Ultra-low-energy ion-beam-synthesis of Ge nanocrystals in thin ALD Al2O3 layers for memory applications

Structural and electrical properties of ALD-grown 5 and 7 nm-thick Al₂O₃ layers before and after implantation of Ge ions (1 keV, 0.5–1 × 10¹⁶ cm^?2) and thermal annealing at temperatures in the 700–1050 °C range are reported. Transmission Electron Microscopy reveals the development of a 1 nm-thick SiO₂-rich layer at the Al₂O₃/Si substrate interface as well as the formation of Ge nanocrystals with a mean diameter of ～5 nm inside the implanted Al₂O₃ layers after annealing at 800 °C for 20 min. Electrical measurements performed on metal–insulator–semiconductor capacitors using Ge-implanted and annealed Al₂O₃ layers reveal charge storage at low-electric fields mainly due to location of the Ge nanocrystals at a tunnelling distance from the substrate and their spatial dispersion inside the Al₂O₃ layers.     

High Energy Storage Performance of Opposite Double‐Heterojunction Ferroelectricity–Insulators

In this study, the excellent energy storage performance is achieved by constructing opposite double‐heterojunction ferroelectricity–insulator–ferroelectricity configuration. The PbZr_0.52Ti_0.48O₃ films and Al₂O₃ films are chosen as the ferroelectricity and insulator, respectively. The microstructures, polarization behaviors, breakdown strength, leakage current density, and energy storage performance are investigated systematically of the constructed PbZr_0.52Ti_0.48O₃/Al₂O₃/PbZr_0.52Ti_0.48O₃ opposite double‐heterojunction. The ultrahigh electric field breakdown strength (≈5711 kV cm^?1) is obtained, which is beneficial to achieve high energy storage density. Meanwhile, the high linearity of hysteresis loops with low energy dissipation is obtained at a proper annealing temperature, which is induced by partially crystallized and is in favor of achieving high energy storage efficiency η. The PbZr_0.52Ti_0.48O₃/Al₂O₃/PbZr_0.52Ti_0.48O₃ annealed at 550 °C exhibits excellent energy storage performance with a storage density of 63.7 J cm^?3 and efficiency of 81.3%, which is ascribed to the synergetic effect of electric breakdown strength (E_BDS = 5711 kV cm^?1) and the polarization (P_m–P_r = 23.74 µC cm^?2). The proposed method in this study opens a new door to improve the energy storage performance of inorganic ferroelectric capacitors.     

Structural, optical and electronic properties of oxidized AIN thin films at different temperatures

We report on the properties of a novel insulator, AlO:N for application in semiconductors produced by thermally oxidizing AlN thin films. The process steps were similar to those used for SiO₂, creating the possibility of a new technology for metal-insulator-semiconductor field effect devices and integrated circuits. Thin films of AlN were deposited by radio-frequency magnetron reactive sputtering on p-type silicon or fused quartz substrates. As-deposited AlN film thickness ranged from 0.05 to 0.7 μm, with polycrystalline structure revealed by x-ray diffraction. Oxidation was performed under O₂ flow at 800 to 1100°C for 1–4 h. AlN films were oxidized partially or fully into Al₂O₃, depending on initial thickness, oxidation temperature and time. X-ray diffraction indicates the presence of several phases of Al₂O₃ at 1000°C, whereas at 1100°C, only the α-Al₂O₃ phase was found. Considering the importance of surface field effect device applications, the surfaces of oxidized films were examined with atomic force microscopy in air, and a clear change was observed in the surface structure of the oxidized film from that of as-deposited AlN films. Capacitance-voltage measurements of metal-oxide-semiconductor structures yielded a dielectric constant of AlO:N between 8–12 and a net oxide-trapped-charge density of ∼10¹¹ cm⁻². Using Fourier transform infrared spectrometry transmittance and reflectance, some α-Al₂O₃ modes were observed. In this paper, we describe the general properties of the oxide thin films, bulk and interface, at different temperatures.     

Some properties of chemically vapor deposited films of AlxOyNz on silicon

Transmission electron microscopy (TEM) studies of films prepared in the AlN-Al₂O₃ pseudobinary system by chemical vapor deposition (as described in a companion paper entitled, “Chemical Vapor Deposition of Al_xO_yN_z Films”) indicates that four different phases can be obtained by altering the NH₃/CO₂ gas ratio and preparation temperature. Films prepared at 900°C yield three polycrystalline phases and an amorphous composition. From zero to 25 at. percent O an AlN phase is observed. Amorphous material is observed from 25 to 47 at. percent O. From 47 to 59 at. percent O an Al_xO_yN_z spinel is observed. At 60 at. percent O (pure Al₂O₃) an alumina phase is observed (KI phase). For 770°C films the AlN phase is observed from zero to 8 at. percent 0; from 8 to 23 at. percent O the zeta-alumina phase is seen; and at 60 at. percent O the KI alumina phase is again observed. For both the 770 and 900°C films, the grain size of the AlN phase was found to decrease with increasing oxygen content. Direct current-voltage, dielectric breakdown and capacitance-voltage measurements were performed on the 900 and 770°C films with a variety of film compositions. For pure AlN and Al₂O₃, current-voltage and dielectric breakdown measurements correlate with the grain size observed by TEM. A maximum in breakdown field was observed for 900°C films at the composition which yielded minimum grain size of the AlN phase. A similar maximum is observed for the zeta-Al₂O₃ phase of the 770°C films. Positive flatband voltages and hysteresis of the capacitance-voltage trace was observed for most samples. Dielectric constants greater than 8 have been observed for some compositions. Several compositions appear to be attractive candidates for charge storage layers in MIOS devices.     

Structural and Electrical Properties of Atomic Layer Deposited Al‐Doped ZnO Films

Structural and electrical properties of Al‐doped ZnO (AZO) films deposited by atomic layer deposition (ALD) are investigated to study the extrinsic doping mechanism of a transparent conducting oxide. ALD‐AZO films exhibit a unique layer‐by‐layer structure consisting of a ZnO matrix and Al₂O₃ dopant layers, as determined by transmission electron microscopy analysis. In these layered AZO films, a single Al₂O₃ dopant layer deposited during one ALD cycle could provide ≈4.5 × 10¹³ cm^?2 free electrons to the ZnO. The effective field model for doping is suggested to explain the decrease in the carrier concentration of ALD‐AZO films when the interval between the Al₂O₃ layers is reduced to less than ≈2.6 nm (>3.4 at% Al). By correlating the electrical and structural properties, an extrinsic doping mechanism of ALD‐AZO films is proposed in which the incorporated Al atoms take oxygen from the ZnO matrix and form doubly charged donors, such as oxygen vacancies or zinc interstitials.     

Formation of aluminum oxide films from aluminum hexafluoroacetylacetonate at 350–450° c

A study of the thermally activated decomposition of Al(hfa)₃ (aluminum hexafluoroacetylacetonate) from the gas phase to form Al₂O₃ on silicon substrates is reported. The decomposition process was carried out in an open tube atmospheric pressure reactor in either argon or oxygen/argon mixtures in the temperature range, 350–450° C. The chemical vapor deposition process resulted in the formation of aluminum oxide films in all instances. The dielectric strength of Al/Al₂O₃/Si capacitors which received a post-metal anneal, but did not receive a high temperature annealing treatment, with aluminum oxide films prepared from Al(hfa)₃ in argon, was found to be in the range 2–6 MV/cm. The difference between the flatband voltage of the MOS structures and the metal-silicon work function difference was positive, indicative of a net negative oxide charge with a density of approximately 3 × 10¹¹ – 3 × 10¹² cm^-2, assuming the charge is located at the oxide-silicon interface. Decomposition of Al(hfa)₃ was also carried out in oxygen/argon mixtures with the oxygen concentration in the range 10–60 vol %. This process led to the deposition of aluminum oxide films with breakdown fields in the range 8–9 MV/cm. However, the flatband voltages of the Al/Al₂O₃/Si capacitors were even more positive than those obtained with Al₂O₃ formed in pure argon. High temperature (800–1000° C) oxygen or nitrogen annealing treatments of alumina films deposited in either argon or oxygen/argon mixtures were evaluated from the point of view of their influence on the oxide film properties. In particular, an annealing process in oxygen at 1000° C for 15 min was found to result in a reduction of the net negative oxide charge, and an improvement of the dielectric strength of films deposited in argon. Films formed in oxygen/argon mixtures did not change appreciably following oxygen annealing, as far as breakdown fields are concerned, but the oxide net negative charge was reduced. As in an earlier study by the authors, of copper film deposition from Cu(hfa)₂, it was found that essentially carbon free films could be obtained under appropriate conditions.     

Nonvolatile Metal–Oxide–Semiconductor Capacitors with Ru-RuOx Composite Nanodots Embedded in Atomic-Layer-Deposited Al2O3 Films

Growth of Ru-RuO _x composite nanodots (RONs) on atomic-layer-deposited Al₂O₃ films has been investigated using magnetic sputtering of a Ru target followed by postdeposition annealing. RONs with a density as high as ~2 × 10¹² cm⁻² were obtained together with good uniformity. Subsequently, metal–oxide–semiconductor capacitors with RONs embedded in Al₂O₃ films have been electrically characterized for different configurations of tunneling layers (T)/blocking layers (B), and the underlying mechanisms of charge storage are discussed. For a 6-nm T/22-nm B device, a memory window of 3.7 V is achieved for a ±7 V programing/erasing voltage for 0.1 ms, and superior charge retention of more than 80% is achieved after 10 years.     

Direct Determination of Energy Band Alignments of Ni/Al2O3/GaN MOS Structures Using Internal Photoemission Spectroscopy

The energy band alignments of Ni/Al₂O₃/GaN heterostructures have been explored by internal photoemission (IPE) and capacitance–voltage (CV) measurements. By performing IPE measurements at both reverse- and forward-bias conditions, the Ni/Al₂O₃ Schottky barrier is found to be 2.9 ± 0.1 eV with the presence of a strong image force lowering effect, while the Al₂O₃/GaN conduction-band offset is determined to be 2.2 ± 0.1 eV and is insensitive to oxide electrical field. CV-based flat-band voltage analysis has further been performed on samples with different oxide thicknesses, not only confirming the IPE-measured band alignment but also revealing the presence of 3.0 × 10¹² cm^-2 net positive charge at the Al₂O₃/GaN interface.     

Reliable impurity trap memory with high charge trap efficiency using ultrathin SiO2 impurity host layer for nonvolatile memory application

We demonstrated reliable impurity trap memory (ITM) with high charge trap efficiency by incorporating only 1 nm-SiO₂ impurity host layer (IHL) between Al₂O₃ diffusion barrier layer and blocking oxide. While the ITM without IHL showed significant retention degradation as the amount of Ti impurity increased from 0.7 to 3 Å for enlarging memory window, the ITM with IHL showed stable retention characteristic which is charge loss less than 1 V after 10⁴ s at 85 °C. We postulated that the chemical reaction between Ti and SiO₂ induced three dimensionally-distributed impurity traps in IHL, which could result in the well-discrete stored charges in program mode.     

Charge-trapping characteristics of BaTiO3 with and without nitridation for nonvolatile memory applications

The charge-trapping characteristics of BaTiO₃ with and without nitrogen incorporation were investigated based on Al/Al₂O₃/BaTiO₃/SiO₂/Si (MONOS) capacitors. The physical properties of the high-k films were analyzed by transmission electron microscopy and X-ray photoelectron spectroscopy. Compared with the MONOS capacitor with BaTiO₃ as charge-trapping layer, the one with nitrided BaTiO₃ showed higher program speed even at lower operating voltage (4.3 V at +8 V for 100 μs), better endurance property and smaller charge loss (charge loss of 10.6% after 10⁴ s at 85 °C), due to the nitrided BaTiO₃ film exhibiting higher charge-trapping efficiency caused by nitrogen incorporation and suppressed leakage induced by nitrogen passivation.     

Enhanced charge storage characteristics by ZrO2 nanocrystallites precipitated from amorphous (ZrO2)0.8(SiO2)0.2 charge trapping layer

Charge trapping memory capacitors using (ZrO₂)_0.8(SiO₂)_0.2 film as charge trapping layer and amorphous Al₂O₃ as the tunneling layer and blocking layer were fabricated for nonvolatile semiconductor memory application. The ZrO₂ nanocrystallites with a size of 3–5 nm precipitated from amorphous (ZrO₂)_0.8(SiO₂)_0.2 during rapid thermal annealing at 800 °C can serve as the storage nodes, with which a large hysteresis memory window of 7.5 V at a sweeping gate voltage of 8 V has been achieved. At 150 °C bake temperature, the memory capacitor exhibited an excellent endurance up to 10⁵ write/erase cycles, after which a small charge loss of about 12% was achieved.     

Profiling of traps in SiO2/Al2O3 gate stack by the charge pumping technique

In this paper, we present our results on the distribution and generation of traps in a SiO₂/Al₂O₃ transistor. The investigation has been carried out by using charge pumping measurements, both variable voltage and frequency techniques, and constant voltage stress.By increasing the amplitude of the gate pulse we observe an increase of the charge recombined per cycle closely related to the contribution of shallow traps near the SiO₂/Al₂O₃ interface. By reducing the pulse frequency we measure an increase in the charge pumping current due to traps located deeper in the Al₂O₃. By combining charge pumping and constant voltage stress measurements, we found that the traps are mostly generated near the Si/SiO₂ interface.     

Improved Interface and Electrical Properties by Inserting an Ultrathin SiO2 Buffer Layer in the Al2O3/Si Heterojunction

An ultrathin SiO₂ interfacial buffer layer is formed using the nitric acid oxidation of Si (NAOS) method to improve the interface and electrical properties of Al₂O₃/Si, and its effect on the leakage current and interfacial states is analyzed. The leakage current density of the Al₂O₃/Si sample (8.1 × 10^?9 A cm^?2) due to the formation of low‐density SiO_x layer during the atomic layer deposition (ALD) process, decreases by approximately two orders of magnitude when SiO₂ buffer layer is inserted using the NAOS method (1.1 × 10^?11 A cm^?2), and further decreases after post‐metallization annealing (PMA) (1.4 × 10^?12 A cm^?2). Based on these results, the influence of interfacial defect states is analyzed. The equilibrium density of defect sites (N_d) and fixed charge density (N_f) are both reduced after NAOS and then further decreased by PMA treatment. The interface state density (D_it) at 0.11 eV decreases about one order of magnitude from 2.5 × 10¹² to 7.3 × 10¹¹ atoms eV^?1 cm^?2 after NAOS, and to 3.0 × 10¹⁰ atoms eV^?1 cm^?2 after PMA. Consequently, it is demonstrated that the high defect density of the Al₂O₃/Si interface is drastically reduced by fabricating ultrathin high density SiO₂ buffer layer, and the insulating properties are improved.     

Effects of Metal Work Function and Contact Potential Difference on Electron Thermionic Emission in Contact Electrification

Triboelectric nanogenerator (TENG) is a direct measure of the surface charge density, thus providing a novel and powerful tool to study the essential mechanism of contact electrification (CE). A variety of TENGs including a Pt‐Al₂O₃ TENG, Au‐Al₂O₃ TENG, Ti‐Al₂O₃ TENG, Al‐Al₂O₃ TENG, and SiO₂‐Al₂O₃ TENG are prepared in this study. After introducing initial charges on the Al₂O₃ surface of the TENGs, the long‐term evolution of surface charge quantity is investigated at different temperatures. The results show that charge variation of all the TENGs is analogous to exponential decay and is in accord with the thermionic emission model, verifying the electron transfer dominated mechanism of CE. Additionally, it is explored for the first time that the potential barrier of materials can be regulated by changing the contacting metals or dielectrics. Regulation of the barrier at high temperatures fully excludes the influence of ions from moisture and functional groups, which further indicates the dominant role played by electron transfer in CE. Surface state models for explaining barrier regulation during CE for both metal–dielectric and dielectric–dielectric pairs are proposed. This study provides a new perspective of the exploration of CE, and a novel method for further increasing or rapidly eliminating electrification of charged materials.     

Extremely High Silver Ionic Conductivity in Composites of Silver Halide (AgBr,AgI) and Mesoporous Alumina

The silver ionic conductivity in heterogeneous systems of AgBr:Al₂O₃ and AgI:Al₂O₃ is highly enhanced by utilizing mesoporous Al₂O₃ as the insulating phase. The highest Ag⁺ conductivity of 3.1 × 10^–3 Ω^–1 cm^–1 (at 25 °C) has been obtained for the AgI:Al₂O₃ composite with an Al₂O₃ volume fraction of 0.3. For AgBr:Al₂O₃, the enhancement of the conductivity is satisfactorily explained in the framework of the ideal space‐charge model, while in the case of AgI:Al₂O₃ stacking disorder is also considered to contribute to the ionic conductivity.     

GaAs structures with a gate dielectric based on aluminum-oxide layers

Different types of dielectrics obtained by low-temperature electron-beam sputtering are studied; these dielectrics include Al₂O₃ layers and Al₂O₃/SiO₂/Al₂O₃ three-layer compositions. The dependence of the electrical strength of Al₂O₃ layers on their thickness is determined. It is established that formation of the three-layer dielectric Al₂O₃/SiO₂/Al₂O₃ makes it possible to increase the range of operating voltages up to 60 V for structures with a gate electrode. It is shown that it is possible to control the density of charge carriers (holes) in the two-dimensional conduction channel of GaAs structures by changing the gate voltage when the Al₂O₃/SiO₂/Al₂O₃ structure is used as a gate dielectric.     

Highly transparent conductive films of thermally evaporated In2O3

Highly transparent (over 90% transmission in the visible range) and highly conductive (resistivity ≈2 × 10^-4 ohm-cm) indium oxide (undoped) films have been produced by thermal evaporation from In₂O₃ + In source in a vacuum chamber con-taining low pressures of O₂, . Film properties are comparable or superior to the best tin-doped indium oxide films that have ever been reported, and excellent reproducibility has been achieved. Hall effect measurements have revealed that the observed low resistivity is primarily a result of the excellent electron mobility (? 70 cm²/V-sec), although the electron concentration is also rather high (≥4 × l0²⁰/cm³). X-ray diffraction measurements show distinctly polycrystal-line In₂O₃ structure with a lattice constant ranging from 10.07Å to 10.11Å. Electrolytic electroreflectance spectra exhibit at least four critical transitions, from which we have determined the direct and indirect optical band gaps (3.56eV and 2.69eV, respectively). Burstein shifts due to the population of electrons in the condition band are also observed. From an internal photoemission study, the work function of the In₂O₃ film has been determined to be 5.0eV. These and other results, along with a discussion of the processing details are reported.     

Approach for Al2O3 rear surface passivation of industrial p‐type Si PERC above 19%

Atomic layer deposition (ALD) of thin Al₂O₃ (≤10 nm) films is used to improve the rear surface passivation of large‐area screen‐printed p‐type Si passivated emitter and rear cells (PERC). A blister‐free stack of Al₂O₃/SiO_x/SiN_x is developed, leading to an improved back reflection and a rear recombination current (J_0,rear) of 92 ± 6 fA/cm². The Al₂O₃/SiO_x/SiN_x stack is blister‐free if a 700°C anneal in N₂ is performed after the Al₂O₃ deposition and prior to the SiO_x/SiN_x capping. A clear relationship between blistering density and lower open‐circuit voltage (V_OC) due to increased rear contacting area is shown. In case of the blister‐free Al₂O₃/SiO_x/SiN_x rear surface passivation stack, an average cell efficiency of 19.0% is reached and independently confirmed by FhG‐ISE CalLab. Compared with SiO_x/SiN_x‐passivated PERC, there is an obvious gain in V_OC and short‐circuit current (J_SC) of 5 mV and 0.2 mA/cm², respectively, thanks to improved rear surface passivation and rear internal reflection. Copyright © 2012 John Wiley & Sons, Ltd.     

Electrical characterization of metal-oxide-high-k dielectric-oxide-semiconductor (MOHOS) structures for memory applications

Conventional SONOS (polysilicon-oxide-nitride-oxide-silicon) non-volatile memory devices use silicon nitride as the charge storage layer. In this work, metal-oxide-high-k dielectric-oxide-silicon (MOHOS) structures are fabricated using HfO₂ and Dy₂O₃ high-k dielectrics as the charge storage layer. The Al/SiO₂/Dy₂O₃/SiO₂/Si capacitors have a C–V memory window of 1.88 V and a leakage current density of 10⁻⁸ A/cm². This leakage current is lower than those of Al/SiO₂/HfO₂/SiO₂/Si capacitors and other similar capacitors reported in the literature. A minimum detection window of 0.5 V for MOHOS capacitors can be maintained up to 2 × 10⁸ s using as-deposited Dy₂O₃. The better performance of the Al/SiO₂/Dy₂O₃/SiO₂/Si structure over Al/SiO₂/HfO₂/SiO₂/Si is attributed to the larger conduction band offset at the Dy₂O₃/SiO₂ interface (2.3 eV) versus 1.6 eV at the HfO₂/SiO₂ interface.     

Structural,Optical and Electrical Properties of Polycrystalline CuO Thin Films Prepared by Magnetron Sputtering

Cupric oxide thin films were deposited on silicon and sapphire substrates by reactive radio frequency magnetron sputtering at different substrate temperatures. The results showed that the CuO films were composed of different sizes of CuO nano-grains and the CuO films deposited on Si substrates showed a more dense and uniform surface than that deposited on Al₂O₃ substrates. It was noted that both the CuO films deposited on Si and Al₂O₃ substrates revealed only CuO related diffractions and the preferred orientation of the CuO films changed from (002) to (111) as the substrate temperature increased. Moreover, the carrier concentration was 1.141?×?10¹⁸ cm^?3 and the mobility was 0.401 cm²/v s at 450°C substrate temperature. The controllable electrical properties of the films can be achieved by the variation of crystal quality arising from the substrate temperature.