Conduction Band Offset Energies Research Articles

InAs MOS devices passivated with molecular beam epitaxy-grown Gd2O3 dielectrics

InAs MOS devices passivated with molecular beam epitaxy (MBE)-grown Gd2O3 2–3 monolayers thick followed by an Al2O3 cap have demonstrated excellent electrical performances and interfacial properties. Band offset energies of in situ atomic-layer-deposited (ALD)-Al2O3/MBE-Gd2O3/InAs and ALD-Al2O3/InAs were determined by in situ x-ray photoelectron spectroscopy in conjunction with Fowler–Nordheim tunneling current analysis. A conduction-band offset energy (ΔEc) and a valence-band offset energy of 2.3 and 3.92 eV for ALD-Al2O3/InAs were determined, respectively. The insertion of a Gd2O3 layer increases the value of ΔEc by nearly 0.1 eV as compared to the case for Al2O3 directly deposited on InAs. The distribution of interfacial density of states (Dit) within the InAs bandgap, deduced by the conductance method at 77 K, gives a low Dit value of 1012 cm−2 eV−1 near the conduction-band edge. Moreover, with energy band engineering in the heterostructure, gate-first depletion channel InAs MOSFETs have produced drain current density of 46 μA/μm and transconductance of 17 μS/μm for 12-μm-gate-length devices at 300 K.

Elimination of GeO 2 and Ge 3N 4 interfacial transition regions and defects at n-type Ge interfaces: A pathway for formation of n-MOS devices on Ge substrates

The contribution from relatively low -K SiON interfacial transition regions (ITRs) between Si and transition metal (TM) gate dielectrics places a significant limitation on equivalent oxide thickness (EOT) scaling for Si complementary metal-oxide-semiconductor (CMOS) devices. This limitation is equally significant and limiting for Ge CMOS devices. Low-K Ge-based ITRs in Ge devices have also been shown to limit performance and reliability, particular for n-MOS field effect transistors. This article identifies the source of significant electron trapping at interfaces between n-Ge or inverted p-Ge, and Ge oxide, nitride and oxynitride ITRs. This is shown to be an interfacial band alignment issue in which native Ge ITRs have conduction band offset energies smaller than those of TM dielectrics, and trap electrons for negative Ge substrate bias. This article also describes a novel remote plasma processing approach for effectively eliminating any significant native Ge ITRs and using a plasma-processing/annealing process sequence for bonding TM gate dielectrics directly to the Ge substrate surface.

Spectroscopic studies of metal high-k dielectrics: transition metal oxides and silicates, and complex rare earth/transition metal oxides

This paper uses X-ray absorption spectroscopy to the study of electronic structure of the transition metal oxides TiO2, ZrO2 and HfO2, Zr and Hf silicate alloys, and the complex oxides, GdScO3, DyScO3 and HfTiO4. Qualitative and quantitative differences are identified between dipole allowed intra-atomic transitions from core p-states to empty d*- and s*-states, and inter-atomic transitions from transition metal and oxide 1s states to O 2p* that are mixed with transition metal d*- and s*-states for transition metal oxides and silicate alloys. The complex oxide studies have focused on the O K1 edge spectra. Differences between the spectral peak energies of the lowest d*-features in the respective O K1 spectra are demonstrated to scale with optical band gap differences for TiO2, ZrO2 and HfO2, as well as the complex oxides providing important information relevant to applications of TM oxides as high-k gate dielectrics in advanced Si devices. This is demonstrated through scaling relationships between (i) conduction band offset energies between Si and the respective dielectrics, and the optical band gaps, and (ii) the optical band gaps, the conduction band offset energies, and the electron tunneling masses as functions of the atomic d-state energies of the transition metal atoms.

X-ray absorption spectra for transition metal high-κ dielectrics: Final state differences for intra- and inter-atomic transitions

This article applies x-ray absorption spectroscopy to a study of the electronic structure of the high-k gate dielectrics, TiO2, ZrO2, and HfO2. Qualitative and quantitative differences are identified between intra-atomic transitions such as the Zr 3p-state, M2,3 core state absorptions which terminate in TM 4d*- and 5s*-states, and inter-atomic transitions such as the Zr 1s- and O 1s-state K1 absorptions which terminate in Zr 4d*- and 5s*-states that are mixed with O atom 2p* states through nearest neighbor bonding interactions. Differences between the spectral peak energies of the lowest d*-features in the O K1 spectra are demonstrated to scale with optical band gap differences for TiO2, ZrO2, and HfO2, providing important information relevant to applications of TM oxides as high-κ gate dielectrics in advanced Si devices. This is demonstrated through additional scaling relationships between (i) conduction band offset energies between Si and the respective dielectrics, and the optical band gaps, and (ii) the conduction band offset energies, and the electron tunneling masses as well.

Band offset energies in zirconium silicate Si alloys

Transition metal silicates, (ZrO 2) x (SiO 2) 1− x , with dielectric constants, k>10 have been proposed as alternative dielectrics for advanced Si devices. Studies by X-ray absorption, X-ray photoelectron and Auger electron spectroscopy are combined to identify the compositional variation of the valence and conduction band offset energies with respect to Si in Zr silicate alloys. The minimum conduction band offset energy, associated with localized Zr 4d ∗-states, is ∼1.4 eV, and is independent of alloy composition, while valence band offsets decrease monotonically with increasing ZrO 2 content. Differences between the coupling of tunneling electrons to localized Zr 4d ∗ and extended Si 3s ∗ states, characterized by respective tunneling masses of ∼0.5 m o and ∼0.2 m o, combine to contribute to a minimum in the direct tunneling current in the mid-silicate-alloy composition range, x∼0.4–0.6.

Electronic structure of transition metal high-k dielectrics: interfacial band offset energies for microelectronic devices

Transition metal silicates, (ZrO2)x(SiO2)1−x, have dielectric constants k>10 that make them attractive for advanced Si devices. Band offset energies relative to Si are an important factor in determining tunneling leakage current, and internal photoemission. Studies by X-ray photoelectron spectroscopy (XPS), Auger electron spectroscopy (AES) and X-ray absorption spectroscopy (XAS) are combined with ab initio calculations to identify the compositional variation of the band-gap, and valence and conduction band offset energies of Zr silicate alloys with respect to Si. The minimum conduction band offset, due to Zr 4d∗ states, is shown to be independent of alloy composition, while valence band offsets decrease monotonically with increasing ZrO2 content. The implications of these results for direct tunneling are discussed.

Nonlinear composition dependence of x-ray photoelectron spectroscopy and Auger electron spectroscopy features in plasma-deposited zirconium silicate alloy thin films

The local bonding of Zr, Si, and O atoms in plasma-deposited, and post-deposition annealed Zr silicate pseudobinary alloys [(ZrO2)x(SiO2)1−x] was studied by x-ray photoelectron spectroscopy (XPS) and Auger electron spectroscopy (AES). Systematic decreases in XPS binding energies, and increases in AES kinetic energies with alloy composition x are consistent with an empirical chemical bonding model based on electronegativity equalization; however, there are significant departures from the predicted linear composition dependencies of that model. Deviations from linearity in the XPS compositional dependencies are correlated with dipolar network atom fields as determined from ab initio calculations. The nonlinearities in the x dependence of ZrMVV and OKVV AES spectral features are determined primarily by oxygen–atom coordination dependent shifts in valence band offset energies. The energy spread in the compositional dependence of binding energies (∼1.85 eV) for the XPS Zr 3d5/2 and Si 2p features combined with x-ray absorption spectroscopy data indicates that the conduction band offset energies between the Si substrate and Zr silicate dielectrics are alloy composition independent. Changes in O 1s XPS features in alloys with x∼0.3 to 0.6 as function of annealing temperature are consistent with a previously identified chemical phase separation that occurs after 60 s anneals at 900 °C in a nonoxidizing ambient, Ar.

A molecular orbital model for the electronic structure of transition metal atoms in silicate and aluminate alloys

A classification scheme that separates non-crystalline dielectrics into three groups with different amorphous morphologies reveals an approximately linear relationship between oxygen atom coordination and average bond ionicity. When applied to transition metal (TM) and rare earth (RE) lanthanide oxides, and their silicate and aluminate alloys, this approach demonstrates a correlation between stability against crystallization and oxygen atom coordination. It also provides a local bonding model for local molecular orbital calculations that are based on the coordination and symmetry of TM and RE atoms and the orbital energies of their oxygen neighbors. These calculations provide important insights into the electronic structure of TM and RE dielectrics, and in particular the role of atomic d-state energies in providing a scaling parameter for conduction band offset energies between gate dielectrics and the Si substrate.

A molecular orbital model for the electronic structure of transition metal atoms in silcate and aluminate alloys

Applied to transition metal oxides and silicate and aluminate alloys, a classification scheme that separates non-crystalline dielectrics into three groups with different amorphous morphologies, demonstrates a direct correlation between stability against crystallization and oxygen atom coordination. It also provides a local bonding model for molecular orbital (MO), calculations that are based on the coordination and symmetry of transition metal atoms and the orbital energies of their oxygen neighbors. These calculations provide important insights into the electronic structure of transition metal dielectrics, e.g. the role of anti-bonding d-states in determining conduction band offset energies with respect to Si.

Correlations between electronic structure of transition metal atoms and performance of high-k gate dielectrics in advanced Si devices

This paper develops a classification scheme for non-crystalline dielectrics that separates them into three groups with different amorphous morphologies, and identifies a linear scaling relationship between average bond ionicity and oxygen atom coordination. The classification scheme is applied to transition metal silicate and aluminate alloys and provides a structural model for molecular orbital, MO, calculations that are based on the coordination and symmetry of transition metal atoms and the orbital energies of their oxygen neighbors. The MO calculations show that conduction band offset energies with respect to Si scale inversely with the energy difference between transition metal atomic n+1 s- and n d-states providing an important insight into the choice of alternative gate dielectrics for advanced Si devices.

Limitations for aggressively scaled CMOS Si devices due to bond coordination constraints and reduced band offset energies at Si-high- k dielectric interfaces

The three chemical bonding effects at Si-dielectric interfaces that are important in substituting alternative gate dielectric materials for SiO 2 in aggressively scaled CMOS are (i) the character of the interface bonds, either isovalent with bond and nuclear charge balanced as in Si–SiO 2, or heterovalent, where there is an inherent mismatch between bond and nuclear charge, (ii) physical bonding constraints related to the average number of bonds/atom, N av and (iii) reduced conduction band offset energies in transition metal (T-M) elemental and binary oxides that are derived from increased ionic bonding and d-state contributions to the lowest conduction bands. These effects are discussed with respect to several different emerging high- k materials including (i) nitrides, (ii) T-M oxides, (iii) alloys of SiO 2 and T-M oxides and (iv) Al 2O 3.

The effects of chemical bonding and band offset constraints at Si-dielectric interfaces on the integration of alternative high-K dielectrics into aggressively-scaled CMOS Si devices

This paper identifies three aspects of the chemical bonding at Si-dielectric interfaces that play crucial roles in the implementation of alternative gate dielectrics for advanced CMOS Si devices: i) the character of the interface bonds, either isovalent with bond and nuclear charge balanced as in SiSiO 2, or heterovalent, with an inherent mismatch between bond and nuclear charge, ii) physical bonding constraints related to the average number of bonds/atom, N av, and iii) reduced conduction band offset energies that are result because of increased ionic bonding and d-state derived conduction bands in transition metal oxides.