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.     

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.     

Comparison of interfacial and electrical properties between Al2O3 and ZnO as interface passivation layer of GaAs MOS device with HfTiO gate dielectric

GaAs metal–oxide–semiconductor(MOS) capacitors with HfTiO as the gate dielectric and Al2O3 or ZnO as the interface passivation layer(IPL) are fabricated. X-ray photoelectron spectroscopy reveals that the Al2O3 IPL is more effective in suppressing the formation of native oxides and As diffusion than the ZnO IPL. Consequently, experimental results show that the device with Al2O3 IPL exhibits better interfacial and electrical properties than the device with ZnO IPL: lower interface-state density(7.21012 eV1cm2/, lower leakage current density(3.60107A/cm2 at Vg D1 V) and good C–V behavior.     

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.     

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.     

Temperature dependent interfacial and electrical characteristics during atomic layer deposition and annealing of HfO2 films in p-GaAs metal-oxide-semiconductor capacitors

We have investigated the temperature dependent interfacial and electrical characteristics of p-GaAs metal-oxide-semiconductor capacitors during atomic layer deposition(ALD) and annealing of HfO₂ using the tetrakis(ethylmethyl) amino hafnium precursor. The leakage current decreases with the increase of the ALD temperature and the lowest current is obtained at 300℃ as a result of the Frenkel-Poole conduction induced leakage current being greatly weakened by the reduction of interfacial oxides at the higher temperature. Post deposition annealing(PDA) at 500℃ after ALD at 300℃ leads to the lowest leakage current compared with other annealing temperatures. A pronounced reduction in As oxides during PDA at 500℃ has been observed using X-ray photoelectron spectroscopy at the interface resulting in a proportional increase in Ga₂O₃. The increment of Ga₂O₃ after PDA depends on the amount of residual As oxides after ALD. Thus, the ALD temperature plays an important role in determining the high-k/GaAs interface condition. Meanwhile, an optimum PDA temperature is essential for obtaining good dielectric properties.     

Characterization of the annealing impact on La2O3/HfO2 and HfO2/La2O3 stacks for MOS applications

The impact of various rapid thermal annealing used during the integration on the La₂O₃/HfO₂ and HfO₂/La₂O₃ stacks deposited by Atomic Layer deposition was analyzed. The consequences of lanthanum localization in such stacks on the evolution of the films during the rapid thermal annealing are investigated in term of morphology, crystalline structure, silicate formation and film homogeneity as a function of the depth. It appeared that the La₂O₃ location has an impact on the temperature of the quadratic phase formation which could be linked to the formation of SiOHfLa silicate and the resistance of the films to dissolution in HF 0.05 wt%.     

Density functional theory study of first-layer adsorption of ZrO2 and HfO2 on Ge(1 0 0)

Density functional theory was used to performed a survey of transition metal oxide (MO₂ = ZrO₂, HfO₂) ordered molecular adsorbate bonding configurations on the Ge(1 0 0)-4 × 2 surface. Surface binding geometries of metal-down (O-M-Ge) and oxygen-down (M-O-Ge) were considered, including both adsorbate and displacement geometries of M-O-Ge. Calculated enthalpies of adsorption show that bonding geometries with metal-Ge bonds (O-M-Ge) are essentially degenerate with oxygen-Ge bonding (M-O-Ge). Calculated electronic structures indicate that adsorbate surface bonding geometries of the form O-M-Ge tend to create a metallic interfaces, while M-O-Ge geometries produce, in general, much more favorable electronic structures. Hydrogen passivation of both oxygen and metal dangling bonds was found to improve the electronic structure of both types of MO₂ adsorbate systems, and induced the opening of true semiconducting band gaps for the adsorbate-type M-O-Ge geometries. Shifts observed in the DOS minima for both O-M-Ge and M-O-Ge adsorbate geometries are consistent with surface band bending induced by the adsorbate films, where such band bending extends much further into the Ge substrate than can be modeled by the Ge slabs used in this work.     

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.     

Improvement on low-temperature deposited HfO2 film and interfacial layer by high-pressure oxygen treatment

In this study, high-pressure oxygen (O₂ and O₂ + UV light) technologies were employed to effectively improve the properties of low-temperature-deposited metal oxide dielectric films and interfacial layer. In this work, 13 nm HfO₂ thin films were deposited by sputtering method at room temperature. Then, the oxygen treatments with a high-pressure of 1500 psi at 150 °C were performed to replace the conventional high temperature annealing. According to the XPS analyses, integration area of the absorption peaks of O-Hf and O-Hf-Si bonding energies apparently raise and the quantity of oxygen in deposited thin films also increases from XPS measurement. In addition, the leakage current density of standard HfO₂ film after O₂ and O₂ + UV light treatments can be improved from 3.12 × 10⁻⁶ A/cm² to 6.27 × 10⁻⁷ and 1.3 × 10⁻⁸ A/cm² at |Vg| = 3 V. The proposed low-temperature and high pressure O₂ or O₂ + UV light treatment for improving high-k dielectric films is applicable for the future flexible electronics.     

Comparative study of AlGaN/GaN metal-oxide-semiconductor heterostructure field-effect transistors with Al2O3 and HfO2 gate oxide

AlGaN/GaN metal-oxide-semiconductor heterostructure field-effect transistors (MOSHFETs) with Al₂O₃ gate oxide which was deposited by atomic layer deposition (ALD) were fabricated and their performance was then compared with that of AlGaN/GaN MOSHFETs with HfO₂ gate oxide. The capacitance (C)-voltage (V) curve of the Al₂O₃/GaN MOS diodes showed a lower hysteresis and lower interface state density than the C-V curve of the HfO₂/GaN diodes, indicating better quality of the Al₂O₃/GaN interface. The saturation of drain current in the I_D-V_GS relation of the Al₂O₃ AlGaN/GaN MOSHFETs was not as pronounced as that of the HfO₂ AlGaN/GaN MOSHFETs. The gate leakage current of the Al₂O₃ MOSHFET was five to eight orders of magnitude smaller than that of the HfO₂ MOSHFETs.     

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.     

Reliability and gate conduction variability of HfO2-based MOS devices: A combined nanoscale and device level study

The electrical properties and reliability of MOS devices based on high-k dielectrics can be affected when the gate stack is subjected to an annealing process, which can lead to the polycrystallization of the high-k layer. In this work, a Conductive Atomic Force Microscope (C-AFM) has been used to study the nanoscale electrical conduction and reliability of amorphous and polycrystalline HfO₂ based gate stacks. The link between the nanoscale properties and the reliability and gate conduction variability of fully processed MOS devices has also been investigated.     

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.     

Analysis of reliability characteristics of high capacitance density MIM capacitors with SiO2-HfO2-SiO2 dielectrics

In this paper, reliability as well as electrical properties of high capacitance density metal-insulator-metal (MIM) capacitor with hafnium-based dielectric is analyzed in depth. The fabricated MIM capacitor exhibits not only high capacitance density but also low voltage coefficient of capacitance (VCC) and low temperature coefficient of capacitance (TCC). It also has a low leakage current level of about ∼1 nA/cm² at room temperature and 1 V. However, it is shown that voltage linearity has a different dependence on the polarity of applied bias as temperature increases maybe due to the bulk traps between the metal electrode and high-k dielectric interface. In addition, the effect of charge trapping and de-trapping on the voltage linearity is analyzed under constant voltage stress.     

介质前后双重臭氧处理实现锗/氧化铪间界面钝化

The physical and electrical properties of a Ge/GeO₂/HfO₂/Al gate stack are investigated.A thin interfacial GeO₂ layer（ 1 nm） is formed between Ge and HfO₂ by dual ozone treatments,which passivates the Ge/high-k interface.Capacitors on p-type Ge substrates show very promising capacitance-voltage（C-V） characteristics by using in situ pre-gate ozone passivation and ozone ambient annealing after high-k deposition,indicating efficient passivation of the Ge/HfO₂ interface.It is shown that the mid-gap interface state density at the Ge/GeO₂ interface is 6.4×10¹¹ cm^-2·eV^-1.In addition,the gate leakage current density of the Ge/GeO₂/HfO₂/Al gate stack passivated by the dual ozone treatments is reduced by about three orders of magnitude compared to that of a Ge/HfO₂/Al gate stack without interface passivation.     

The correlation of the electrical properties with electron irradiation and constant voltage stress for MIS devices based on high-k double layer (HfTiSiO:N and HfTiO:N) dielectrics

This paper describes the influence of e-beam irradiation and constant voltage stress on the electrical characteristics of metal-insulator-semiconductor structures, with double layer high-k dielectric stacks containing HfTiSiO:N and HfTiO:N ultra-thin (1 and 2 nm) films. The changes in the electrical properties were caused by charge trapping phenomena which is similar for e-beam irradiation and voltage stress cases. The current flow mechanism was analyzed on the basis of pre-breakdown, soft-breakdown and post-breakdown current-voltage (J-V) experiments. Based on α-V analysis (α=d[ln(J)]/d[ln(V)]) of the J-V characteristics, a non-ideal Schottky diode-like current mechanism with different parameters in various ranges of J-V characteristics is established, which limits the current flow in these structures independent of irradiation dose or magnitude of applied voltage during stress.     

Effect of biasing at elevated temperature on the electronic structure of Pt/HfO2/Si stacks

The spatial distribution of charges in a Pt/HfO₂/Si stack has been manipulated by applying a cyclic bias voltage ±2.5 V in combination with moderate (T ∼ 630 K) heating. The modifications were monitored in situ by room temperature capacitance-voltage (C-V) and current-voltage (I-V) measurements and analyzed ex situ by hard X-ray photoelectron spectroscopy which additionally provides information on possible chemical changes at the interfaces. The experimental data on the charge/potential distributions resulting from the different steps of bias-temperature stress (BTS) are consistent with the model that additional oxygen vacancies, which are generated in HfO₂ and positively charged by charge transfer across the interface with a high work function metal (Pt), are driven across the HfO₂ layer. These vacancies ultimately control the observed growth/dissolution of SiO_x at the bottom interface upon negative/positive BTS, respectively.     

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.     

Interface composition of atomic layer deposited HfO2 and Al2O3 thin films on InAs studied by X-ray photoemission spectroscopy

We present a synchrotron-based XPS investigation on the interface between InAs and Al₂O₃ or HfO₂ layers, deposited by ALD at different temperatures, for InAs substrates with different surface orientations as well as for InAs nanowires. We reveal the composition of the native Oxide and how the high-κ layer deposition reduces Oxide components. We demonstrate some of the advantages in using synchrotron radiation revealing the variation in Oxide composition as a function of depth into the subsurface region and how we can indentify Oxides even on nanowires covering only a small fraction of the surface.