Reliability/Uniformity improvement induced by an ultrathin TiO2 insertion in Ti/HfO2/Pt resistive switching memories

Reliability/Uniformity of resistance switching in Ti/HfO₂/Pt memory structure was improved by inserting an interfacial layer of 5 nm-thick TiO₂ between Ti and 45 nm-thick HfO₂. As a native oxide of Ti, TiO₂, effectively limits the disorder migration of oxygen from HfO₂ to Ti layer, and provides the more chemically-stable and morphologically-uniform interfaces with both the Ti electrode and the HfO₂ layer. Meanwhile, more stable resistive switching was observed in Ti/TiO₂/HfO₂/Pt than that in Ti/HfO₂/Pt memory, and the random variation during endurance test observed in Ti/HfO₂/Pt was also greatly limited in Ti/TiO₂/HfO₂/Pt memory. From these results, a thin TiO₂ insertion between the Ti electrode with the HfO₂ active layer, could greatly improve the reliability/uniformity of the Ti/HfO₂/Pt memory devices.     

Unipolar nonvolatile memory devices with composites of poly(9-vinylcarbazole) and titanium dioxide nanoparticles

Organic-based devices with an 8 × 8 array structure using titanium dioxide nanoparticles (TiO₂ NPs) embedded in poly(9-vinylcarbazole) (PVK) film exhibited bistable resistance states and a unipolar nonvolatile memory effect. TiO₂ NPs were a key factor for realizing the bistability and the concentration of TiO₂ NPs influenced ON/OFF ratio. From electrical measurements, switching mechanism of PVK:TiO₂ NPs devices was closely associated with filamentary conduction model and it was found that the OFF state was dominated by thermally activated transport while the ON state followed tunneling transport. PVK:TiO₂ NPs memory devices in 8 × 8 array structure showed a uniform cell-to-cell switching, stable switching endurance, and a high retention time longer than 10⁴ s.     

Characteristics of RF reactive sputter-deposited Pt/SiO2/n-InGaN MOS Schottky diodes

All RF sputtering-deposited Pt/SiO₂/n-type indium gallium nitride (n-InGaN) metal–oxide–semiconductor (MOS) diodes were investigated before and after annealing at 400 °C. By scanning electron microscopy (SEM), the thickness of Pt, SiO_2, n-InGaN layer was measured to be ~250, 70, and 800 nm, respectively. AFM results also show that the grains become a little bigger after annealing, the surface topography of the as-deposited film was smoother with the rms roughness of 1.67 nm and had the slight increase of 1.92 nm for annealed sample. Electrical properties of MOS diodes have been determined by using the current–voltage (I–V) and capacitance–voltage (C–V) measurements. The results showed that Schottky barrier height (SBH) increased slightly to 0.69 eV (I–V) and 0.82 eV (C–V) after annealing at 400 °C for 15 min in N₂ ambient, compared to that of 0.67 eV (I–V) and 0.79 eV (C–V) for the as-deposited sample. There was the considerable improvement in the leakage current, dropped from 6.5×10⁻⁷ A for the as-deposited to 1.4×10⁻⁷ A for the 400 °C-annealed one. The annealed MOS Schottky diode had shown the higher SBH, lower leakage current, smaller ideality factor (n), and denser microstructure. In addition to the SBH, n, and series resistance (R_s) determined by Cheungs׳ and Norde methods, other parameters for MOS diodes tested at room temperature were also calculated by C–V measurement.     

Structural and electrical properties of radio frequency magnetron sputtered tantalum oxide films: Influence of post-deposition annealing

The as-deposited and annealed radio frequency reactive magnetron sputtered tantalum oxide (Ta₂O₅) films were characterized by studying the chemical binding configuration, structural and electrical properties. X-ray photoelectron spectroscopy and X-ray diffraction analysis of the films elucidate that the film annealed at 673 K was stoichiometric with orthorhombic β-phase Ta₂O₅. The dielectric constant values of the tantalum oxide capacitors with the sandwich structure of Al/Ta₂O₅/Si were in the range from 14 to 26 depending on the post-deposition annealing temperature. The leakage current density was <20 nA cm^?2 at the gate bias voltage of 0.04 MV/cm for the annealed films. The electrical conduction mechanism observed in the films was Poole–Frenkel.     

Influence of N2 and O2 annealing treatment on the optical bandgap of polycrystalline Ga2O3:Cu films

Cu-doped Ga₂O₃ thin films were deposited by electron beam evaporation with subsequent annealing at 1000 °C in N₂ and O₂ for 1 h. The influence of the annealing atmosphere on the crystal structure, surface morphology and optical properties of Ga₂O₃:Cu films was investigated by X-ray diffraction (XRD), high-resolution transmission electron microscopy (HRTEM), atomic force microscopy (AFM), and transmittance and photoluminescence (PL) spectroscopy. The optical bandgap deduced from the absorption spectrum was greater for the O₂ annealed than for N₂ annealed samples. In both cases the bandgap was wider than for bulk β-Ga₂O₃. The grain size and surface roughness were sensitive to the annealing atmosphere. Results confirmed that the annealed samples were polycrystalline β-Ga₂O₃ with some amorphous phase. We hypothesize that annealing in oxygen led to recrystallization of the Ga₂O₃:Cu film. Annealing treatment improved the crystal quality of Ga₂O₃:Cu films and the PL intensity of the samples increased.     

Improved reliability of NO treated NH3-nitrided oxide with regard to O2 annealing

NH₃-nitrided oxide has been annealed in NO or O₂ gas at 1000°C for 1 min and the electrical characteristics, charge trapping and time-dependent dielectric breakdown (TDDB) have been studied. It was observed that in the F–N region before stress the conduction current is the same for all the samples but intrinsic breakdown is earlier for O₂ annealed NH₃-nitrided oxide. After stress, the leakage current increases abruptly for the O₂ annealed NH₃-nitrided oxide. The TDDB characteristics have been measured for wet, NO and O₂ annealed NH₃-nitrided oxide. It was observed that the endurance of wet and NO annealed NH₃-nitrided oxide is the same, but the O₂ annealed NH₃-nitrided oxide has a lot of initial failure at the same stress of −11 MV cm⁻¹. From the experimental results, it can be said that NO annealing not only removes H which comes from the NH₃ nitridation but also improves the oxide reliability by replacing strained Si–O bonds for a stable Si–N bond.     

Multilevel characteristics for bipolar resistive random access memory based on hafnium doped SiO2 switching layer

We fabricated TiN/Hf:SiO₂/Pt memory cell with the small size of 1×1 um² by lithography and sputtering technology, which demonstrated excellent bipolar resistive switching (RS) characteristics. The device presents good endurance and outstanding uniformity. The coefficient of variation of V_set, V_reset, R_on and R_off were found to be 5.05%, 4.78%, 4.18%, and 15.78%, respectively. For the device with hafnium doped SiO₂ switching layer, multilevel storage capability can be successfully obtained by varying either the stop voltage or the compliance current in the SET process. In addition, the impact of forming current on the RS properties was studied. We found that the ratio of On/Off current for the device increased with the decrease of the forming current, which would be beneficial for the design of low power device. Possible RS mechanisms aiming to explain the impact of forming current on the RS characteristics and multilevel storage were also deduced.     

Annealing effects on the electrical properties of spin coated poly (3-hexylthiophene) (P3HT) thin films

Poly (3-hexylthiophene-2, 5-diyl) (P3HT) thin films were prepared using spin coating technique and the effect of annealing on the bias switching for memory applications were studied. Due to annealing, the threshold voltage for switching was reduced considerably. In bias switching, threshold voltage was least for the sample annealed at 100 °C. Addition of phenyl-C₆₁-butyric acid-methyl-ester (PCBM) into P3HT also reduced the threshold voltage. It was also found that the devices with gold (Au) top electrode switched at a lower threshold voltage compared to their aluminium (Al) counterparts.     

Resistive switching properties of a thin SiO2 layer with CeOx buffer layer on n+ and p+ Si bottom electrodes

Resistive switching properties of a 2-nm-thick SiO₂ with a CeO_x buffer layer on p⁺ and n⁺ Si bottom electrodes were characterized. The distribution of set voltage (V_set) with the p⁺ Si bottom electrode devices reveals a Gaussian distribution centered in 4.5 V, which reflects a stochastic nature of the breakdown of the thin SiO₂. Capacitance–voltage (C–V) measurements indicate the trapping of electrons by positively shifting the C–V curve by 0.2 V during the first switching cycle. On the other hand, devices with the n⁺ Si bottom electrodes showed a broad distribution in V_set with a mean value higher than that of p⁺ Si bottom electrode devices by 0.9 V. Although no charge trapping was observed with n⁺ Si bottom electrode devices, a degradation in interface states was confirmed, causing a tail in the lower side of the V_set distribution. Based on the above measurements, the difference in the V_set can be understood by the work function difference and the contribution of electron trapping.     

A fundamental understanding of nickel oxide based resistive random access memory with high percentage of oxygen

In this paper, we report the fundamental properties of NiO_x based Resistive RAM (RRAM) devices with Al top electrode and Ni bottom electrode. The NiO_x deposition was performed in a relatively high oxygen environment. The initial J–V curves in positive and negative bias indicated symmetric behavior in spite of a significant difference in the vacuum work functions of Al and Ni. The capacitance–voltage characterizations indicated NiO_x to be a p-type semiconductor with acceptor doping density between 6 × 10¹⁸ cm^?3 and 5 × 10²⁰ cm^?3. Switching behavior was observed after electroforming the devices. The devices failed after multiple switching cycles by switching into a relatively low conductive state. The mechanism of failure was attributed to the formation of Al₂O₃ due to a slow oxidation of Al electrodes with repeated cycles.     

N2O treatment enhancement-mode InAlN/GaN HEMTs with HfZrO2 High-k insulator

A normally-off InAlN/GaN MIS-HEMT with HfZrO₂ gate insulator was realized and investigated. By using N₂O plasma treatment beneath the gate region, 13 nm InAlN Schottky layer was oxidized to AlON_x + 4 nm InAlN Schottky layer. The strong polarization induced carriers in traditional InAlN/GaN 2 DEG quantum well was reduced for enhancement-mode operation. High-k thin film HfZrO₂ was used for gate insulator of E-mode device to further suppress gate leakage current and enhance device gate operation range. The maximum drain current of E-mode InAlN/GaN MIS-HEMT was 498 mA/mm and this value was higher than previous published InAlN/GaN E-mode devices. The measurement results of low-frequency noise also concluded that the low frequency noise is attributed to the mobility fluctuation of the channel and N₂O plasma treatment did not increase fluctuation center of gate electrode.     

The effect of annealing temperature on the electronic parameters and carrier transport mechanism of Pt/n-type Ge Schottky diode

The Pt nano-film Schottky diodes on Ge substrate have been fabricated to investigate the effect of annealing temperature on the characteristics of the device. The germanide phase between Pt nano-films and Ge substrate changed and generated interface layer PtGe at 573 K and 673 K, Pt₂Ge₃ at 773 K. The current–voltage(I - V) characteristics of Pt/n-Ge Schottky diodes were measured in the temperature range of 183–303 K. Evaluation of the I - V data has revealed an increase of zero-bias barrier height Φ_B0 but the decrease of ideality factor n with the increase in temperature. Such behaviors have been successfully modeled on the basis of the thermionic emission mechanism by assuming the presence of Gaussian distributions. The variation of electronic transport properties of these Schottky diodes has been inferred to be attributed to combined effects of interfacial reaction and phase transformation during the annealing process. Therefore, the control of Schottky barrier height at metal/Ge interface is important to realize high performance Ge-based CMOS devices.     

Characterization of ZrTiO4 thin films prepared by sol–gel method

The electrical properties, memory switching behavior, and microstructures of ZrTiO₄ thin films prepared by sol–gel method at different annealing temperatures were investigated. All films exhibited ZrTiO₄ (111) and (101) orientations perpendicular to the substrate surface, and the grain size increased with increasing annealing temperature. A low leakage current density of 1.47×10^?6 A/cm² was obtained for the prepared films. The I–V characteristics of ZrTiO₄ capacitors can be explained in terms of ohmic conduction in the low electric field region and Schottky emission in the high electric field region. An on/off ratio of 10² was measured in our glass/ITO/ZrTiO₄/Pt structure with an annealing temperature of 600 °C. Considering the primary memory switching behavior of ZrTiO₄, ReRAM based on ZrTiO₄ shows promise for future nonvolatile memory applications.     

Control of the Ti diffusion in Pt/Ti bottom electrodes for the fabrication of PZT thin film transducers

For the achievement of microactuators based on piezoelectric thin films, a Pt/Ti/Si bottom electrode is widely used. This study presents the experimental results for Ti out-diffusion in Pt and Si for both sputtered Pt/Ti and Pt/TiO_x electrodes. These results have been compared before and after a rapid thermal annealing (RTA). The diffusion has been characterized by secondary ion mass spectroscopy (SIMS) analysis using Cs⁺ as a primary ion source. The Pt orientation has been observed by XRD measurements. Ti thin films (20 nm) have been sputtered in pure Ar whereas TiO_x films have been obtained by reactive sputtering in a mixture of Ar/O₂ (90/10). Finally, the Pt (100 nm) has been sputtered without vacuum breaking. After RTA (400°C, 30 s, in N₂), the Pt film exhibited a (1 1 1) orientation for both Ti and TiO_x adhesion films. The roughness of the Pt film measured by AFM with TiO_x underlayer was 80% less than that of the Pt/Ti bi-layer. The TiO_x film, as shown by SIMS analysis, has drastically reduced the diffusion of Ti in both Pt and Si. This phenomenon is accompanied by a very low Pt roughness. These results are analyzed in terms of diffusion and regrowth mechanisms inside the Pt film.     

Investigation of Si/SiGe/Si heterostructure implanted by H ion and annealed in vacuum and dry O2 ambient

The 20-nm-thick Si cap layer/74-nm-thick Si_0.72Ge_0.28 epilayer/Si heterostructures implanted by 25 keV H⁺ ion to a dose of 1×10¹⁶ cm⁻² were annealed in ultra-high vacuum ambient and dry O₂ ambient at the temperature of 800 °C for 30 min, respectively. Rutherford backscattering/ion channeling (RBS/C), Raman spectra, high-resolution X-ray diffraction (HRXRD) and atomic force microscopy (AFM) were used to characterize the structural characteristics of the Si_0.72Ge_0.28 layer. Investigations by RBS/C demonstrated that the crystal quality of the Si/Si_0.72Ge_0.28/Si heterostructure sample implanted by 25 keV H⁺ in conjunction with subsequent annealing in dry O₂ ambient is superior to that of identical sample annealing in ultra-high vacuum ambient. The less strain relaxation of SiGe layer of the Si/Si_0.72Ge_0.28/Si heterostructures implanted by H ion and annealed in dry O₂ ambient at the temperature of 800 °C for 30 min could be doublechecked by Raman spectra as well as HRXRD, which was compared with that in an identical sample annealed in ultra-high vacuum ambient for identical thermal budget. In addition, the SiGe layer of the H-implanted Si/SiGe/Si heterostructural sample annealed in dry O₂ ambient accompanied by better crystal quality and less strain relaxation made its surface morphology superior to that of the sample annealed in ultra-high vacuum ambient at the temperature of 800 °C for 30 min, which was also verified by AFM images.     

Improvement of memory properties for MANOS-type nonvolatile memory devices with high-pressure wet vapor annealing

Effects of high-pressure wet vapor annealing (HPWA) on the memory properties of Metal/Alumina/Nitride/Oxide/Silicon (MANOS)-type flash memory devices are studied. The Oxide/Nitride/Alumina (ONA) stacks were annealed in a high-pressure wet vapor ambient (N₂:D₂O = 10 atm:2 atm) at 250 °C for 5 min. It is found that HPWA can effectively passivate the intrinsic defects of the Al₂O₃ film by oxygen species, leading to the improvement of blocking efficiency. The HPWA significantly improved the electrical and reliability characteristics of ONA stacks, such as leakage current density, saturation level of erase, charge loss rate through the blocking oxide, and memory window after the program and erase cycles. HPWA shows promise for future MANOS-type flash memory devices.     

Effect of post annealing on the resistive switching of TiO2 thin film

The effect of annealing on the resistive switching of 35-nm-thick TiO₂ thin film deposited with magnetron sputtering system was studied. Pt and Ag were used as a top electrode (TE), and Pt was used as a bottom electrode (BE). For Pt/as-deposited TiO₂/Pt structure, both unipolar (URS) and bipolar resistive switching (BRS) were observed depending on the current compliance level. For Pt/400 °C annealed TiO₂/Pt structure, only BRS was observed regardless of the current compliance level. The increase in the work function of the TiO₂ film after annealing lowers the potential barrier height and changes the electron transfer process which was also confirmed from Ag/as-deposited TiO₂/Pt structure. Above 600 °C, the film becomes leaky with the increase in grain size and roughness and the resistive switching behavior was not observed.     

Improvement of charge/discharge performance for lithium ion batteries with tungsten trioxide electrodes

Although a large amount of research on Li ion transportation has been carried out with the aim of improving the properties of lithium ion batteries, there has been little detailed research on electron conduction. Hence, we have been focusing on improving the charge/discharge performance of lithium ion batteries by increasing the electron conductivity of the electrodes. The electron conductivity of crystalline tungsten trioxide (WO₃) was found to be increased by N₂ annealing owing to the generation of oxygen vacancies. It was clarified that increasing the conductivity of the electrodes can improve the performance of lithium ion batteries, particularly their charge/discharge speed and reversibility. Additionally, the best performance was observed in a sample subjected to high-temperature annealing at 700 °C in N₂ ambient, which decreased the resistivity of the WO₃ electrode by five orders of magnitude and simultaneously changed the monoclinic crystalline structure into a cubiclike structure into which Li ions are more easily intercalated. Therefore, to enhance the charge/discharge performance of lithium ion batteries, electron conduction should be a focus of research. Crystalline WO₃ was also demonstrated to be a promising material for electrodes since oxygen vacancy generation can be induced by a simple annealing treatment, improving the electron conduction and Li ion transportation.     

Electron transport mechanism of tungsten trioxide powder thin film studied by investigating effect of annealing on resistivity

We report a new approach for improving the recharging and discharging speed of lithium ion batteries based on understanding of the electron conduction mechanism of tungsten trioxide (WO₃) powder thin films fabricated from nanoparticles and used in lithium ion battery electrodes. Resistivity measurements are carried out after annealing in N₂ or 5% O₂ + 95% N₂ ambient. Annealing in N₂ ambient decreases the resistivity owing to the increased number of oxygen vacancies in the WO₃ thin film. Fitting results obtained from the resistivity are used to propose the simultaneous existence of two types of electron conduction mechanism, band conduction and nearest-neighbor hopping (NNH) conduction, contributing to electron conduction in WO₃ thin films.     

Effect of annealing on structural,optical and electrical properties of pulse electrodeposited tin sulfide films

Polycrystalline tin sulfide (SnS) thin films were grown on conducting glass substrates by pulse electrodeposition. The effect of annealing on the physical properties such as structure, morphology, optical, and opto-electronic properties were evaluated to understand the effect of post-deposition treatment for SnS films. Annealing at temperatures higher than 250 °°C resulted in the formation of SnS₂ as a second phase, however, no significant grain growth or morphological changes were observed for films after annealing at 350 °C. A small change in band gap of 0.1 eV observed for films annealed at 350 °C was interpreted as due to the formation of SnS₂ rather than due to morphological changes. This interpretation was supported by X-ray diffractometry, scanning electron microscopy, and Raman spectral data. The electric conduction in the films is controlled by three shallow trap levels with activation energies 0.1, 0.05, and 0.03 eV. The trap with energy 0.03 eV disappeared after annealing at higher temperature, however, the other two traps were unaffected by annealing.