F. S. Aguirre-Tostado

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.

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.

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.

Copper-metal deposition on self assembled monolayer for making top contacts in molecular electronic devices.

Molecular electronics is an attractive option for low-cost devices because it involves highly uniform self-assembly of molecules with a variety of possible functional groups. However, the potential of molecular electronics can only be turned into practical applications if reliable contacts can be established without damaging the organic layer or contaminating its interfaces. Here, a method is described to prepare tightly packed carboxyl-terminated alkyl self-assembled monolayers (SAMs) that are covalently attached to silicon surfaces and to deposit thin metallic copper top contact electrodes without damage to this layer. This method is based on a two-step procedure for SAM preparation and the implementation of atomic layer deposition (ALD) using copper di-sec-butylacetamidinate [Cu(sBu-amd)](2). In situ and ex situ infrared spectroscopy (IRS), X-ray photoelectron spectroscopy (XPS), atomic force microscopy (AFM), and electrical measurements are used to characterize the chemical modification of the Si/SAM interface, the perturbation of the SAM layer itself, and the metal homogeneity and interaction with the SAM headgroups. This work shows that (i) carboxyl-terminated alkyl monolayers can be prepared with the same high density and quality as those achieved for less versatile methyl-terminated alkyl monolayers, as evidenced by electrical properties that are not dominated by interface defects; (ii) Cu is deposited with ALD, forming a bidentate complexation between the Cu and the COOH groups during the first half cycle of the ALD reaction; and (iii) the Si/SAM interface remains chemically intact after metal deposition. The nondamaging thin Cu film deposited by ALD protects the SAM layer, making it possible to deposit a thicker metal top contact leading ultimately to a controlled preparation of molecular electronic devices.

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.

Interface studies of GaAs metal-oxide-semiconductor structures using atomic-layer-deposited HfO2∕Al2O3 nanolaminate gate dielectric

A systematic capacitance-voltage study has been performed on GaAs metal-oxide-semiconductor (MOS) structures with atomic-layer-deposited HfO2∕Al2O3 nanolaminates as gate dielectrics. A HfO2∕Al2O3 nanolaminate gate dielectric improves the GaAs MOS characteristics such as dielectric constant, breakdown voltage, and frequency dispersion. A possible origin for the widely observed larger frequency dispersion on n-type GaAs than p-type GaAs is discussed. Further experiments show that the observed hysteresis is mainly from the mobile changes and traps induced by HfO2 in bulk oxide instead of those at oxide/GaAs interface.

Indium stability on InGaAs during atomic H surface cleaning

Atomic H exposure of a GaAs surface at 390°C is a relatively simple method for removing the native oxides without altering the surface stoichiometry. In-situ reflection high energy electron diffraction and angle-resolved x-ray photoelectron spectroscopy have been used to show that this procedure applied to In0.2Ga0.8As effectively removes the native oxides resulting in an atomically clean surface. However, the bulk InGaAs stoichiometry is not preserved from this treatment. The In:Ga ratio from the substrate is found to decrease by 33%. The implications for high-mobility channel applications are discussed as the carrier mobility increases nearly linearly with the In content.

Comparison of n-type and p-type GaAs oxide growth and its effects on frequency dispersion characteristics

The electrical characteristics of n- and p-type gallium arsenide (GaAs) capacitors show a striking difference in the “accumulation” capacitance frequency dispersion. This difference has been attributed by some to a variation in the oxide growth, possibly due to photoelectrochemical properties of the two substrates. We show that the oxide growth on n- and p-type GaAs substrates is identical when exposed to identical environmental and chemical conditions while still maintaining the diverse electrical characteristics. The difference in electron and hole trap time constants is suggested as the source of the disparity of the frequency dispersion for n-type versus p-type GaAs devices.

S passivation of GaAs and band bending reduction upon atomic layer deposition of HfO2/Al2O3 nanolaminates

A systematic study of the interface engineering and dielectric properties of nanolaminated hafnium aluminate on GaAs is presented. The dielectrics were deposited using atomic layer deposition of alternating cycles of HfO2 and Al2O3 on GaAs substrates. High resolution x-ray photoelectron spectroscopy XPS showed differences in space charge amounts at the interface for the two surface treatments NH4OH or NH42S. In-situ XPS analysis shows that chemical bonding to oxygen across the nanolaminate film is independent of the interface formation conditions. In addition, the GaAs surface treated with NH42S shows a decreased band bending and slightly thinner films with respect to NH4OH.