Integration of HfxTayN metal gate with SiO2 and HfOxNy gate dielectrics for MOS device applications

Interaction of Hf_xTa_yN metal gate with SiO₂ and HfO_xN_y gate dielectrics has been extensively studied. Metal-oxide-semiconductor (MOS) device formed with SiO₂ gate dielectric and Hf_xTa_yN metal gate shows satisfactory thermal stability. Time-of-flight secondary ion mass spectroscopy (TOF-SIMS) analysis results show that the diffusion depths of Hf and Ta are less significant in SiO₂ gate dielectric than that in HfO_xN_y. Compared to HfO_xN_y gate dielectric, SiO₂ shows better electrical properties, such as leakage current, hysteresis, interface trap density and stress-induced flat-band voltage shift. With an increase in post metallization annealing (PMA) temperature, the electrical characteristics of the MOS device with SiO₂ gate dielectric remain almost unchanged, indicating its superior thermal and electrical stability.     

Fabrication and electrical characteristics of ultrathin (HfO2)x(SiO2)1−x films by surface sol-gel method and reaction-anneal treatment

Hafnium oxide (HfO₂) films were deposited on Si substrates with a pre-grown oxide layer using hafnium chloride (HfCl₄) source by surface sol-gel process, then ultrathin (HfO₂)_x(SiO₂)_1−x films were fabricated due to the reaction of SiO₂ layer with HfO₂ under the appropriate reaction-anneal treatment. The observation of high-resolution transmission electron microscopy indicates that the ultrathin films show amorphous nature. X-ray photoelectron spectroscopy analyses reveal that surface sol-gel derived ultrathin films are Hf-Si-O alloy instead of HfO₂ and pre-grown SiO₂ layer, and the composition was Hf_0.52Si_0.48O₂ under 500 °C reaction-anneal. The lowest equivalent oxide thickness (EOT) value of 0.9 nm of film annealed at 500 °C has been obtained with small flatband voltage of −0.31 V. The experimental results indicate that a simple and feasible solution route to fabricate (HfO₂)_x(SiO₂)_1−x composite films has been developed by means of combination of surface sol-gel and reaction-anneal treatment.     

The effect of oxygen in Ru gate electrode on effective work function of Ru/HfO2 stack structure

Effective work function (φ_m,eff) values of Ru gate electrode on SiO₂ and HfO₂ MOS capacitors were carefully examined and discussed from the viewpoint of an effect of oxygen incorporation in Ru gate electrode on φ_m,eff. Annealing at 400 °C in the reduction (3%H₂) and the oxidation (1%O₂) ambient resulted in similar changes in the φ_m,eff of Ru/HfO₂/SiO₂ and Ru/SiO₂ MOS capacitors. Furthermore, the Ru gate MOS capacitor after annealing in the oxidation condition have shown almost the same φ_m,eff value to that of RuO₂ gate MOS capacitors. The oxygen concentration in the Ru/HfO₂ interface after annealing in oxidizing atmosphere is approximately one order of magnitude higher than that after annealing in reducing atmosphere as confirmed by secondary ion mass spectroscopy analysis. Furthermore, the higher oxygen concentration at the Ru/dielectric interface leads to the higher φ_m,eff value, regardless of SiO₂ or HfO₂ dielectrics. This indicates that φ_m,eff of Ru gate MOS capacitor is dominantly determined by the oxygen concentration at the Ru/dielectric layer interface rather than the dipoles originated from the oxygen vacancy in HfO₂.     

Effects of high doping on the bandgap bowing for AlxGa1−xN

This paper gives the composition dependence of the bandgap energy for highly doped n-type Al_xGa_1−xN. We report results of the bowing parameter obtained using a random simulation. Three groups of Al_xGa_1−xN semiconductors were considered and which are distinguishable by their non degenerate or degenerate character in the doping density (10¹⁷?N_D?10²⁰ cm⁻³). A striking feature is the large discrepancy of the bandgap bowing (−2.02?b?2.94 eV), as was demonstrated from our calculations. This suggests that high doping may be a possible cause able to induce the large range of bowing parameters reported for Al_xGa_1−xN alloys.     

Materials characterization of WNxCy, WNx and WCx films for advanced barriers

A ternary WN_xC_y system was deposited in a thermal ALD (atomic layer deposition) reactor from ASM at 300 °C in a process sequence using tungsten hexafluoride (WF₆), triethyl borane (TEB) and ammonia (NH₃) as precursors. The WC_x layers were deposited by a novel ALD process at a process temperature of 250 °C. The WN_x layers were deposited at 375 °C using bis(tert-butylimido)-bis-(dimethylamido)tungsten (^tBuN)₂(Me₂N)₂W (imido-amido) and NH₃ as precursors. WN_x grows faster on plasma enhanced chemical vapor deposition (PECVD) oxide than WC_x does on chemical oxide. WN_xC_y grows better on PECVD oxide than on thermal oxide, which is opposite of what is seen for WN_x. In the case of the ternary WN_xC_y system, the scalability towards thinner layers and galvanic corrosion behavior are disadvantages for the incorporation of the layer into Cu interconnects. ALD WC_x based barriers have a low resistivity, but galvanic corrosion in a model slurry solution of 15% peroxide (H₂O₂) is a potential problem. Higher resistivity values are determined for the binary WN_x layers. WN_x shows a constant composition and density throughout the layer.     

Electrodepositing ZnxMnyOz alloys from zinc oxide to manganese oxide

Electrodeposition has emerged as a practical and simple method to synthesise semiconductor materials under different forms, thin films or nanostructured layers. This work reports on the cathodic electrodeposition of ZnMnO thin layers using both zinc and manganese chlorides as precursors. The composition of thin films can be varied from binary zinc oxide to manganese oxide varying the Mn/(Mn+Zn) ratio between 0 and 1. The composition of Zn_xMn_yO_z films was obtained by energy dispersive spectroscopy. Zn_1−xMn_xO films with Mn/Zn ratio less than 10% exhibit a crystalline wurtzite structure typical of ZnO fully oriented in the (0 0 2) direction. Higher Mn content leads to deformation of the ZnO lattice and the wurtzite structure is no longer maintained. X-ray photoelectron spectroscopy points out that Mn₃O₄ tends to be deposited when a high Mn/Zn ratio is used in the starting solution. Magnetic measurements on films with Mn/(Zn+Mn) ratio near 1 reveal magnetic characteristics similar to Mn₃O₄ compounds. The transmission spectra of Zn_xMn_yO_z show the typical absorption edge of crystalline ZnO while the wurtzite structure is maintained and it shifts to higher wavelengths when Mn content increases.     

Field electron emission from amorphous CNx:B films

CN_x:B thin films were prepared on titanium coated ceramic substrate by pulsed laser deposition technique (PLD). The microstructure of the film was examined using scanning electron microscopy (SEM), X-ray diffraction (XRD), X-ray photoelectron spectroscopy (XPS) and Raman spectroscopy. The analyses indicate that the deposited samples are amorphous CN_x:B thin films. Field electron emission characteristics of amorphous CN_x:B thin films were measured in a vacuum chamber with a base pressure of about 3.2×10⁻⁵ Pa. The turn-on field of the film was 3.5 V/μm. The current density was 60 μA/cm² at an electric field of 9 V/μm. The experimental results indicate that this film could be a promising material applicable to cold cathodes.     

Interfacial reactions and electrical properties of Hf/p-Si0.85Ge0.15

Interfacial reactions and electrical properties of Hf/p-Si_0.85Ge_0.15 as a function of the annealing temperature were studied. Hf₃(Si_1−xGe)₂ and Hf(Si_1−xGe)₂ were initially formed at 500°C and 600°C, respectively. At temperatures above 400°C, Ge segregation out of the reacted layers associated with strain relaxation of the unreacted Si_0.85Ge_0.15 films appeared. At 780°C, agglomeration occurred in the Hf(Si_1−xGe_x)₂ films. All the as-deposited and annealed Hf/p-Si_0.85Ge_0.15 samples showed the formation of an ohmic contact. The lowest specific contact resistance around 10⁻⁵ ω cm² could be obtained for the Hf₃ (Si_1−xGe_x)₂ contacts to p-Si_0.85Ge_0.15 formed at 500°C. Below 500°C, the decrease of specific contact resistance with the annealing temperature is mainly caused by the formation of Hf₃(Si_1−xGe_x)₂ and an interfacial Ge-rich layer between the Hf₃(Si_1−xGe_x)₂ and unreacted Si_0.85Ge_0.15 films, while above 600°C, the increase of specific contact resistance may be due to the formation of Hf(Si_1−xGe_x)₂ and SiC as well as the roughness of the Hf(Si_1−xGe_x)₂ films.     

Precise determination of metal effective work function and fixed oxide charge in MOS capacitors with high-κ dielectric

Effective metal work function, Φ_m,eff, and oxide charge, Q_ox, were determined on MOS capacitors with slanted high-κ dielectric. Φ_m,eff and Q_ox were extracted using flat-band voltage shift versus equivalent oxide thickness data, both deduced from the capacitance–voltage measurements. Slanted HfSiO_x dielectric (initial thickness was 9 nm) was prepared by gradual etching in HF-based solution. As a metal electrode, thin Ru-films were deposited by MOCVD-derived technique—Atomic Vapor Deposition^® on the slanted HfSiO_x as well as SiO₂ dielectrics. The Φ_m,eff of Ru was found to be 4.74 and 4.81 eV for Ru/HfSiO_x and Ru/SiO₂ gate stacks, respectively. Ultraviolet photoelectron spectroscopy yields the work function of 4.62 eV in agreement with the capacitance–voltage data. We also studied the I–V characteristics of the Ru/HfSiO_x/Si MOS capacitors. The barrier height was found to be constant within the HfSiO_x bulk.     

Study of thick film Ni(1−x)CoxMn2O4,(0?x?1) using overlay technique on thick film microstrip ring resonator

The effect of thick film Ni_(1−x)Co_xMn₂O₄ in-touch overlay on the X band resonance characteristics of thick film microstrip ring resonator is studied. The thick film overlay decreases the resonance frequency and increases the peak output. From the frequency shift the dielectric constant of the thick film Ni_(1−x)Co_xMn₂O₄ has been calculated. For the first time Ag thick film microstrip ring resonator has been used to study thick film Ni_(1−x)Co_xMn₂O₄ in the X band.     

High performance TaYOx-based MIM capacitors

TaYO_x-based metal-insulator-metal (MIM) capacitors with excellent electrical properties have been fabricated. Ultra-thin TaYO_x films in the thickness range of 15-30 nm (EOT ∼ 2.4-4.7 nm) were deposited on Au/SiO₂ (100 nm)/Si (100) structures by rf-magnetron co-sputtering of Ta₂O₅ and Y₂O₃ targets. TaYO_x layers were characterized by X-ray photoelectron spectroscopy (XPS), energy dispersive X-ray (EDX) and X-ray diffraction (XRD) to examine the composition and crystallinity. An atomic percentage of Ta:Y = 58.32:41.67 was confirmed from the EDX analysis while XRD revealed an amorphous phase (up to 500 °C) during rapid thermal annealing. Besides, a high capacitance density of ∼3.7-5.4 fF/μm² at 10 kHz (ε_r ∼ 21), a low value of VCC (voltage coefficients of capacitance, α and β) have been achieved. Also, a highly stable temperature coefficient of capacitance, TCC has been obtained. Capacitance degradation phenomena in TaYO_x-based MIM capacitors under constant current stressing (CCS at 20 nA) have been studied. It is observed that degradation depends strongly on the dielectric thickness and a dielectric breakdown voltage of 3-5 MV/cm was found for TaYO_x films. The maximum energy storage density was estimated to be ∼5.69 J/cm³. Post deposition annealing (PDA) in O₂ ambient at 400 °C has been performed and further improvement in device reliability and electrical performances has been achieved.     

ALD of LaHfOx nano-laminates for high-κ gate dielectric applications

Electrical properties and thermal stability of LaHfO_x nano-laminate films deposited on Si substrates by atomic layer deposition (ALD) have been investigated for future high-κ gate dielectric applications. A novel La precursor, tris(N,N′-diisopropylformamidinato) lanthanum [La(ⁱPrfAMD)₃], was employed in conjunction with conventional tetrakis-(ethylmethyl)amido Hf (TEMA Hf) and water (H₂O). The capacitance-voltage curves of the metal oxide semiconductor capacitors (MOSCAPs) showed negligible hysteresis and frequency dispersion, indicating minimal deterioration of the interface and bulk properties. A systematic shift in the flat-band voltage (V_fb) was observed with respect to the change in structure of nano-laminate stacks as well as La₂O₃ to HfO₂ content in the films. The EOTs obtained were in the range of ∼1.23-1.5 nm with leakage current densities of ∼1.3 × 10⁻⁸ A/cm² to 1.3 × 10⁻⁵ A/cm² at V_fb − 1 V. In addition, the films with a higher content of La₂O₃ remained amorphous up to 950 °C indicating very good thermal stability, whereas the HfO₂ rich films crystallized at lower temperatures.     

Properties of ALD HfTaxOy high-k layers deposited on chemical silicon oxide

HfTa_xO_y high-k dielectric layers with different compositions were deposited using ALD on 1 nm SiO₂ generated by ozone based cleaning of 200 mm Si(1 0 0) surface. Physical characterization of blanket layers and C-V mapping demonstrates that the ALD layers have excellent uniformity and controllable compositions. The layers with a composition of HfTaO_5.5 remain amorphous after annealing at 900 °C. The C-V measurements of MOS capacitors show no hysteresis, negligible frequency dispersion and interfacial state density smaller than 3 × 10¹¹ (cm⁻² eV⁻¹). k-value of the amorphous layers varies in the range from 20 to 25, depending on layer composition. The flat band voltage does not shift with the increase of EOT, implying that the effect of fixed charge densities in the layers is negligible. The I-V measurements show a leakage reduction comparable to that of the ALD HfO₂ layers.     

Impact of strain relaxation of AlmGa1−mN layer on 2-DEG sheet charge density and current voltage characteristics of lattice mismatched AlmGa1−mN/GaN HEMTs

An accurate charge control model to investigate the effect of aluminum composition, strain relaxation, thickness and doping of the Al_mGa_1−mN barrier layer on the piezoelectric and spontaneous polarization induced 2-DEG sheet charge density, threshold voltage and output characteristics of partially relaxed Al_mGa_1−mN/GaN HEMTs is proposed. The strain relaxation of the barrier imposes an upper limit on the maximum 2-DEG density achievable in high Al content structures and is critical in determining the performance of lattice mismatched Al_mGa_1−mN/GaN HEMTs. The model incorporates the effects of field dependent mobility, parasitic source/drain resistance and velocity saturation to evaluate the output characteristics of Al_mGa_1−mN/GaN HEMTs. Close proximity with published results confirms the validity of the proposed model.     

Unterminated 4H-SiC Schottky barrier diodes with novel HfNxBy electrodes

4H-SiC Schottky barrier diodes (SBDs) were fabricated and characterized from room temperature to 573 K using HfN_xB_y as Schottky electrodes. The results are compared to SBDs fabricated using other electrodes that include Ni, Pt, Ti and Au. The Schottky barrier height Φ_b for as-deposited HfN_xB_y/n−/n+ diodes, determined from room temperature current-voltage characteristics, is 0.887 eV. This is lower than those of SBDs fabricated using other metals such as Au, where Φ_b is 1.79 eV. The HfN_xB_y/n−/n+ diodes studied have a much higher on-resistance R_on of around 38.24 mΩ-cm², which is about four times that of Au/n−/n+ diodes, due to the higher sheet resistance of the sputtered HfN_xB_y electrode layer. The barrier height Φ_b and ideality factor η of the HfN_xB_y/n−/n+ diodes remain almost unchanged after 400 and 750 °C anneal in N₂. This suggests excellent thermal and chemical stability of HfN_xB_y in contact with 4H-SiC.     

HfAlOx high-k gate dielectric on SiGe: Interfacial reaction, energy-band alignment, and charge trapping properties

Ultra thin HfAlO_x high-k gate dielectric has been deposited directly on Si_1−xGe_x by RF sputter deposition. The interfacial chemical structure and energy-band discontinuities were studied by using X-ray photoelectron spectroscopy (XPS), time of flight secondary ion mass spectroscopy (TOF-SIMS) and electrical measurements. It is found that the sputtered deposited HfAlO_x gate dielectric on SiGe exhibits excellent electrical properties with low interface state density, hysteresis voltage, and frequency dispersion. The effective valence and conduction band offsets between HfAlO_x (E_g = 6.2 eV) and Si_1−xGe_x (E_g = 1.04 eV) were found to be 3.11 eV and 2.05 eV, respectively. In addition, the charge trapping properties of HfAlO_x/SiGe gate stacks were characterized by constant voltage stressing (CVS).     

Leakage currents and dielectric breakdown of Si1−x−yGexCy thermal oxides

A detailed study of the leakage currents and dielectric wear-out of thermal oxides grown on Si_1−xGe_x, Si_1−yC_y and Si_1−x−yGe_xC_y epilayers to determine their quality and reliability for Si_1−x−yGe_xC_y MOS technology is presented. After applying electrical stress to the samples, we have determined the conduction mechanisms and the dependence of leakage currents upon epilayer composition (Ge and C content). Conduction takes place mainly via Fowler-Nordheim tunneling injection. Ge and C introduce traps in the oxide which assist injection and thus lower the effective height of the tunneling barrier. We have also monitored the oxide reliability, focusing on time-dependent dielectric breakdown (TDDB). The nature of trapped charge in the oxide depends on the initial epilayer composition. We have found that the formation of defects induced by the presence of C leads to extrinsic oxide failure. While the presence of Ge in the oxide does not seem to introduce significant differences with respect to Si breakdown statistics, C in the oxide truly modifies the statistical profile.     

Influence of the deposition parameters on the growth of SiGe nanocrystals embedded in Al2O3 matrix

Si_1−xGe_x nanocrystals (NCs), embedded in Al₂O₃ matrix, were fabricated on Si (100) substrates by RF-magnetron sputtering technique with following annealing procedure at 800 °C, in nitrogen atmosphere. The presence of Si_1−xGe_x NCs was confirmed by grazing incidence X-ray diffraction (GIXRD), grazing incidence small angle X-ray scattering (GISAXS) and Raman spectroscopy. The influence of the growth conditions on the structural properties and composition of Si_1−xGe_x NCs inside the alumina matrix was analyzed. Optimal conditions to grow Si_1−xGe_x (x∼ 0.8) NCs sized between 3 and 4 nm in Al₂O₃ matrix were established.     

Damascene TiN-Gd2O3-gate stacks: Gentle fabrication and electrical properties

In this work, we present MOS capacitors and field effect transistors with a crystalline gadolinium oxide (Gd₂O₃) gate dielectric and metal gate electrode (titanium nitride) fabricated in a gentle damascene gate last process. Details of the gate last process and initial results on MOS devices with equivalent oxide thicknesses (EOT) of 3.0 nm and 1.5 nm, respectively, are shown.     

Transport and interface states in high-κ LaSiOx dielectric

The paper presents the results of capacitance-voltage, conductance-frequency and current-voltage characterization in the wide temperature range (140-300 K) as well as results of low temperature (5-20 K) thermally stimulated currents (TSC) measurements of metal-oxide-semiconductor (MOS) structures with a high-κ LaSiO_x dielectric deposited on p- and n-type Si(1 0 0) substrate. Interface states (D_it) distribution determined by several techniques show consistent result and demonstrates the adequacy of techniques used. Typical maxima of interface states density were found as 4.6 × 10¹¹ eV⁻¹cm⁻² at 0.2 eV and 7.9 × 10¹¹ eV⁻¹cm⁻² at 0.77 eV from the silicon valence band. The result of admittance spectroscopy showed the presence of local states in bandgap with activation energy E_a = 0.38 eV from silicon conductance band, which is in accord with interface states profile acquired by conductance method. Low-temperature TSC spectra show the presence of shallow traps at the interface with activation energies ranging from 15 to 32 meV. The charge carrier transport through the dielectric film was found to occur via Poole-Frenkel mechanism at forward bias.