In contrast, the removal of the Ga 3+ oxidation state (Ga2O3) is shown to result in the reduction of frequency dispersion in capacitors and greatly improved performance in III-V based devices.

Half-cycle atomic layer deposition reaction studies of Al2O3 on In0.2Ga0.8As (100) surfaces

The reduction in III–V interfacial oxides by atomic layer deposition of Al2O3 on InGaAs is studied by interrupting the deposition following individual trimethyl aluminum (TMA) and water steps (half cycles) and interrogation of the resultant surface reactions using in situ monochromatic x-ray photoelectron spectroscopy (XPS). TMA is found to reduce the interfacial oxides during the initial exposure. Concentrations of Ga oxide on the surface processed at 300 °C are reduced to a concentration on the order of a monolayer, while AsOx species are below the level of detection of XPS.

HfO2 on MoS2 by Atomic Layer Deposition: Adsorption Mechanisms and Thickness Scalability

We report our investigation of the atomic layer deposition (ALD) of HfO2 on the MoS2 surface. In contrast to previous reports of conformal growth on MoS2 flakes, we find that ALD on MoS2 bulk material is not uniform. No covalent bonding between the HfO2 and MoS2 is detected. We highlight that individual precursors do not permanently adsorb on the clean MoS2 surface but that organic and solvent residues can dramatically change ALD nucleation behavior. We then posit that prior reports of conformal ALD deposition on MoS2 flakes that had been exposed to such organics and solvents likely rely on contamination-mediated nucleation. These results highlight that surface functionalization will be required before controllable and low defect density high-κ/MoS2 interfaces will be realized. The band structure of the HfO2/MoS2 system is experimentally derived with valence and conduction band offsets found to be 2.67 and 2.09 eV, respectively.

Impurities and Electronic Property Variations of Natural MoS2 Crystal Surfaces

Room temperature X-ray photoelectron spectroscopy (XPS), inductively coupled plasma mass spectrometry (ICPMS), high resolution Rutherford backscattering spectrometry (HR-RBS), Kelvin probe method, and scanning tunneling microscopy (STM) are employed to study the properties of a freshly exfoliated surface of geological MoS2 crystals. Our findings reveal that the semiconductor 2H-MoS2 exhibits both n- and p-type behavior, and the work function as measured by the Kelvin probe is found to vary from 4.4 to 5.3 eV. The presence of impurities in parts-per-million (ppm) and a surface defect density of up to 8% of the total area could explain the variation of the Fermi level position. High resolution RBS data also show a large variation in the MoSx composition (1.8 < x < 2.05) at the surface. Thus, the variation in the conductivity, the work function, and stoichiometry across small areas of MoS2 will have to be controlled during crystal growth in order to provide high quality uniform materials for future device fabrication.

Frequency dispersion reduction and bond conversion on n-type GaAs by in situ surface oxide removal and passivation

The method of surface preparation on n-type GaAs, even with the presence of an amorphous-Si interfacial passivation layer, is shown to be a critical step in the removal of accumulation capacitance frequency dispersion. In situ deposition and analysis techniques were used to study different surface preparations, including NH4OH, Si-flux, and atomic hydrogen exposures, as well as Si passivation depositions prior to in situ atomic layer deposition of Al2O3. As–O bonding was removed and a bond conversion process with Si deposition is observed. The accumulation capacitance frequency dispersion was removed only when a Si interlayer and a specific surface clean were combined.

Investigation of postoxidation thermal treatments of Si/SiO2 interface in relationship to the kinetics of amorphous Si suboxide decomposition

Interfacial Si suboxides (SiOx, x 500 °C initially there is a rapid segregation into amorphous Si (a-Si) surrounded by a SiO2 shell which acts as a diffusion barrier decelerating the reaction. Phenomenological modeling of kinetics with a one-dimensional Avrami–Erofe’ve treatment gives an upper limit for a-Si lateral growth rates of 1.2 A/s at 900 °C with an activation energy of 120 kJ/mol. PL, Raman, transmission electron microscopy and ellipsometry confirm this segregation model in the amorphous state. Due to the ra...

Suppression of subcutaneous oxidation during the deposition of amorphous lanthanum aluminate on silicon

Amorphous LaAlO3 thin films have been deposited by molecular beam deposition directly on silicon without detectable oxidation of the underlying substrate. We have studied these abrupt interfaces by Auger electron spectroscopy, high-resolution transmission electron microscopy, medium-energy ion scattering, transmission infrared absorption spectroscopy, and x-ray photoelectron spectroscopy. Together these techniques indicate that the films are fully oxidized and have less than 0.2 A of SiO2 at the interface between the amorphous LaAlO3 and silicon. These heterostructures are being investigated for alternative gate dielectric applications and provide an opportunity to control the interface between the silicon and the gate dielectric.

Half-cycle atomic layer deposition reaction studies of Al2O3 on (NH4)2S passivated GaAs(100) surfaces

“Half-cycle” atomic layer deposition reactions of trimethyl aluminum (TMA) and water on GaAs exposed to wet chemical sulfur treatments are studied for the formation of Al2O3. Trivalent oxides of gallium and arsenic are completely reduced following the first TMA pulse. The same processing step also removes As–S bonding below the level of detection, while the relative concentration of gallium suboxides as well as Ga–S bonds is not affected. A concomitant decrease in the S 2p peak intensity is observed, indicating that sulfur is lost through a volatile reaction product. Further precursor exposures do not measurably affect substrate surface chemistry.