Thermal stability of Hf/sub x/Ta/sub y/N metal gate electrodes for advanced MOS devices

In this letter, the composition effects of hafnium (Hf) and tantalum (Ta) in Hf/sub x/Ta/sub y/N metal gate on the thermal stability of MOS devices were investigated. The work function of the Hf/sub x/Ta/sub y/N metal gate can reach a value of /spl sim/4.6 eV (midgap of silicon) by suitably adjusting the Hf and Ta compositions. In addition, with a small amount of Hf incorporated into a TaN metal gate, excellent thermal stability of electrical properties, including the work function, the equivalent oxide thickness, interface trap density and defect generation rate characteristics, can be achieved after a post-metal anneal up to 950/spl deg/C for 45 s. Experimental results indicate that Ta-rich Hf/sub x/Ta/sub y/N is a promising metal gate for advanced MOS devices.     

Metal gate-HfO/sub 2/ MOS structures on GaAs substrate with and without Si interlayer

In this letter, we studied the effects of post-deposition anneal (PDA) time and Si interface control layer (ICL) on the electrical characteristics of the MOS capacitor with high-/spl kappa/ (HfO/sub 2/) material on GaAs. Thin equivalent oxide thickness (EOT<3 nm) with excellent capacitance-voltage (C-V) characteristics has been obtained. The thickness of the Si ICL and PDA time were correlated with C-V characteristics. It was found that high temperature Si ICL deposition and longer PDA time at 600/spl deg/C improved the C-V shape, leakage current, and especially frequency dispersion (<5%).     

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.     

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 properties of HfO/sub 2/ dielectric on germanium and the substrate doping effect

MOS devices built on various germanium substrates, with chemical vapor deposited (CVD) or physical vapor deposited (PVD) HfO/sub 2/ high-/spl kappa/ dielectric and TaN gate electrode, were fabricated. The electrical properties of these devices, including the capacitance equivalent thickness (CET), gate leakage current density (J/sub g/), slow trap density (D/sub st/), breakdown voltage (V/sub bd/), capacitance-voltage (C-V) frequency dispersion, and thermal stability, are investigated. The process conditions such as surface nitridation treatment, O/sub 2/ introduction in CVD process and postdeposition anneal temperature in PVD process, exhibit significant impacts on the devices' electrical properties. The devices built on germanium substrates with different dopant types and doping concentrations show remarkable variations in electrical characteristics, revealing the role of the substrate doping in the reactions occurring at the dielectric/Ge interface, which can significantly affect the interfacial layer formation and Ge updiffusion. A possible mechanism is suggested that two competing processes (oxide growth and desorption) take place at the interface, which govern the formation of the interfacial layer. Doped p-type (Ga) and n-type (Sb) impurities may enhance the different process at the interface and cause the variations in the interfacial layer formation and so on in electrical properties. The high diffusivities of impurities and Ge atoms in Ge and the induced structural defects near the substrate surface could be one possible cause for this doping effect. As another behavior of the substrate doping effect, Ge n-MOS and p-MOS stacks show quite different C-V characteristics after high temperature postmetallization anneal treatments, which can be explained by the same mechanism.     

Positive bias temperature instability effects of Hf-based nMOSFETs with various nitrogen and silicon profiles

Positive bias temperature instability (PBTI) effects of HfO/sub 2/-based nMOSFETs with various nitrogen profiles in HfO/sub 2/ were investigated. The nitrogen profile was modulated by an inserting Si layer (/spl sim/6/spl Aring/) into hafnium oxynitride gate dielectrics. The Si layer is used to trap nitrogen and to suppress nitrogen out-diffusion during subsequent anneals. Compared to control HfO/sub x/N/sub y/ without Si insertion, the Si-inserted HfO/sub x/N/sub y/ samples exhibited reduced PBTI degradation, especially if the Si layer was placed further from the Si interface. The improvement can be attributed to the reduction of oxide bulk trapped as well as reduced interface trapped charge generation resulting from compensation effect of inserted Si layer.     

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.     

Leakage suppression of gated diodes fabricated under low-temperature annealing with substitutional carbon Si/sub 1-y/C/sub y/ incorporation

We have demonstrated the fabrication of n/sup +/-p gated diodes using low-temperature annealing of 700/spl deg/C for 30 s with a significantly reduced junction leakage current. This is achieved with the incorporation of an epitaxially grown Si/sub 1-y/C/sub y/(y=0.0007) layer in the substrate located at the end-of-range (EOR) of arsenic implantations. The carbon devices show effectively suppressed EOR defects in the cross-sectional transmission electron microscopy images and leakage characteristics similar to the controlled silicon device fabricated under high-temperature annealing of 950/spl deg/C for 30 s. Arrhenius measurement of the leakage profiles has indicated identical leakage mechanism for both the pure silicon and carbon devices, thus signifying the substantial elimination of the secondary EOR defects resulted from the implantations despite the low-temperature annealing of the latter.     

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.     

MOS Characteristics of synthesized HfAlON-HfO/sub 2/ stack using AlN-HfO/sub 2/

We demonstrate a top-surface aluminized and nitrided HfO/sub 2/ gate dielectric using a synthesis of ultrathin aluminum nitride (AlN) and HfO/sub 2/. The reaction of AlN with HfO/sub 2/ through a subsequent high-temperature annealing incorporates Al and N into an HfO/sub 2/ layer, which results in a synthesis of HfAlON near the top surface of HfO/sub 2/, forming an HfAlON-HfO/sub 2/ stack structure. This approach suppresses interfacial layer growth and improves thermal stability of the dielectric, resulting in significant improvement in leakage current. It also shows no adverse effects caused by N and Al incorporation at the bottom interface.     

Interface structure of ultrathin oxide prepared by N/sub 2/O oxidation

With X-ray photoelectron spectroscopy (XPS) measurements, we found in the N/sub 2/O-grown oxide that the nitrogen incorporation should involve the NO or N reaction with the Si-Si bond and P/sub b/ centers at the interface. Consequently, nitrogen content is very low and accumulated mainly at the interface. In addition, we found that the nitrogen atoms at the interface exist in the form of Si-N bonding and the interface oxynitride layer is a mixture of SiO/sub 2/ and Si/sub 3/N/sub 4/ clusters. This structure will result in several undesirable effects. It will give rise to the permittivity and bandgap fluctuations at the interface and hence induced gigantic surface potential fluctuation and mobility degradation in the channel of MOS devices. This bonding structure also explains the interface trap generation during the electrical stressing. The sources of trap generation are attributed to the Si-Si bonds, P/sub b/ centers, and nitride-related defects due to the over-constrained silicon atoms in the Si/sub 3/N/sub 4/ clusters at the interface.     

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.     

High-k Al/sub 2/O/sub 3/ gate dielectrics prepared by oxidation of aluminum film in nitric acid followed by high-temperature annealing

A simple, cost-effective, and room temperature process was proposed to prepare high-k gate dielectrics. An aluminum oxide (Al/sub 2/O/sub 3/) gate dielectric was prepared by oxidation of ultrathin Al film in nitric acid (HNO/sub 3/) at room temperature then followed by high-temperature annealing in O/sub 2/ or N/sub 2/. The substrate injection current behavior and interface trap-induced capacitance were introduced to investigate the interfacial property between the gate dielectric and Si substrate. Al/sub 2/O/sub 3/ gate dielectric MOS capacitors with and without initial SiO/sub 2/ layers were characterized. It was shown that the Al/sub 2/O/sub 3/ gate dielectrics with initial oxide exhibit better electrical properties than those without. The 650/spl deg/C N/sub 2/-POA Al/sub 2/O/sub 3/-SiO/sub 2/ sample with an equivalent oxide thickness of 18 /spl Aring/ exhibits three orders of magnitude reduction in gate leakage current in comparison with the conventional thermal SiO/sub 2/ sample.     

Origin of the threshold voltage instability in SiO/sub 2//HfO/sub 2/ dual layer gate dielectrics

The magnitude of the V/sub T/ instability in conventional MOSFETs and MOS capacitors with SiO/sub 2//HfO/sub 2/ dual-layer gate dielectrics is shown to depend strongly on the details of the measurement sequence used. By applying time-resolved measurements (capacitance-time traces and charge-pumping measurements), it is demonstrated that this behavior is caused by the fast charging and discharging of preexisting defects near the SiO/sub 2//HfO/sub 2/ interface and in the bulk of the HfO/sub 2/ layer. Based on these results, a simple defect model is proposed that can explain the complex behavior of the V/sub T/ instability in terms of structural defects as follows. 1) A defect band in the HfO/sub 2/ layer is located in energy above the Si conduction band edge. 2) The defect band shifts rapidly in energy with respect to the Fermi level in the Si substrate as the gate bias is varied. 3) The rapid energy shifts allows for efficient charging and discharging of the defects near the SiO/sub 2//HfO/sub 2/ interface by tunneling.     

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.     

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.     

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.     

Physically based quantum-mechanical compact model of MOS devices substrate-injected tunneling current through ultrathin (EOT /spl sim/ 1 nm) SiO/sub 2/ and high-/spl kappa/ gate stacks

Building on a previously presented compact gate capacitance (C/sub g/-V/sub g/) model, a computationally efficient and accurate physically based compact model of gate substrate-injected tunneling current (I/sub g/-V/sub g/) is provided for both ultrathin SiO/sub 2/ and high-dielectric constant (high-/spl kappa/) gate stacks of equivalent oxide thickness (EOT) down to /spl sim/ 1 nm. Direct and Fowler-Nordheim tunneling from multiple discrete subbands in the strong inversion layer are addressed. Subband energies in the presence of wave function penetration into the gate dielectric, charge distributions among the subbands subject to Fermi-Dirac statistics, and the barrier potential are provided from the compact C/sub g/-V/sub g/ model. A modified version of the conventional Wentzel-Kramer-Brillouin approximation allows for the effects of the abrupt material interfaces and nonparabolicities in complex band structures of the individual dielectrics on the tunneling current. This compact model produces simulation results comparable to those obtained via computationally intense self-consistent Poisson-Schro/spl uml/dinger simulators with the same MOS devices structures and material parameters for 1-nm EOTs of SiO/sub 2/ and high-/spl kappa//SiO/sub 2/ gate stacks on (100) Si, respectively. Comparisons to experimental data for MOS devices with metal and polysilicon gates, ultrathin dielectrics of SiO/sub 2/, Si/sub 3/N/sub 4/, and high-/spl kappa/ (e.g., HfO/sub 2/) gate stacks on (100) Si with EOTs down to /spl sim/ 1-nm show excellent agreement.     

Atomic layer deposition of high-/spl kappa/ dielectric for germanium MOS applications - substrate

In this letter, we present the use of atomic layer deposition (ALD) for high-/spl kappa/ gate dielectric formation in Ge MOS devices. Different Ge surface cleaning methods prior to high-/spl kappa/ ALD have been evaluated together with the effects on inserting a Ge oxynitride (GeO/sub x/N/sub y/) interlayer between the high-/spl kappa/ layer and the Ge substrate. By incorporating a thin GeO/sub x/N/sub y/ interlayer, we have demonstrated excellent MOS capacitors with very small capacitance-voltage hysteresis and low gate leakage. Physical characterization has also been done to further investigate the quality of the oxynitride interlayer.     

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/.