The nitrides of most of the group IVb-Vb-VIb transition metals (TiN, ZrN, HfN, VN, NbN, TaN, MoN, WN) constitute the unique category of conductive ceramics. Having substantial electronic conductivity, exceptionally high melting points and covering a wide range of work function values, they were considered for a variety of electronic applications, which include diffusion barriers in metallizations of integrated circuits, Ohmic contacts on compound semiconductors, and thin film resistors, since early eighties. Among them, TiN and ZrN are recently emerging as significant candidates for plasmonic applications. So the possible plasmonic activity of the rest of transition metal nitrides (TMN) emerges as an important open question. In this work, we exhaustively review the experimental and computational (mostly ab initio) works in the literature dealing with the optical properties and electronic structure of TMN spanning over three decades of time and employing all the available growth techniques. We critically evaluate the optical properties of all TMN and we model their predicted plasmonic response. Hence, we provide a solid understanding of the intrinsic (e.g. the valence electron configuration of the constituent metal) and extrinsic (e.g. point defects and microstructure) factors that dictate the plasmonic performance. Based on the reported optical spectra, we evaluate the quality factors for surface plasmon polariton and localized surface plasmon for various TMN and critically compare them to each other. We demonstrate that, indeed TiN and ZrN along with HfN are the most well-performing plasmonic materials in the visible range, while VN and NbN may be viable alternatives for plasmonic devices in the blue, violet and near UV ranges, albeit in expense of increased electronic loss. Furthermore, we consider the alloyed ternary TMN and by critical evaluation and comparison of the reported experimental and computational works, we identify the emerging optimal tunable plasmonic conductors among the immense number of alloying combinations.

Conductive nitrides: Growth principles, optical and electronic properties, and their perspectives in photonics and plasmonics

The dependence of the metal-gate work function on the annealing temperature is experimentally studied. We observe increased Fermi-level pinning of the metal-gate work function with increased annealing temperature. This effect is more significant for SiO/sub 2/ than for HfO/sub 2/ gate dielectric. A metal-dielectric interface model that takes the role of extrinsic states into account is proposed to explain the work function thermal instability. This letter provides new understanding on work function control for metal-gate transistors and on metal-dielectric interfaces.

Fermi pinning-induced thermal instability of metal-gate work functions

In this Letter, the mechanism of double forming process phenomenon revealing in ZrO2/HfO2 bilayer resistive random access memory structure is investigated. This phenomenon caused by the formation of TiON interfacial layer can be well explained by using the energy band diagram. The TiON interfacial layer will be a tunneling barrier during the first forming process when a negative voltage applied on the device, while it will breakdown when applying a positive voltage. Besides, due to the double forming process, an asymmetric conductive filament with narrower size at ZrO2/HfO2 interface is formed in the device. The point for formation and rupture of the conductive filament can be confined at the ZrO2/HfO2 interface, and it will suppress the consumption of oxygen ions during endurance test. Therefore, high speed (40 ns) and large endurance (107 cycles) characteristics are achieved in this device structure.

https://ir.nctu.edu.tw:443/bitstream/11536/23787/1/000331803800060.pdf

Switching mechanism of double forming process phenomenon in ZrOx/HfOy bilayer resistive switching memory structure with large endurance

Remote plasma atomic layer deposition (ALD) of TaNx films from Ta[N(CH3)2]5 and H2, H2-N2, and NH3 plasmas is reported. From film analysis by in situ spectroscopic ellipsometry and various ex situ techniques, data on growth rate, atomic composition, mass density, TaNx microstructure, and resistivity are presented for films deposited at substrate temperatures between 150 and 250°C. It is established that cubic TaNx films with a high mass density (12.1gcm−3) and low electrical resistivity (380μΩcm) can be deposited using a H2 plasma with the density and resistivity of the films improving with plasma exposure time. H2-N2 and NH3 plasmas resulted in N-rich Ta3N5 films with a high resistivity. It is demonstrated that the different TaNx phases can be distinguished in situ by spectroscopic ellipsometry on the basis of their dielectric function with the magnitude of the Drude absorption yielding information on the resistivity of the films. In addition, the saturation of the ALD surface reactions can be determined...

/pdf/synthesis-and-in-situ-characterization-of-low-resistivity-5c5sre22qj.pdf

Synthesis and in situ characterization of low-resistivity TaNx films by remote plasma atomic layer deposition

We demonstrate that the use of a monolayer graphene as a gate electrode on top of a high-κ gate dielectric eliminates mechanical-stress-induced-gate dielectric degradation, resulting in a quantum leap of gate dielectric reliability. The high work function of hole-doped graphene also helps reduce the quantum mechanical tunneling current from the gate electrode. This concept is applied to nonvolatile Flash memory devices, whose performance is critically affected by the quality of the gate dielectric. Charge-trap flash (CTF) memory with a graphene gate electrode shows superior data retention and program/erase performance that current CTF devices cannot achieve. The findings of this study can lead to new applications of graphene, not only for Flash memory devices but also for other high-performance and mass-producible electronic devices based on MOS structure which is the mainstream of the electronic device industry.

Graphene gate electrode for MOS structure-based electronic devices.

Tantalum nitride (TaN) films were prepared by reactive sputtering in a gas Ar and N2 for gate electrode applications. Resistivity, crystallinity, and work function of the films were investigated as a function of nitrogen flow rate. As the nitrogen flow rate increased from 0 to 20 sccm, the resistivity of as-deposited TaN films increased from 132 to 1.4×105 μΩ cm. With a nitrogen flow rate of 8 and 10 sccm, the fcc TaN phase was obtained. The work function of the TaN films was investigated using TaN-gated nmetal–oxide–semiconductor capacitors with SiO2 gate dielectrics of various thicknesses. As the nitrogen flow rate increased from 4 to 12 sccm, the work function decreased from 4.1 to 3.4 eV for as-deposited films. After annealing at 950 °C for 1 min, the work function increased to 4.5–4.7 eV, with less dependency on the nitrogen flow rate.

K. Onishi

Papers

Characterization of resistivity and work function of sputtered-TaN film for gate electrode applications