MOCVD fluorine free WSix metal gate electrode on high-k dielectric for NMOS technology

We report material and electrical properties of tungsten silicide metal gate deposited on 12 in. wafers by chemical vapor deposition (CVD) using a fluorine free organo-metallic (MO) precursor. We show that this MOCVD WSi_x thin film deposited on a high-k dielectric (HfSiO:N) shows a N+ like behavior (i.e. metal workfunction progressing toward silicon conduction band). We obtained a high-k/WSi_x/polysilicon “gate first” stack (i.e. high thermal budget) providing stable equivalent oxide thickness (EOT) of ∼1.2 nm, and a reduction of two decades in leakage current as compared to SiO₂/polysilicon standard stack. Additionally, we obtained a metal gate with an equivalent workfunction (EWF) value of ∼4.4 eV which matches with the +0.2 eV above Si midgap criterion for NMOS in ultra-thin body devices.     

A nanoanalytical investigation of elemental distributions in high-k dielectric gate stacks on silicon

Two high-k gate stacks with the structure Si/SiO₂/HfO₂/TiN/poly-Si are characterised using nanoanalytical electron microscopy. The effect of two key changes to the processing steps during the fabrication of the stacks is investigated. Electron energy-loss spectroscopy is used to show that the TiN layer has a very similar composition whether it is deposited by PVD or ALD. Spectrum imaging in the electron microscope was used to profile the distribution of elements across the layers in the stack. It was found that when the anneal after HfO₂ deposition is carried out in a NH₃ atmosphere instead of an O₂ atmosphere, there is diffusion of N into the SiO₂ and HfO₂ layers. There is also significant intermixing of the layers at the interfaces for both wafers.     

Influence of the sidewall crystal orientation, HfSiO nitridation and TiN metal gate thickness on n-MuGFETs under analog operation

This work characterizes the analog performance of SOI n-MuGFETs with HfSiO gate dielectric and TiN metal gate with respect to the influence of the high-k post-nitridation, TiN thickness and device rotation. A thinner TiN metal gate is found favorable for improved analog characteristics showing an increase in intrinsic voltage gain. The devices where the high-k material is subjected to a nitridation step indicated a degradation of the Early voltage (V_EA) values which resulted in a lower voltage gain. The 45° rotated devices have a smaller V_EA than the standard ones when a HfSiO dielectric is used. However, the higher transconductance of these devices, due to the increased mobility in the (1 0 0) sidewall orientation, compensates this V_EA degradation of the voltage gain, keeping it nearly equal to the voltage gain values of the standard devices.     

Study of nitrogen impact on VFB-EOT roll-off by varying interfacial SiO2 thickness

Flat band voltage (V_FB) roll-off in long channel devices at thin equivalent oxide thickness (EOT) is studied on SiO₂/nitrided-HfSiO stacks. V_FB increases when SiO₂ interfacial layer thickness decreases, and charges pumping (CP) frequency sweep analysis shows higher trap density near Si/SiO₂ interface. Based on this observation, an atomic diffusion model is introduced. Higher concentration of nitrogen atom in the HfSiO(N) layer diffuses to the Si/SiO₂ interface through the SiO₂ layer in thinner SiO₂ device, and accumulates near Si/SiO₂ interface which can introduce higher density of interfacial traps. Lifetime extracted from negative bias temperature instability (NBTI), and mobility are also degraded in thinner SiO₂ devices due to the higher interfacial trap density.The V_FB roll-off can be improved by lowering nitrogen concentration in the HfSiO(N) layer from optimizing plasma nitridation pressure, decreasing post deposition anneal temperature, or using defect absorbing layer on the high-k oxide.     

在metal/high-k 栅叠层中插入Ti/TiN金属层实现远距离吸氧技术

High permittivity materials have been required to replace traditional SiO₂ as the gate dielectric to extend Moore’s law.However,growth of a thin SiO₂-like interfacial layer（IL） is almost unavoidable during the deposition or subsequent high temperature annealing.This limits the scaling benefits of incorporating high-k dielectrics into transistors.In this work,a promising approach,in which an O-scavenging metal layer and a barrier layer preventing scavenged metal diffusing into the high-k gate dielectric are used to engineer the thickness of the IL,is reported. Using a Ti scavenging layer and TiN barrier layer on a HfO₂ dielectric,the effective removal of the IL and almost no Ti diffusing into the HfO₂ have been confirmed by high resolution transmission electron microscopy and X-ray photoelectron spectroscopy.     

Fully strained Si0.75Ge0.25 epitaxial films with HfSiO gate dielectrics for high mobility channel metal-oxide semiconductor devices

The authors report on fully strained Si_0.75Ge_0.25 metal-oxide-semiconductor capacitors with HfSiO₂ high-k gate dielectric and TaN metal gate fabricated on Si substrates. Fully strained Si_0.75Ge_0.25 films are directly grown on Si substrates below the critical thickness. HfSiO₂ high-k gate dielectrics exhibit an equivalent oxide thickness of 13-18 Å with a permittivity of 17.7 and gate leakage current density lower than SiO₂ gate oxides by >100×. Interfacial oxide of the HfSiO₂/Si_0.75Ge_0.25 stack consists primarily of SiO₂ with a small amount of Ge and Hf. High performance SiGe field effect transistors are highly manufacturable with excellent electrical characteristics afforded by the fully strained HfSiO₂/SiGe gate stack.     

Annealing effect on the metal gate effective work function modulation for the Al/TiN/SiO2/p-Si structure

In this work, the thermal annealing effect on the metal gate effective work function (EWF) modulation for the Al/TiN/SiO₂/p-Si(1 0 0) structure was investigated. Compared with the sample of TiN/SiO₂/p-Si(1 0 0) structure, for the sample additionally capped with Al the flat band voltage has a very obvious shift as large as 0.54 V to the negative direction after forming gas annealing. It is also revealed that the thermal budget can effectively influence both the EWF of the gate electrode and the thickness of the gate dielectric layer when a post annealing at 600 °C with different soak times was applied to the samples with Al cap. Material characterization indicates that the diffusion of Al and the formation of Al oxide during annealing should be responsible for all the phenomena. The interface trap density Dit calculated from the high-frequency C-V and the laser-assisted high-frequency C-V curves show that the introduction of Al does not cause reliability problem in the Al/TiN/SiO₂/p-Si structure.     

Performance improvement of flash memory using AlN as charge-trapping Layer

Potential of high-k dielectric films for future scaled charge storage non-volatile memory (NVM) device applications is discussed. To overcome the problems of charge loss encountered in conventional flash memories with silicon-nitride (Si₃N₄) films and polysilicon-oxide-nitride-oxide-silicon (SONOS) and nonuniformity issues in nanocrystal memories (NC), such as Si, Ge and metal, it is shown that the use of high-k dielectrics allows more aggressive scaling of the tunnel dielectric, smaller operating voltage, better endurance, and faster program/erase speeds. Charge-trapping characteristics of high-k AlN films with SiO₂ as a blocking oxide in p-Si/SiO₂/AlN/SiO₂/poly-silicon (SOHOS) memory structures have been investigated in detail. The experimental results of program/erase characteristics obtained as the functions of gate bias voltage and pulse width are presented.     

Improved retention characteristic of charge-trapped flash device with sealing layer/Al2O3 or Al2O3/high-k stacked blocking layers

Although programming and erase speeds of charge trapping (CT) flash memory device are improved by using Al₂O₃ as blocking layer, its retention characteristic is still a main issue. CT flash memory device with Al₂O₃/high-k stacked blocking layer is proposed in this work to enhance data retention. Moreover, programming and erase speeds are slightly improved. In addition, sealing layer (SL), which is formed by an advanced clustered horizontal furnace between charge trapping layer and Al₂O₃ as one of the blocking layers is also studied. The retention characteristic is enhanced by SL approach due to lower gate leakage current with less defect. With the combination of SL and Al₂O₃/high-k stacked blocking layer approaches, retention property can be further improved.     

Scaling the MOSFET gate dielectric: From high-k to higher-k? (Invited Paper)

We discuss options for metal–oxide-semiconductor field-effect transistor (MOSFET) gate stack scaling with thin titanium nitride metal gate electrodes and high-permittivity (‘high-k’) gate dielectrics, aimed at gate-first integration schemes. Both options are based on further increasing permittivity of the dielectric stack. First, we show that hafnium-based stacks such as TiN/HfO₂ can be scaled to capacitance equivalent thickness in inversion (T_inv) of 10 Å and equivalent oxide thickness (EOT) of 6 Å by using silicon nitride instead of silicon oxide as a high-k/channel interfacial layer. This is based on the higher dielectric constant of Si₃N₄ and on its resistance to oxidation. Although the nitrogen introduces positive fixed charges, carrier mobility is not degraded. Secondly, we investigate whether Ti-based ‘higher-k’ dielectrics have the potential to ultimately replace Hf. We discuss oxygen loss from TiO₂ as a main challenge, and identify two migration pathways for such oxygen atoms: In addition to well-known down-diffusion and channel Si oxidation, we have newly observed oxygen up-diffusion through the TiN metal gate, forming SiO₂ at the poly-Si contact. We further address the performance of Si₃N₄ and HfO₂ as oxygen barrier layers.     

Physical and electrical characterization of polysilicon vs. TiN gate electrodes for HfO2 transistors

The effects of pre-deposition substrate treatments and gate electrode materials on the properties and performance of high-k gate dielectric transistors were investigated. The performance of O₃ vs. HF-last/NH₃ pre-deposition treatments followed by either polysilicon (poly-Si) or TiN gate electrodes was systematically studied in devices consisting of HfO₂ gate dielectric produced by atomic layer deposition (ALD). High-angle annular dark field scanning transmission electron microscopy (HAADF-STEM) using X-ray spectra and Electron Energy Loss Spectra (EELS) were used to produce elemental profiles of nitrogen, oxygen, silicon, titanium, and hafnium to provide interfacial chemical information and to convey their changes in concentration across these high-k transistor gate-stacks of 1.0–1.8 nm equivalent oxide thickness (EOT). For the TiN electrode case, EELS spectra illustrate interfacial elemental overlap on a scale comparable to the HfO₂ microroughness. For the poly-Si electrode, an amorphous reaction region exists at the HfO₂/poly-Si interface. Using fast transient single pulse (SP) electrical measurements, electron trapping was found to be greater with poly-Si electrode devices, as compared to TiN. This may be rationalized as a result of a higher density of trap centers induced by the high-k/poly-Si material interactions and may be related to increased physical thickness of the dielectric film, as illustrated by HAADF-STEM images, and may also derive from the approximately 0.5 nm larger EOT associated with polysilicon electrodes on otherwise identical gate stacks.     

Influence of the SiO2 layer thickness on the degradation of HfO2/SiO2 stacks subjected to static and dynamic stress conditions

The substitution of the SiO₂ gate oxide in MOS devices by a material with a high-k dielectric constant is being deeply studied nowadays to solve the problem of the leakage currents that appear with the progressive scaling of SiO₂ thickness. To improve the quality of the high-k/Si interface a very thin SiO₂ film is grown between both materials. In this work, HfO₂/SiO₂ stacks with different SiO₂ thickness were subjected to different types of stress (static and dynamic) to analyze the effect of this interfacial layer of SiO₂ in the degradation of the stack. The results show that the dielectric degradation depends on the stress applied and that the thickness of the SiO₂ interfacial layer influences the advanced stages of the stack degradation.     

Tunneling component suppression in charge pumping measurement and reliability study for high-k gated MOSFETs

Although charge pumping (CP) is a powerful technique to measure the energy and spatial distributions of interface trap and oxide trap in MOS devices, the parasitic gate leakage current in it is the bottleneck. A CP method was modified and applied to high-k gate dielectric in this work to separate the CP current from the parasitic tunneling component in MOS devices. The stress-induced variations of electrical parameters in high-k gated MOS devices were investigated and the physical mechanism was studied by the modified CP technique. The stress-induced trap generation for devices with HfO₂-dominated high-k gate dielectrics is like mobile defect; while that with SiO₂-dominated ones is similar to the near-interface/border trap.     

Investigation of the Interfaces in Ni-FUSI/Hf-Based/Si and Ni-FUSI/SiO<Subscript>2</Subscript>/Si Stacks by Physical and Electrical Characterization Techniques

The combination of full Ni silicidation (Ni-FUSI) gate electrodes and hafnium-based high-k gate dielectrics is one of the most promising replacements for poly-Si/SiO₂/Si gate stacks for the future complementary metal–oxide–semiconductor (CMOS) sub-45-nm technology node. The key challenges to successfully adopting the Ni-FUSI/high-k dielectric/Si gate stack for advanced CMOS technology are mostly due to the interfacial properties. The origins of the electrical and physical characteristics of the Ni-FUSI/dielectric oxide interface and dielectric oxide/bulk interface were studied in detail. We found that Ni-FUSI undergoes a phase transformation during silicide formation, which depends more on annealing temperature than on the underlying gate dielectric material. The correlations of Ni–Si phase transformations with their electrical and physical changes were established by sheet resistance measurements, x-ray diffraction (XRD), atomic force microscopy (AFM), and x-ray photoelectron spectroscopy (XPS) analyses. The leakage current density–voltage (J–V) and capacitance–voltage (C–V) measurement techniques were employed to study the dielectric oxide/Si interface. The effects of the postdeposition annealing (PDA) treatment on the interface charges of dielectric oxides were studied. We found that the PDA can effectively reduce the trapping density and leakage current and eliminate hysteresis in the C–V curves. In addition, the changes in chemical bonding features at HfO₂/Si and HfSiO/Si interfaces due to PDA treatment were evaluated by XPS measurements. XPS analysis provides a better interpretation of the electrical outcomes. As a result, HfSiO films exhibited superior performance in terms of thermal stability and electrical characteristics.     

A low-frequency noise model for advanced gate-stack MOSFETs

A new unified noise model is presented that accurately predicts the low-frequency noise spectrum exhibited by MOSFETs with high dielectric constant (high-k), multi-stack gate dielectrics. The proposed multi-stack unified noise (MSUN) model is based on number and correlated mobility fluctuations theory developed for native oxide MOSFETs, and offers scalability with respect to the high-k/interfacial layer thicknesses. In addition, it incorporates the various electronic properties of high-k/interfacial layer materials such as energy barrier heights between different gate layers, and dielectric trap density with respect to band energy and position in the dielectric. For verification of the new model, the low-frequency noise, DC and conventional split C-V measurements were performed in the 78-350 K temperature range on TaSiN/HfO₂ n-channel MOSFETs. The interfacial layer in these devices was either thermal SiO₂ by Stress Relieved Pre-Oxide (SRPO) pretreatment or chemical SiO₂ resulting from standard RCA (Radio Corporation of America) clean process. Using the experimental noise data, the channel carrier number fluctuations mechanism was at first established to be the underlying mechanism responsible for the noise observed at all temperatures considered. Secondly, the normalized noise exhibited a weak dependence on temperature implying that the soft optical phonons, although known to result in mobility degradation, have no effect on the noise characteristics in these high-k gate stack MOSFETs. Finally, the new model was shown to be in excellent agreement with the measured noise in 1-100 Hz frequency range at temperatures of 78-350 K for both gate stacks.     

Electrical characterization of high-k gate dielectrics fabricated using plasma oxidation and post-deposition annealing of a Hf/SiO2/Si structure

High permittivity (high-k) gate dielectrics were fabricated using the plasma oxidation of Hf metal/SiO₂/Si followed by the post-deposition annealing (PDA), which induced a solid-phase reaction between HfO_x and SiO₂. The oxidation time and PDA temperature affected the equivalent oxide thickness (EOT) and the leakage current density of the high-k dielectric films. The interfacial structure of the high-k dielectric film/Si was transformed from HfO_x/SiO₂/Si to HfSi_xO_y/Si after the PDA, which led to a reduction in EOT to 1.15 nm due to a decrease in the thickness of SiO₂. These high-k dielectric film structures were investigated by X-ray photoelectron spectroscopy. The leakage current density of high-k dielectric film was approximately four orders of magnitude lower than that of SiO₂.     

Gate leakage properties of MOS devices with tri-layer high-k gate dielectric

Gate leakage of deep-submicron MOSFET with stack high-k dielectrics as gate insulator is studied by building a model of tunneling current. Validity of the model is checked when it is used for MOSFET with SiO₂ and high-k dielectric material as gate dielectrics, respectively, and simulated results exhibit good agreement with experimental data. The model is successfully used for a tri-layer gate-dielectric structure of HfON/HfO₂/HfSiON with a U-shape nitrogen profile and a like-Si/SiO₂ interface, which is proposed to solve the problems of boron diffusion into channel region and high interface-state density between Si and high-k dielectric. By using the model, the optimum structural parameters of the tri-layer dielectric can be determined. For example, for an equivalent oxide thickness of 2.0 nm, the tri-layer gate-dielectric MOS capacitor with 0.3-nm HfON, 0.5-nm HfO₂ and 1.2-nm HfSiON exhibits the lowest gate leakage.     

Characteristics of metal-oxide-semiconductor (MOS) device with Er metal gate on SiO2 film

We have investigated the structural and electrical properties of metal-oxide-semiconductor (MOS) devices with Er metal gate on SiO₂ film. Rapid thermal annealing (RTA) process leads to the formation of a high-k Er-silicate gate dielectric. The in situ high-voltage electron microscopy (HVEM) results show that thermally driven Er diffusion is responsible for the decrease in equivalent oxide thickness (EOT) with an increase in annealing temperature. The effective work function (Φ_m,eff) of Er metal gate, extracted from the relations of EOT versus flat-band voltage (V_FB), is calculated to be ∼2.86 eV.     

X-ray metrology for high-k atomic layer deposited HfxZr1−xO2 films

Hafnium-based dielectrics are the most promising material for SiO₂ replacement in future nodes of CMOS technology. While devices that utilize HfO₂ gate dielectrics suffer from lower carrier mobility and degraded reliability, our group has recently reported improved device characteristics with a modified Hf_xZr_1−xO₂ [R.I. Hegde, D.H. Triyoso, P.J. Tobin, S. Kalpat, M.E. Ramon, H.-H. Tseng, J.K. Schaeffer, E. Luckowski, W.J. Taylor, C.C. Capasso, D.C. Gilmer, M. Moosa, A. Haggag, M. Raymond, D. Roan, J. Nguyen, L.B. La, E. Hebert, R. Cotton, X.-D. Wang, S. Zollner, R. Gregory, D. Werho, R.S. Rai, L. Fonseca, M. Stoker, C. Tracy, B.W. Chan, Y.H. Chiu, B.E. White, Jr., in: Technical Digest - International Electron Devices Meet, vol. 39, 2005, D.H. Triyoso, R.I. Hegde, J.K. Schaeffer, D. Roan, P.J. Tobin, S.B. Samavedam, B.E. White, Jr., R. Gregory, X.-D. Wang, Appl. Phys. Lett. 88 (2006) 222901]. These results have lead to evaluation of X-ray reflectivity (XRR) for monitoring high-k film thickness and control of Zr addition to HfO₂ using measured film density. In addition, a combination of XRR and spectroscopic ellipsometry (SE) is shown to be a fast and non-intrusive method to monitor thickness of interfacial layer between high-k and the Si substrate.     

Temperature dependent time-to-breakdown (TBD) of TiN/HfO2 n-channel MOS devices in inversion

Effect of temperature on time-to-breakdown (T_BD) of n⁺-ringed n-channel MOS capacitors with atomic layer deposited TiN/HfO₂ based gate stacks is studied. While interfacial layer (IL) growth condition and thickness varied the high-κ layer thickness and processing was unchanged. These devices were investigated by applying a constant voltage stress (CVS) in inversion (substrate injection) at room and elevated temperatures. For high electric fields (10-15 MV/cm) across IL, it is observed that T_BD is thermally activated irrespective of IL condition. Activation energies (2-3 eV after correction), found from Arrhenius plots of T_BD for different IL conditions, show good matches with those associated with field-driven thermochemical model of breakdown developed for SiO₂.