Many materials systems are currently under consideration as potential replacements for SiO2 as the gate dielectric material for sub-0.1 μm complementary metal–oxide–semiconductor (CMOS) technology. A systematic consideration of the required properties of gate dielectrics indicates that the key guidelines for selecting an alternative gate dielectric are (a) permittivity, band gap, and band alignment to silicon, (b) thermodynamic stability, (c) film morphology, (d) interface quality, (e) compatibility with the current or expected materials to be used in processing for CMOS devices, (f) process compatibility, and (g) reliability. Many dielectrics appear favorable in some of these areas, but very few materials are promising with respect to all of these guidelines. A review of current work and literature in the area of alternate gate dielectrics is given. Based on reported results and fundamental considerations, the pseudobinary materials systems offer large flexibility and show the most promise toward success...

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High-κ gate dielectrics: Current status and materials properties considerations

The scaling of complementary metal oxide semiconductor transistors has led to the silicon dioxide layer, used as a gate dielectric, being so thin (14?nm) that its leakage current is too large It is necessary to replace the SiO2 with a physically thicker layer of oxides of higher dielectric constant (?) or 'high K' gate oxides such as hafnium oxide and hafnium silicate These oxides had not been extensively studied like SiO2, and they were found to have inferior properties compared with SiO2, such as a tendency to crystallize and a high density of electronic defects Intensive research was needed to develop these oxides as high quality electronic materials This review covers both scientific and technological issues?the choice of oxides, their deposition, their structural and metallurgical behaviour, atomic diffusion, interface structure and reactions, their electronic structure, bonding, band offsets, electronic defects, charge trapping and conduction mechanisms, mobility degradation and flat band voltage shifts The oxygen vacancy is the dominant electron trap It is turning out that the oxides must be implemented in conjunction with metal gate electrodes, the development of which is further behind Issues about work function control in metal gate electrodes are discussed

https://iopscience.iop.org/article/10.1088/0034-4885/69/2/R02/pdf

High dielectric constant gate oxides for metal oxide Si transistors

An object is to provide a semiconductor device of which a manufacturing process is not complicated and by which cost can be suppressed, by forming a thin film transistor using an oxide semiconductor film typified by zinc oxide, and a manufacturing method thereof. For the semiconductor device, a gate electrode is formed over a substrate; a gate insulating film is formed covering the gate electrode; an oxide semiconductor film is formed over the gate insulating film; and a first conductive film and a second conductive film are formed over the oxide semiconductor film. The oxide semiconductor film has at least a crystallized region in a channel region.

Semiconductor device, and manufacturing method thereof

The scaling of complementary metal oxide semiconductor (CMOS) transistors has led to the silicon dioxide layer used as a gate dielectric becoming so thin (1.4 nm) that its leakage current is too large. It is necessary to replace the SiO2 with a physically thicker layer of oxides of higher dielectric constant (κ) or 'high K' gate oxides such as hafnium oxide and hafnium silicate. Little was known about such oxides, and it was soon found that in many respects they have inferior electronic properties to SiO2 ,s uch as a tendency to crystallise and a high concentration of electronic defects. Intensive research is underway to develop these oxides into new high quality electronic materials. This review covers the choice of oxides, their structural and metallurgical behaviour, atomic diffusion, their deposition, interface structure and reactions, their electronic structure, bonding, band offsets, mobility degradation, flat band voltage shifts and electronic defects. The use of high K oxides in capacitors of dynamic random access memories is also covered.

/pdf/high-dielectric-constant-oxides-cotu2e70vd.pdf

High dielectric constant oxides

The high dielectric constant of insulators currently investigated as alternatives to SiO2 in metal–oxide–semiconductor structures is due to their large ionic polarizability. This is usually accompanied by the presence of soft optical phonons. We show that the long-range dipole field associated with the interface excitations resulting from these modes and from their coupling with surface plasmons, while small in the case of SiO2, for most high-κ materials causes a reduction of the effective electron mobility in the inversion layer of the Si substrate. We study the dispersion of the interfacial coupled phonon-plasmon modes, their electron-scattering strength, and their effect on the electron mobility for Si-gate structures employing films of SiO2, Al2O3, AlN, ZrO2, HfO2, and ZrSiO4 for “SiO2-equivalent” thicknesses ranging from 5 to 0.5 nm.

Effective electron mobility in Si inversion layers in metal–oxide–semiconductor systems with a high-κ insulator: The role of remote phonon scattering

Electrical and reliability properties of ultrathin HfO/sub 2/ have been investigated. Pt electroded MOS capacitors with HfO/sub 2/ gate dielectric (physical thickness /spl sim/45-135 /spl Aring/ and equivalent oxide thickness /spl sim/13.5-25 /spl Aring/) were fabricated. HfO/sub 2/ was deposited using reactive sputtering of a Hf target with O/sub 2/ modulation technique. The leakage current of the 45 /spl Aring/ HfO/sub 2/ sample was about 1/spl times/10/sup -4/ A/cm/sup 2/ at +1.0 V with a breakdown field /spl sim/8.5 MV/cm. Hysteresis was <100 mV after 500/spl deg/C annealing in N/sub 2/ ambient and there was no significant frequency dispersion of capacitance (<1%/dec.). It was also found that HfO/sub 2/ exhibits negligible charge trapping and excellent TDDB characteristics with more than ten years lifetime even at V/sub DD/=2.0 V.

Electrical characteristics of highly reliable ultrathin hafnium oxide gate dielectric

Physical, electrical and reliability characteristics of ultra thin HfO/sub 2/ as an alternative gate dielectric were studied for the first time. Crucial process parameters of oxygen modulated dc magnetron sputtering were optimized to achieve an equivalent oxide thickness (EOT) of 11.5 /spl Aring/ without deducting the quantum mechanical effect. Leakage current was 3/spl times/10/sup -2/ A/cm/sup 2/ at +1 V. Excellent dielectric properties such as high dielectric constant, low leakage current, good thermal stability, negligible dispersion and good reliability were demonstrated.

Ultrathin hafnium oxide with low leakage and excellent reliability for alternative gate dielectric application

Hafnium oxynitride (HfOxNy) gate dielectric was prepared using reactive sputtering followed by postdeposition annealing at 650 °C in a N2 ambient. Nitrogen incorporation in the dielectric was confirmed by x-ray photoelectron spectroscopy analysis. In comparison to HfO2 of the same physical thickness, HfOxNy gate dielectric showed lower equivalent oxide thickness (EOT) and lower leakage density (J). Even after a high-temperature postmetal anneal at 950 °C, an EOT of 9.6 A with J of 0.8 mA/cm2 @−1.5 V was obtained. In contrast, J of ∼20 mA/cm2 @−1.5 V for HfO2 with an EOT of 10 A was observed. The lower leakage current and superior thermal stability of HfOxNy can be attributed to the formation of silicon–nitrogen bonds at the gate dielectric/Si interface and strengthened immunity to oxygen diffusion by the incorporated nitrogen.

Bonding states and electrical properties of ultrathin HfOxNy gate dielectrics

MOSCAP and MOSFET characteristics using ZrO/sub 2/ gate dielectric deposited directly on Si have been investigated Thin equivalent oxide thickness (EOT), low leakage, negligible frequency dispersion, interface density less than 10/sup 11/ cm/sup -2/ eV/sup -1/, small hysteresis, excellent reliability characteristics have been demonstrated The ZrO/sub 2/ film has been shown to be amorphous A thin interfacial Zr-silicate layer (k>8) exists and is beneficial in maintaining good interfacial quality This Zr-silicate layer grows after annealing and can be minimized through process optimization Well-behaved p-channel MOS transistor characteristics with a subthreshold swing of 80 mV/decade have also been achieved

MOSCAP and MOSFET characteristics using ZrO/sub 2/ gate dielectric deposited directly on Si

Zirconium silicate (ZrSixOy) films have been sputtered by comagnetron-reactive sputtering. The composition of ZrSixOy has been controlled by adjusting the sputtering powers of Si and Zr targets to achieve various effective dielectric constants. The sputtered silicate layers showed low equivalent oxide thickness of 14.5 A with a low leakage of 3.3×10−3 A/cm2 at −1.5 V relative to flat band voltage. The silicate films also exhibited good high-temperature stability and smooth interfacial properties on silicon substrate.

Katsunori Onishi

Papers

Electrical characteristics of highly reliable ultrathin hafnium oxide gate dielectric

Ultrathin hafnium oxide with low leakage and excellent reliability for alternative gate dielectric application

Bonding states and electrical properties of ultrathin HfOxNy gate dielectrics

MOSCAP and MOSFET characteristics using ZrO/sub 2/ gate dielectric deposited directly on Si

Ultrathin zirconium silicate film with good thermal stability for alternative gate dielectric application