Yves J. Chabal

Ideal hydrogen termination of the Si (111) surface

Aqueous HF etching of silicon surfaces results in the removal of the surface oxide and leaves behind silicon surfaces terminated by atomic hydrogen. The effect of varying the solution pH on the surface structure is studied by measuring the SiH stretch vibrations with infrared absorption spectroscopy. Basic solutions ( pH=9–10) produce ideally terminated Si(111) surfaces with silicon monohydride ( 3/4 SiH) oriented normal to the surface. The surface is found to be very homogeneous with low defect density (<0.5%) and narrow vibrational linewidth (0.95 cm−1 ).

Surface infrared spectroscopy

Abstract Infrared spectroscopy has become a useful tool to investigate surfaces. The theoretical and experimental foundation of surface IR spectroscopy is described and selected examples are presented to illustrate the kind of information derived in several important areas of surface science such as chemistry, structure, dynamics and kinetics at surfaces.

Infrared spectroscopy of Si(111) and Si(100) surfaces after HF treatment: Hydrogen termination and surface morphology

Multiple internal infrared reflection spectroscopy has been used to identify the chemical nature of chemically oxidized and subsequently HF stripped silicon surfaces. These very inert surfaces are found to be almost completely covered by atomic hydrogen. Results using polarized radiation on both flat and stepped Si(111) and Si(100) surfaces reveal the presence of many chemisorption sites (hydrides) that indicate that the surfaces are microscopically rough, although locally ordered. In particular, the HF‐prepared Si(100) surface appears to have little in common with the smooth H‐saturated Si(100) surface prepared in ultrahigh vacuum.

Comparison of Si(111) surfaces prepared using aqueous solutions of NH4F versus HF

Vacuum scanning tunneling microscopy has been used to investigate the hydrogen‐terminated Si(111) surfaces obtained upon dissolution of the native oxide in HF and NH4F solutions. Whereas etching in aqueous HF acid produces an atomically rough surface, comparable treatment in NH4F results in atomically flat surfaces. These atomically flat surfaces are extremely well ordered and exhibit terraces which extend thousands of angstroms.

Infrared spectroscopy of Si(111) surfaces after HF treatment: Hydrogen termination and surface morphology

Polarized internal reflection spectroscopy has been used to characterize HF‐treated Si(111) surfaces. The silicon‐hydrogen stretching vibrations indicate that the surface is well ordered, but is microscopically rough, with coupled monohydride, dihydride, and trihydride termination.

Enhanced Binding Affinity, Remarkable Selectivity, and High Capacity of CO2 by Dual Functionalization of a rht‐Type Metal–Organic Framework

This work was supported by the Foundation of the National Natural Science Foundation of China (grant numbers 20971054 and 90922034) and the Key Project of the Chinese Ministry of Education. The RU and UTD teams would like to acknowledge support from DOE (grant number DE-FG02-08ER46491). We thank Prof. Xianhe Bu and Dr. Ze Chang (Nankai University, China) and Dr. Ruiping Chen (Fujian Institute of Research on the Structure of Matter, Chinese Academy of Sciences) for part of the gas adsorption measurements.

On the mechanism of the hydrogen-induced exfoliation of silicon

We have investigated the fundamental mechanism underlying the hydrogen-induced exfoliation of silicon, using a combination of spectroscopic and microscopic techniques. We have studied the evolution of the internal defect structure as a function of implanted hydrogen concentration and annealing temperature and found that the mechanism consists of a number of essential components in which hydrogen plays a key role. Specifically, we show that the chemical action of hydrogen leads to the formation of (100) and (111) internal surfaces above 400 °C via agglomeration of the initial defect structure. In addition, molecular hydrogen is evolved between 200 and 400 °C and subsequently traps in the microvoids bounded by the internal surfaces, resulting in the build-up of internal pressure. This, in turn, leads to the observed “blistering” of unconstrained silicon samples, or complete layer transfer for silicon wafers joined to a supporting (handle) wafer which acts as a mechanical “stiffener.”

Properties of high κ gate dielectrics Gd2O3 and Y2O3 for Si

We present the materials growth and properties of both epitaxial and amorphous films of Gd2O3 (κ=14) and Y2O3 (κ=18) as the alternative gate dielectrics for Si. The rare earth oxide films were prepared by ultrahigh vacuum vapor deposition from an oxide source. The use of vicinal Si (100) substrates is key to the growth of (110) oriented, single domain films in the Mn2O3 structure. Compared to SiO2 gate oxide, the crystalline Gd2O3 and Y2O3 oxide films show a reduction of electrical leakage at 1 V by four orders of magnitude over an equivalent oxide thickness range of 10–20 A. The leakage of amorphous Y2O3 films is about six orders of magnitude better than SiO2 due to a smooth morphology and abrupt interface with Si. The absence of SiO2 segregation at the dielectric/Si interface is established from infrared absorption spectroscopy and scanning transmission electron microscopy. The amorphous Gd2O3 and Y2O3 films withstand the high temperature anneals to 850 °C and remain electrically and chemically intact.

Intermixing at the tantalum oxide/silicon interface in gate dielectric structures

Metal oxides with high dielectric constants have the potential to extend scaling of transistor gate capacitance beyond that of ultrathin silicon dioxide. However, during deposition of most metal oxides on silicon, an interfacial region of SiOx can form that limits the specific capacitance of the gate structure. We have examined the composition of this layer using high-resolution depth profiling of medium ion energy scattering combined with infrared spectroscopy and transmission electron microscopy. We find that the interfacial region is not pure SiO2, but is a complex depth-dependent ternary oxide of Si–Tax–Oy with a dielectric constant at least twice that of pure SiO2 as inferred from electrical measurements. High-temperature annealing crystallizes the Ta2O5 film and converts the composite oxide to a more pure SiO2 layer with a lower capacitance density. Using low postanneal temperatures, a stable composite oxide structure can be obtained with good electrical properties and an effective SiO2 thickness of...

HfO2 and Al2O3 gate dielectrics on GaAs grown by atomic layer deposition

High-performance metal-oxide-semiconductor field effect transistors (MOSFETs) on III–V semiconductors have long proven elusive. High-permittivity (high-κ) gate dielectrics may enable their fabrication. We have studied hafnium oxide and aluminum oxide grown on gallium arsenide by atomic layer deposition. As-deposited films are continuous and predominantly amorphous. A native oxide remains intact underneath HfO2 during growth, while thinning occurs during Al2O3 deposition. Hydrofluoric acid etching prior to growth minimizes the final interlayer thickness. Thermal treatments at ∼600°C decompose arsenic oxides and remove interfacial oxygen. These observations explain the improved electrical quality and increased gate stack capacitance after thermal treatments.