Hf-doped Ta2O5 stacks under constant voltage stress

The stress-induced leakage current in Hf-doped Ta₂O₅ layers (7; 10 nm) under constant voltage stress at gate injection was investigated in order to assess the mechanisms of conduction, the traps involved and the effect of Hf doping. The amount of Hf is found to affect the conduction mechanisms, the temperature dependence of the leakage current and the current response to the stress. A significant leakage current increase is observed only when the stress voltage and/or stress time exceed the corresponding threshold values, where the charge trapping at the pre-existing traps dominates below and defect generation above these threshold values. The energy levels of the traps responsible for the current transport are estimated. The stress effect on dominant conduction mechanisms appears quite weak, and the nature of the traps controlling the current transport before and after the stress seems to be nearly identical. The results indicate that the constant voltage stress affects the pre-existing traps in Hf-doped Ta₂O₅ and modifies their parameters, but there is no evidence for stress-induced generation of traps with completely new nature different from oxygen-vacancy related defects.     

Investigation of Ta2O5/SiO2/4H-SiC MIS capacitors

Tantalum pentoxide (Ta₂O₅) deposited by pulsed DC magnetron sputtering technique as the gate dielectric for 4H-SiC based metal-insulator-semiconductor (MIS) structure has been investigated. A rectifying current-voltage characteristic was observed, with the injection of current occurred when a positive DC bias was applied to the gate electrode with respect to the n type 4H-SiC substrate. This undesirable behavior is attributed to the relatively small band gap of Ta₂O₅ of around 4.3 eV, resulting in a small band offset between the 4H-SiC and Ta₂O₅. To overcome this problem, a thin thermal silicon oxide layer was introduced between Ta₂O₅ and 4H-SiC. This has substantially reduced the leakage current through the MIS structure. Further improvement was obtained by annealing the Ta₂O₅ at 900 °C in oxygen. The annealing has also reduced the effective charge in the dielectric film, as deduced from high frequency C-V measurements of the Ta₂O₅/SiO₂/4H-SiC capacitors.     

Influence of oxidation temperature on the microstructure and electrical properties of Ta2O5 on Si

The effect of the oxidation temperature (673-873 K) on the microstructural and electrical properties of thermal Ta₂O₅ thin films on Si has been studied. Auger electron spectroscopy and X-ray photoelectron spectroscopy results revealed that the films are non-stoichiometric in the depth; an interfacial transition layer between tantalum oxide and Si substrate, containing presumably SiO₂ was detected. It has been found by X-ray diffraction that the amorphous state of Ta₂O₅ depends on both the oxidation temperature and the thickness of the films—the combination of high oxidation temperature (>823 K) and thickness smaller than 50 nm is critical for the appearance of a crystal phase. The Ta₂O₅ layers crystallize to the monoclinic phase and the temperature of the phase transition is between 773 and 823 K for the thinner layers (<50 nm) and very close to 873 K for the thicker ones. The electrical characterization (current/voltage; capacitance/voltage) reveals that the optimal oxidation temperature for achieving the highest dielectric constant (∼32) and the lowest leakage current (10⁻⁸ A/cm² at 1 MV/cm applied field) is 873 K. The results imply that the poor oxidation related defects are rather the dominant factor in the leakage current than the crystallization effects.     

High-k HfO2-Ta2O5 mixed layers: Electrical characteristics and mechanisms of conductivity

Electrical properties of mixed HfO₂-Ta₂O₅ films (10;15 nm) deposited by rf sputtering on Si have been studied from the view point of their applications as high-k layers, by standard capacitance-voltage and temperature dependent current-voltage characteristics. The effect of HfO₂ addition to the Ta₂O₅ is thickness dependent and the thicker layers exhibit advantages over the pure Ta₂O₅ (higher dielectric constant, enhanced charge storage density and improved interface quality). The process of HfO₂ and Ta₂O₅ mixing introduces negative oxide charge, tends to creates shallow bulk traps and modifies the dominant conduction mechanisms in the stack capacitors as compared to the Ta₂O₅-based one (a contribution of tunneling processes through traps located below the conduction band of mixed layers to the leakage current in the HfO₂-Ta₂O₅ stacks is observed). The traps involved in both Poole-Frenkel and tunneling processes are identified.     

Conduction mechanisms in Ta2O5 stack in response to rapid thermal annealing

The influence of the rapid thermal annealing (RTA) in vacuum at 1000 °C on the leakage current characteristics and conduction mechanisms in thermal Ta₂O₅ (7-40 nm) on Si has been studied. It was established that the effect of RTA depends on both the initial parameters of the films (defined by the oxidation temperature and film thickness) and annealing time (15-60 s). The RTA tends to change the distribution and the density of the traps in stack, and this reflects on the dielectric and leakage properties. The thinner the film and the poorer the oxidation, the more susceptible the layer to heating. The short (15 s) annealing is effective in improving the leakage characteristics of poorly oxidized samples. The RTA effect, however, is rather deleterious than beneficial, for the thinner layers with good oxygen stoichiometry. RTA modifies the conduction mechanism of Ta₂O₅ films only in the high-field region. The annealing time has strong impact on the appearance of a certain type of reactions upon annealing resulting to variation of the ratio between donors and traps into Ta₂O₅, causing different degree of compensation, and consequently to domination of one of the two mechanisms at high fields (Schottky emission or Poole-Frenkel effect). Trends associated with simultaneous action of annealing and generation of traps during RTA processing, and respectively the domination of one of them, are discussed.     

Towards metal electrode interface scavenging of rare-earth scandates: A Sc2O3 and Gd2O3 study

Amorphous Gd₂O₃ and Sc₂O₃ thin films were deposited on Si by high-pressure sputtering (HPS). In order to reduce the uncontrolled interfacial SiO_x growth, firstly a metallic film of Gd or Sc was sputtered in pure Ar plasma. Subsequently, they were in situ plasma oxidized in an Ar/O₂ atmosphere. For post-processing interfacial SiO_x thickness reduction, three different top metal electrodes were studied: platinum, aluminum and titanium. For both dielectrics, it was found that Pt did not react with the films, while Al reacted with them forming an aluminate-like interface and, finally, Ti was effective in scavenging the SiO₂ interface thickness without severely compromising gate dielectric leakage.     

Infrared spectroscopy and X-ray diffraction studies on the crystallographic evolution of La2O3 films upon annealing

Rare earth oxides (REOs) have lately received extensive attention in relation to the continuous scaling down of non-volatile memories (NVMs). In particular, La₂O₃ films are promising for integration into future NVMs because they are expected to crystallize above 400 °C in the hexagonal phase (h-La₂O₃) which has a higher κ value than the cubic phase (c-La₂O₃) in which most of REOs crystallize. In this work, La₂O₃ films are grown on Si by atomic layer deposition using La(C₅H₅)₃ and H₂O. Within the framework of the h-La₂O₃ formation, we systematically study the crystallographic evolution of La₂O₃ films versus annealing temperature (200-600 °C) by Fourier transform infrared spectroscopy (FTIR) and grazing incidence X-ray diffraction (GIXRD). As-grown films are chemically unstable in air since a rapid transformation into monoclinic LaO(OH) and hexagonal La(OH)₃ occurs. Vacuum annealing of sufficiently thick (>100 nm) La(OH)₃ layers induces clear changes in FTIR and GIXRD spectra: c-La₂O₃ gradually forms in the 300-500 °C range while annealing at 600 °C generates h-La₂O₃ which exhibits, as inferred from our electrical data, a desirable κ ∼ 27. A quick transformation from h-La₂O₃ into La(OH)₃ occurs due to H₂O absorption, indicating that the annealed films are chemically unstable. This study extends our recent work on the h-La₂O₃ formation.     

Characterization of transient currents in HfO2 capacitors in the short timescale

We present a detailed experimental investigation of transient currents in HfO₂ capacitors in the short timescale. We show that the transient currents flowing through the capacitor plates when the gate voltage is reset to zero after a low voltage stress period follow a power-law time dependence t^−α (with α ? 1) over more than eight decades of time and down to the μs timescale. As transient currents in HfO₂ are largely increased with respect to the SiO₂ case, these results confirm that transient effects can be a severe issue for the successful integration of high-k dielectrics.     

Hot carrier effects in n-MOSFETs with SiO2/HfO2/HfSiO gate stack and TaN metal gate

Charge trapping and trap generation in field-effect transistors with SiO₂/HfO₂/HfSiO gate stack and TaN metal gate electrode are investigated under uniform and non-uniform charge injection along the channel. Compared to constant voltage stress (CVS), hot carrier stress (HCS) exhibits more severe degradation in transconductance and subthreshold swing. By applying a detrapping bias, it is demonstrated that charge trapping induced degradation is reversible during CVS, while the damage is permanent for hot carrier injection case.     

Effect of RuO2 electrode on laser-MBE prepared HfO2 gate dielectrics

In this paper, we report our recent study of the effect of RuO₂ as an alternative top electrode for pMOS devices to overcome the serious problems of polysilicon (poly-Si) gate depletion, high gate resistance and dopant penetration in the trend of down to 50 nm devices and beyond. The conductive oxide RuO₂, prepared by RF sputtering, was investigated as the gate electrode on the Laser MBE (LMBE) fabricated HfO₂ for pMOS devices. Structural, dielectric and electric properties were investigated. RuO₂/HfO₂/n-Si capacitors showed negligible flatband voltage shift (<10 mV), very strong breakdown strength (>10 MV cm⁻¹). Compared to the SiO₂ dielectric with the same EOT value, RuO₂/HfO₂/n-Si capacitors exhibited at least 4 orders of leakage current density reduction. The work function value of the RuO₂ top electrode was calculated to be about 5.0 eV by two methods, and the effective fixed oxide charge density was determined to be 3.3 × 10¹² cm⁻². All the results above indicate that RuO₂ is a promising alternative gate electrode for LMBE grown HfO₂ gate dielectrics.     

Effect of thin Si insertion at metal gate/high-k interface on electrical characteristics of MOS device with La2O3

The effect of a thin Si layer insertion at W/La₂O₃ interface on the electrical characteristics of MOS capacitors and transistors is investigated. A suppression in the EOT increase can be obtained with Si insertion, indicating the inhibition of diffusion of oxygen atoms into La₂O₃ layer by forming an amorphous La-silicate layer at the W/La₂O₃ interface. In addition, positive shifts in V_fb and V_th caused by Si insertion implies the formation of amorphous La-silicate layer at the top of La₂O₃ dielectrics reduces the positive fixed charges induced by the metal electrode. Consequently, a large improvement in mobility has been confirmed for both at peak value and at high E_eff of 1 MV/cm with Si inserted nFETs. Although a degradation trend on EOT scaling has been observed, the insertion of thin Si layer is effective in pushing the scaling limit.     

Resistive switching effects of HfO2 high-k dielectric

Resistive switching behavior of HfO₂ high-k dielectric has been studied as a promising candidate for emerging non-volatile memory technology. The low resistance ON state and high resistance OFF state can be reversibly altered under a low SET/RESET voltage of ±3 V. The memory device shows stable retention behavior with the resistance ratio between both states maintained greater than 103. The bipolar nature of the voltage-induced hysteretic switching properties suggests changes in film conductivity related to the formation and removal of electronically conducting paths due to the presence of oxygen vacancies induced by the applied electric field. The effect of annealing on the switching behavior was related to changes in compositional and structural properties of the film. A transition from bipolar to unipolar switching behavior was observed upon O₂ annealing which could be related to different natures of defect introduced in the film which changes the film switching parameters. The HfO₂ resistive switching device offers a promising potential for high density and low power memory application with the ease of processing integration.     

Investigation of high-K gate stacks with epitaxial Gd2O3 and FUSI NiSi metal gates down to CET=0.86 nm

Novel gate stacks with epitaxial gadolinium oxide (Gd₂O₃) high-k dielectrics and fully silicided (FUSI) nickel silicide (NiSi) gate electrodes are investigated. Ultra-low leakage current densities down to 10^–7 A cm^–2 are observed at a capacitance equivalent oxide thickness of CET=1.8 nm. The influence of a titanium nitride (TiN) capping layer during silicidation is studied. Furthermore, films with an ultra-thin CET of 0.86 nm at a Gd₂O₃ thickness of 3.1 nm yield current densities down to 0.5 A cm⁻² at V_g=+1 V. The extracted dielectric constant for these gate stacks ranges from k=13 to 14. These results emphasize the potential of NiSi/Gd₂O₃ gate stacks for future material-based scaling of CMOS technology.     

用于GaAs射频集成电路的不同厚度氧化铝MIM 电容的研究

本文研究了不同厚度的氧化铝对MIM电容直流和射频特性的影响。在1MHz下,对于20nm氧化铝MIM电容,其拥有3850 pF/mm₂的高电容密度和可接受的681 ppm/V₂的VCC-α电压系数。1MHz时突出的74 ppm/V₂VCC-α电压系数,8.2GHz谐振频率以及2GHz时41的Q值可以从100nm氧化铝MIM电容获得。采用GaAs工艺以及原子层淀积制造的高性能ALD氧化铝MIM电容很有可能成为GaAs射频集成电路很有前景的候选器件。     

Nanostructure effect of V2O5 buffer layer on performance of polymer-fullerene devices

Nanostructure of solar cell materials is often essential for the device performance. V₂O₅ nanobelt structure is synthesized with a solution process and further used as an anode buffer layer in polymer solar cells, resulting insignificantly improved power conversion efficiency (PCE of 2.71%) much higher than that of devices without the buffer layer (PCE of 0.14%) or with V₂O₅ powder as the buffer layer (1.08%). X-ray diffraction (XRD) results indicate that the V₂O₅ nanobelt structure has better phase separation while providing higher surface area for the P3HT:PCBM active layer to enhance photocurrent. The measured impedance spectrums show that the V₂O₅ nanobelt structure has faster charge transport than the powder material. This work clearly demonstrates that V₂O₅ nanobelt has great potential as a substitute of the conventionally used PEDOT-PSS buffer layer for high performance devices.     

Excellent performance of gas sensor based on In2O3-Fe2O3 nanotubes

In₂O₃-Fe₂O₃ nanotubes are synthesized by an electrospinning method. The as-synthesized materials are characterized by scanning electron microscope and X-ray powder diffraction. The gas sensing results show that In₂O₃-Fe₂O₃ nanotubes exhibit excellent sensing properties to acetone and formaldehyde at different operating temperatures. The responses of gas sensors based on In₂O₃-Fe₂O₃ nanotubes to 100 ppm acetone and 100 ppm formaldehyde are 25 (240℃) and 15 (260℃), and the response/recovery times are 3/7 s and 4/7 s, respectively. The responses of In₂O₃-Fe₂O₃ nanotubes to 1 ppm acetone (240℃) and formaldehyde (260℃) are 3.5 and 1.8, respectively. Moreover, the gas sensor based on In₂O₃-Fe₂O₃ nanotubes also possesses an excellent selectivity to acetone and formaldehyde.     

Initial leakage current related to extrinsic breakdown in HfO2/Al2O3 nanolaminate ALD dielectrics

Multiple successive breakdown events are reported for HfO₂/Al₂O₃ nanolaminate dielectrics grown by atomic-layer deposition. The first breakdown distribution is not a Weibull distribution and shows a long TBD tail at high failure percentiles. Analysis of the correlation between time-to-breakdown and initial current leakage allows identifying this tail with extrinsic breakdown. Screening of the data to eliminate the extrinsic tail demonstrates that the successive breakdown events are completely uncorrelated and perfectly match the successive breakdown theory. The statistical correlation between initial current and extrinsic breakdown distribution is explained in terms of variations of the unintentional interfacial SiO_x layer at the silicon substrate/dielectric interface.     

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.     

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.     

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.