Effects of interstitial oxygen defects at HfO/sub x/N/sub y//Si interface on electrical characteristics of MOS devices

Effects of the defects at high-/spl kappa/ dielectric/Si interface on the electrical characteristics of MOS devices are important issues. To study these issues, a low defect (denuded zone) at Si surface was formed by a high-temperature annealing in hydrogen atmosphere in this paper. Our results reveal that HfO/sub x/N/sub y/ demonstrates significant improvement on the electrical properties of MOS devices due to its low amount of the interstitial oxygen [O/sub i/] and the crystal-originated particles defects as well as small surface roughness at HfO/sub x/N/sub y//Si interface. The current-conduction mechanism of the HfO/sub x/N/sub y/ film at the low- and high-electrical field and high-temperature (T>100/spl deg/C) is dominated by Schottky emission and Frenkel-Poole (FP) emission, respectively. The trap energy level involved in FP conduction was estimated to be around 0.5eV. Reduced gate leakage current, stress-induced leakage current and defect generation rate, attributable to the reduction of defects at HfO/sub x/N/sub y//Si interface, were observed for devices with denuded zone. The variable rise and fall time bipolar-pulse-induced current technique was used to determine the energy distribution of interface trap density (D/sub it/). The results exhibit that relatively low D/sub it/ can be attributed to the reduction of defects at Si surface. By using denuded zone at the Si surface, HfO/sub x/N/sub y/ has demonstrated significant improvement on electrical properties as compared to SiO/sub x/N/sub y/.     

Effect of the composition on the electrical properties of TaSi/sub x/N/sub y/ metal gate electrodes

In this letter, the effect of silicon and nitrogen on the electrical properties of TaSi/sub x/N/sub y/ gate electrode were investigated. The TaSi/sub x/N/sub y/ films were deposited on SiO/sub 2/ using reactive cosputtering of Ta and Si target in Ar and N/sub 2/ ambient. The thermal stability of TaSi/sub x/N/sub y//SiO/sub 2//p-type Si stacks was evaluated by measuring the flatband voltage and equivalent oxide thickness at 400/spl deg/C and 900/spl deg/C in Ar. It was found that under high temperature anneals, Si-rich TaSi/sub x/N/sub y/ films increased and this was attributed to the formation of a reaction layer at the electrode-dielectric interface. Reducing the Si content alone did not prevent the formation of this reaction layer while removing Si completely by utilizing TaN resulted in work functions that were too high. The presence of both Si and N was deemed necessary and their content was critical in obtaining optimized TaSi/sub x/N/sub y/ gates that are suitable for NMOS devices.     

The electrical and material characterization of hafnium oxynitride gate dielectrics with TaN-gate electrode

Electrical and material characteristics of hafnium oxynitride (HfON) gate dielectrics have been studied in comparison with HfO/sub 2/. HfON was prepared by a deposition of HfN followed by post-deposition-anneal (PDA). By secondary ion mass spectroscopy (SIMS), incorporated nitrogen in the HfON was found to pile up at the dielectric/Si interface layer. Based on the SIMS profile, the interfacial layer (IL) composition of the HfON films appeared to be like hafnium-silicon-oxynitride (HfSiON) while the IL of the HfO/sub 2/ films seemed to be hafnium-silicate (HfSiO). HfON showed an increase of 300/spl deg/C in crystallization temperature compared to HfO/sub 2/. Dielectric constants of bulk and interface layer of HfON were 21 and 14, respectively. The dielectric constant of interfacial layer in HfON (/spl sim/14) is larger than that of HfO/sub 2/ (/spl sim/7.8). HfON dielectrics exhibit /spl sim/10/spl times/ lower leakage current (J) than HfO/sub 2/ for the same EOTs before post-metal anneal (PMA), while /spl sim/40/spl times/ lower J after PMA. The improved electrical properties of HfON over HfO/sub 2/ can be explained by the thicker physical thickness of HfON for the same equivalent oxide thickness (EOT) due to its higher dielectric constant as well as a more stable interface layer. Capacitance hysteresis (/spl Delta/V) of HfON capacitor was found to be slightly larger than that of HfO/sub 2/. Without high temperature forming gas anneal, nMOSFET with HfON gate dielectric showed a peak mobility of 71 cm/sup 2//Vsec. By high temperature forming gas anneal at 600/spl deg/C, mobility improved up to 256 cm/sup 2//Vsec.     

Aggressively scaled ultra thin undoped HfO/sub 2/ gate dielectric (EOT<0.7 nm) with TaN gate electrode using engineered interface layer

The ultrathin HfO/sub 2/ gate dielectric (EOT<0.7 nm) has been achieved by using a novel "oxygen-scavenging effect" technique without incorporation of nitrogen or other "dopants" such as Al, Ti, or La. Interfacial oxidation growth was suppressed by Hf scavenging layer on HfO/sub 2/ gate dielectric with appropriate annealing, leading to thinner EOT. As the scavenging layer thickness increases, EOT becomes thinner. This scavenging technique produced a EOT of 7.1 /spl Aring/, the thinnest EOT value reported to date for "undoped" HfO/sub 2/ with acceptable leakage current, while EOT of 12.5 /spl Aring/ was obtained for the control HfO/sub 2/ film with the same physical thickness after 450/spl deg/C anneal for 30 min at forming gas ambient. This reduced EOT is attributed to "scavenging effect" that Hf metal layer consumes oxygen during anneal and suppresses interfacial reaction effectively, making thinner interface layer. Using this fabrication approach, EOT of /spl sim/ 0.9 nm after conventional self-aligned MOSFETs process was successfully obtained.     

Modeling of tunneling currents through HfO/sub 2/ and (HfO/sub 2/)/sub x/(Al/sub 2/O/sub 3/)/sub 1-x/ gate stacks

We present a physical modeling of tunneling currents through ultrathin high-/spl kappa/ gate stacks, which includes an ultrathin interface layer, both electron and hole quantization in the substrate and gate electrode, and energy band offsets between high-/spl kappa/ dielectrics and Si determined from high-resolution XPS. Excellent agreements between simulated and experimentally measured tunneling currents have been obtained for chemical vapor deposited and physical vapor deposited HfO/sub 2/ with and without NH/sub 3/-based interface layers, and ALD Al/sub 2/O/sub 3/ gate stacks with different EOT and bias polarities. This model is applied to more thermally stable (HfO/sub 2/)/sub x/(Al/sub 2/O/sub 3/)/sub 1-x/ gate stacks in order to project their scalability for future CMOS applications.     

Mechanism of positive-bias temperature instability in sub-1-nm TaN/HfN/HfO/sub 2/ gate stack with low preexisting traps

In this letter, the positive-bias temperature instability (PBTI) characteristics of a TaN/HfN/HfO/sub 2/ gate stack with an equivalent oxide thickness (EOT) of 0.95 nm and low preexisting traps are studied. The negligible PBTI at room temperature, the so-called "turn-around" phenomenon, and the negative shifts of the threshold voltage (V/sub t/) are observed. A modified reaction-diffusion (R-D) model, which is based on the electric stress induced defect generation (ESIDG) mechanism, is proposed to explain the above-mentioned PBTI characteristics. In this modified R-D model, PBTI is attributed to the electron-induced breaking of Si-O bonds at interfacial layer (IL) between HfO/sub 2/ and Si substrate and the diffusion/drift of oxygen ions (O/sup -/) from Si-O bonds into HfO/sub 2/ layer under positive-bias temperature stressing. The ESIDG mechanism is responsible for the breaking of Si-O bonds. The measured activation energy (E/sub a/) is consistent with the one predicted by the ESIDG mechanism.     

Electrical and physical characterization of remote plasma oxidized HfO/sub 2/ gate dielectrics

Bi-layer gate stacks consisting of a HfO/sub 2/ and an interfacial layer are fabricated by remote plasma oxidation (RPO) of Hf metal deposited on an Si substrate. Hf metal is fully oxidized by the RPO even at a temperature as low as 400/spl deg/C due to radical oxygens, leading to an improvement in the quality of HfO/sub 2/ with less impact to the interfacial layer growth. An insufficient oxidation leads to a deterioration of mobility with increasing interface traps and positive bias temperature instability, which is likely caused by the oxygen vacancies acting as traps induced by the remaining Hf metal. The SiO/sub 2/-like interface improves the mobility with reduced interface states. Full oxidation and the controlled SiO/sub 2/-like interface demonstrate RPO as a promising way for gate-stack optimization.     

Hafnium Titanate bilayer structure multimetal dielectric nMOSCAPs

A novel approach of fabricating laminated TiO/sub 2//HfO/sub 2/ bilayer multimetal oxide dielectric has been developed for high-performance CMOS applications. Ultrathin equivalent oxide thickness (/spl sim/8 /spl Aring/) has been achieved with increased effective permittivity (k/spl sim/36). Hysteresis was significantly reduced using the bilayer dielectric. Top TiO/sub 2/ layer was found to induce effective negative charge from the flatband voltage shift. Leakage current characteristic was slightly higher than control HfO/sub 2/, and this is believed to be due to the lower band offset of TiO/sub 2/. However, the interface state density of this bilayer structure was found to be similar to that of HfO/sub 2/ MOSCAP because the bottom layer is HfO/sub 2/. These results demonstrate the feasibility of new multimetal dielectric application for future CMOS technology.     

MOS capacitors on epitaxial Ge-Si/sub 1-x/Ge/sub x/ with high-/spl kappa/ dielectrics using RPCVD

We report the successful growth of MOS capacitor stacks with low temperature strained epitaxial Ge or Si/sub 1-x/Ge/sub x/(x=0.9) layer directly on Si substrates, and with HfO/sub 2/(EOT=9.7 /spl Aring/) as high-/spl kappa/ dielectrics, both using a novel remote plasma-assisted chemical vapor deposition technique. These novel MOS capacitors, which were fabricated entirely at or below 400/spl deg/C, exhibit normal capacitance-voltage and current-voltage characteristics.     

ScN/sub x/ gate on atomic layer deposited HfO/sub 2/ and effect of high-pressure wet post deposition annealing

For nMOS devices with HfO/sub 2/, a metal gate with a very low workfunction is necessary. In this letter, the effective workfunction (/spl Phi//sub m,eff/) values of ScN/sub x/ gates on both SiO/sub 2/ and atomic layer deposited (ALD) HfO/sub 2/ are evaluated. The ScN/sub x//SiO/sub 2/ samples have a wide range of /spl Phi//sub m,eff/ values from /spl sim/ 3.9 to /spl sim/ 4.7 eV, and nMOS-compatible /spl Phi//sub m,eff/ values can be obtained. However, the ScN/sub x/ gates on conventional post deposition-annealed HfO/sub 2/ show a relatively narrow range of /spl Phi//sub m,eff/ values from /spl sim/ 4.5 to /spl sim/ 4.8 eV, and nMOS-compatible /spl Phi//sub m,eff/ values cannot be obtained due to the Fermi-level pinning (FLP) effect. Using high-pressure wet post deposition annealing, we could dramatically reduce the extrinsic FLP. The /spl Phi//sub m,eff/ value of /spl sim/ 4.2 eV was obtained for the ScN/sub x/ gate on the wet-treated HfO/sub 2/. Therefore, ScN/sub x/ metal gate is a good candidate for nMOS devices with ALD HfO/sub 2/.     

Gate-first Germanium nMOSFET with CVD HfO/sub 2/ gate dielectric and silicon surface passivation

A gate-first self-aligned Ge n-channel MOSFET (nMOSFET) with chemical vapor deposited (CVD) high-/spl kappa/ gate dielectric HfO/sub 2/ was demonstrated. By tuning the thickness of the ultrathin silicon-passivation layer on top of the germanium, it is found that increasing the silicon thickness helps to reduce the hysteresis, fixed charge in the gate dielectric, and interface trap density at the oxide/semiconductor interface. About 61% improvement in peak electron mobility of the Ge nMOSFET with a thick silicon-passivation layer over the CVD HfO/sub 2//Si system was achieved.     

Low-frequency noise in submicrometer MOSFETs with HfO/sub 2/, HfO/sub 2//Al/sub 2/O/sub 3/ and HfAlO/sub x/ gate stacks

Low-frequency noise measurements were performed on p- and n-channel MOSFETs with HfO/sub 2/, HfAlO/sub x/ and HfO/sub 2//Al/sub 2/O/sub 3/ as the gate dielectric materials. The gate length varied from 0.135 to 0.36 /spl mu/m with 10.02 /spl mu/m gate width. The equivalent oxide thicknesses were: HfO/sub 2/ 23 /spl Aring/, HfAlO/sub x/ 28.5 /spl Aring/ and HfO/sub 2//Al/sub 2/O/sub 3/ 33 /spl Aring/. In addition to the core structures with only about 10 /spl Aring/ of oxide between the high-/spl kappa/ dielectric and silicon substrate, there were "double-gate oxide" structures where an interfacial oxide layer of 40 /spl Aring/ was grown between the high-/spl kappa/ dielectric and Si. DC analysis showed low gate leakage currents in the order of 10/sup -12/A(2-5/spl times/10/sup -5/ A/cm/sup 2/) for the devices and, in general, yielded higher threshold voltages and lower mobility values when compared to the corresponding SiO/sub 2/ devices. The unified number-mobility fluctuation model was used to account for the observed 1/f noise and to extract the oxide trap density, which ranged from 1.8/spl times/10/sup 17/ cm/sup -3/eV/sup -1/ to 1.3/spl times/10/sup 19/ cm/sup -3/eV/sup -1/, somewhat higher compared to conventional SiO/sub 2/ MOSFETs with the similar device dimensions. There was no evidence of single electron switching events or random telegraph signals. The aim of this paper is to present a general discussion on low-frequency noise characteristics of the three different high-/spl kappa//gate stacks, relative comparison among them and to the Si--SiO/sub 2/ system.     

Low-frequency noise in submicrometer MOSFETs with HfO/sub 2/, HfO/sub 2//Al/sub 2/O/sub 3/ and HfAlO/sub x/ gate stacks

Low-frequency noise measurements were performed on p- and n-channel MOSFETs with HfO/sub 2/, HfAlO/sub x/ and HfO/sub 2//Al/sub 2/O/sub 3/ as the gate dielectric materials. The gate length varied from 0.135 to 0.36 /spl mu/m with 10.02 /spl mu/m gate width. The equivalent oxide thicknesses were: HfO/sub 2/ 23 /spl Aring/, HfAlO/sub x/ 28.5 /spl Aring/ and HfO/sub 2//Al/sub 2/O/sub 3/ 33 /spl Aring/. In addition to the core structures with only about 10 /spl Aring/ of oxide between the high-K dielectric and silicon substrate, there were "double-gate oxide" structures where an interfacial oxide layer of 40 /spl Aring/ was grown between the high-K dielectric and Si. DC analysis showed low gate leakage currents in the order of 10/sup -12/ A(2-5 /spl times/ 10/sup -5/ A/cm/sup 2/) for the devices and, in general, yielded higher threshold voltages and lower mobility values when compared to the corresponding SiO/sub 2/ devices. The unified number-mobility fluctuation model was used to account for the observed 1/f noise and to extract the oxide trap density, which ranged from 1.8 /spl times/ 10/sup 17/ cm/sup -3/ eV/sup -1/ to 1, 3 /spl times/ 10/sup 19/ cm/sup -3/ eV/sup -1/ somewhat higher compared to conventional SiO/sub 2/ MOSFETs with the similar device dimensions. There was no evidence of single electron switching events or random telegraph signals. The aim of this paper is to present a general discussion on low-frequency noise characteristics of the three different high-K/gate stacks, relative comparison among them and to the Si-SiO/sub 2/ system.     

Improved device performance and reliability in high /spl kappa/ HfTaTiO gate dielectric with TaN gate electrode

The device performance and reliability of higher-/spl kappa/ HfTaTiO gate dielectrics have been investigated in this letter. HfTaTiO dielectrics have been reported to have a high-/spl kappa/ value of 56 and acceptable barrier height relative to Si (1.0 eV). Through process optimization, an ultrathin equivalent oxide thickness (EOT) (/spl sim/9 /spl Aring/) has been achieved. HfTaTiO nMOSFET characteristics have been studied as well. The peak mobility of HfTaTiO is 50% higher than that of HfO/sub 2/ and its high field mobility is comparable to that of HfSiON with an intentionally grown SiO/sub 2/ interface, indicative of superior quality of the interface and bulk dielectric. In addition, HfTaTiO dielectric has a reduced stress-induced leakage current (SILC) and improved breakdown voltage compared to HfO/sub 2/ dielectric.     

Fabrication and mobility characteristics of SiGe surface channel pMOSFETs with a HfO/sub 2//TiN gate stack

This paper describes an extensive experimental study of TiN/HfO/sub 2//SiGe and TiN/HfO/sub 2//Si cap/SiGe gate stacked-transistors. Through a careful analysis of the interface quality (interface states and roughness), we demonstrate that an ultrathin silicon cap is mandatory to obtain high hole mobility enhancement. Based on quantum mechanical simulations and capacitance-voltage characterization, we show that this silicon cap is not contributing any silicon parasitic channel conduction and degrades by only 1 /spl Aring/ the electrical oxide thickness in inversion. Due to this interface optimization, Si/sub 0.72/Ge/sub 0.28/ pMOSFETs exhibit a 58% higher mobility at high effective field (1 MV/cm) than the universal SiO/sub 2//Si reference and a 90% higher mobility than the HfO/sub 2//Si reference. This represents one of the best hole mobility results at 1 MV/cm ever reported with a high-/spl kappa//metal gate stack. We thus validate a possible solution to drastically improve the hole mobility in Si MOSFETs with high-/spl kappa/ gate dielectrics.     

Bias-temperature instabilities of polysilicon gate HfO/sub 2/ MOSFETs

Bias-temperature instabilities (BTI) of HfO/sub 2/ metal oxide semiconductor field effect transistors (MOSFETs) have been systematically studied for the first time. NMOS positive BTI (PBTI) exhibited a more significant V/sub t/ instability than that of PMOS negative BTI (NBTI), and limited the lifetime of HfO/sub 2/ MOSFETs. Although high-temperature forming gas annealing (HT-FGA) improved the interface quality by passivating the interfacial states with hydrogen, BTI behaviors were not strongly affected by the technique. Charge pumping measurements were extensively used to investigate the nature of the BTI degradation, and it was found that V/sub t/ degradation of NMOS PBTI was primarily caused by charge trapping in bulk HfO/sub 2/ rather than interfacial degradation. Deuterium (D/sub 2/) annealing was found to be an excellent technique to improve BTI immunity as well as to enhance the mobility of HfO/sub 2/ MOSFETs.     

Ultrathin Al/sub 2/O/sub 3/ and HfO/sub 2/ gate dielectrics on surface-nitrided Ge

We have studied ultrathin Al/sub 2/O/sub 3/ and HfO/sub 2/ gate dielectrics on Ge grown by ultrahigh vacuum-reactive atomic-beam deposition and ultraviolet ozone oxidation. Al/sub 2/O/sub 3/-Ge gate stack had a t/sub eq//spl sim/23 /spl Aring/, and three orders of magnitude lower leakage current compared to SiO/sub 2/. HfO/sub 2/-Ge allowed even greater scaling, achieving t/sub eq//spl sim/11 /spl Aring/ and six orders of magnitude lower leakage current compared to SiO/sub 2/. We have carried out a detailed study of cleaning conditions for the Ge wafer, dielectric deposition condition, and anneal conditions and their effect on the electrical properties of metal-gated dielectric-Ge capacitors. We show that surface nitridation is important in reducing hysteresis, interfacial layer formation and leakage current. However, surface nitridation also introduces positive trapped charges and/or dipoles at the interface, resulting in significant flatband voltage shifts, which are mitigated by post-deposition anneals.     

Low-frequency noise in TaSiN/HfO/sub 2/ nMOSFETs and the effect of stress-relieved preoxide interfacial layer

Low-frequency noise characteristics are reported for TaSiN-gated n-channel MOSFETs with atomic-layer deposited HfO/sub 2/ on thermal SiO/sub 2/ with stress-relieved preoxide (SRPO) pretreatment. For comparison, control devices were also included with chemical SiO/sub 2/ resulting from standard Radio Corporation of America clean process. The normalized noise spectral density values for these devices are found to be lower when compared to reference poly Si gate stack with similar HfO/sub 2/ dielectric. Consequently, a lower oxide trap density of /spl sim/4/spl times/10/sup 17/ cm/sup -3/eV/sup -1/ is extracted compared to over 3/spl times/10/sup 18/ cm/sup -3/eV/sup -1/ values reported for poly Si devices indicating an improvement in the high-/spl kappa/ and interfacial layer quality. In fact, this represents the lowest trap density values reported to date on HfO/sub 2/ MOSFETs. The peak electron mobility measured on the SRPO devices is over 330 cm/sup 2//V/spl middot/s, much higher than those for equivalent poly Si or metal gate stacks. In addition, the devices with SRPO SiO/sub 2/ are found to exhibit at least /spl sim/10% higher effective mobility than RCA devices, notwithstanding the differences in the high-/spl kappa/ and interfacial layer thicknesses. The lower Coulomb scattering coefficient obtained from the noise data for the SRPO devices imply that channel carriers are better screened due to the presence of SRPO SiO/sub 2/, which, in part, contributes to the mobility improvement.     

A novel high-/spl kappa/ SONOS memory using TaN/Al/sub 2/O/sub 3//Ta/sub 2/O/sub 5//HfO/sub 2//Si structure for fast speed and long retention operation

A novel high-/spl kappa/ silicon-oxide-nitride-oxide-silicon (SONOS)-type memory using TaN/Al/sub 2/O/sub 3//Ta/sub 2/O/sub 5//HfO/sub 2//Si (MATHS) structure is reported for the first time. Such MATHS devices can keep the advantages of our previously reported TaN/HfO/sub 2//Ta/sub 2/O/sub 5//HfO/sub 2//Si device structure to obtain a better tradeoff between long retention and fast programming as compared to traditional SONOS devices. While at the same time by replacing hafnium oxide (HfO/sub 2/) with aluminum oxide (Al/sub 2/O/sub 3/) for the top blocking layer, better blocking efficiency can be achieved due to Al/sub 2/O/sub 3/'s much larger barrier height, resulting in greatly improved memory window and faster programming. The fabricated devices exhibit a fast program and erase speed, excellent ten-year retention and superior endurance up to 10/sup 5/ stress cycles at a tunnel oxide of only 9.5 /spl Aring/ equivalent oxide thickness.     

MIM capacitors using atomic-layer-deposited high-/spl kappa/ (HfO/sub 2/)/sub 1-x/(Al/sub 2/O/sub 3/)/sub x/ dielectrics

Metal-insulator-metal (MIM) capacitors with (HfO/sub 2/)/sub 1-x/(Al/sub 2/O/sub 3/)/sub x/ high-/spl kappa/ dielectric films were investigated for the first time. The results show that both the capacitance density and voltage/temperature coefficients of capacitance (VCC/TCC) values decrease with increasing Al/sub 2/O/sub 3/ mole fraction. It was demonstrated that the (HfO/sub 2/)/sub 1-x/(Al/sub 2/O/sub 3/)/sub x/ MIM capacitor with an Al/sub 2/O/sub 3/ mole fraction of 0.14 is optimized. It provides a high capacitance density (3.5 fF//spl mu/m/sup 2/) and low VCC values (/spl sim/140 ppm/V/sup 2/) at the same time. In addition, small frequency dependence, low loss tangent, and low leakage current are obtained. Also, no electrical degradation was observed for (HfO/sub 2/)/sub 1-x/(Al/sub 2/O/sub 3/)/sub x/ MIM capacitors after N/sub 2/ annealing at 400/spl deg/C. These results show that the (HfO/sub 2/)/sub 0.86/(Al/sub 2/O/sub 3/)/sub 0.14/ MIM capacitor is very suitable for capacitor applications within the thermal budget of the back end of line process.