Microstructure and electrical characteristics of Ba0.65Sr0.35TiO3 thin films etched in CF4/Ar/O2 plasma

Radio frequency magnetron sputtered Ba_0.65Sr_0.35TiO₃ (BST) thin films were etched in CF₄/Ar/O₂ plasma by magnetically enhanced reactive ion etching technique. The etching characteristics of BST films were characterized in terms of microstructure and electrical properties. Atomic force microscopy and X-ray diffraction results indicate that the microstructure of the etched BST film is degraded because of the rugged surface and lowered intensities of BST (1 0 0), (1 1 0), (1 1 1) and (2 0 0) peaks compared to the unetched counterparts. Dielectric constant and dielectric dissipation of the unetched, etched and postannealed-after-etched BST film capacitors are 419, 346, 371, 0.018, 0.039 and 0.031 at 100 kHz, respectively. The corresponding dielectric tunability, figure of merit and remnant polarization are 19.57%, 11.56%, 17.25%, 10.87, 2.96, 5.56, 3.62 μC/cm², 2.32 and 2.81 μC/cm² at 25 V, respectively. The leakage current density of 1.75 × 10⁻⁴ A/cm² at 15 V for the etched BST capacitor is over two orders of magnitude higher than 1.28 × 10⁻⁶ A/cm² for the unetched capacitor, while leakage current density of the postannealed-after-etched capacitor decreases slightly. It means that the electrical properties of the etched BST film are deteriorated due to the CF₄/Ar/O₂ plasma-induced damage. Furthermore, the damage is alleviated, and the degraded microstructure and electrical properties are partially recovered after the etched BST film is postannealed at 923 K for 20 min under a flowing O₂ ambience.     

Effects of fluorine-implanted treatment on Ba0.7Sr0.3TiO3 films

The effects of F-ion implantation on the leakage and dielectric properties of the Ba_0.7Sr_0.3TiO₃ (BST) films were investigated. The BST film implanted with 1×10¹⁵ cm^–2 shows the optimum leakage performance. The leakage current density can be decreased by one order of magnitude as compared to that of the non-implanted sample at an applied voltage of 2 V. On increasing the implanted dose from 5×10¹⁴ to 5×10¹⁵ cm^–2, the dielectric constant first increases and then decreases due to the deteriorated crystallinity. It is found that the suitable F-ion dose can reduce the –OH contaminants and improve the dielectric and leakage properties.     

Electrical properties of sputtered (Ba, Sr)TiO3 thin films prepared by two-step deposition method

The influence of two-step deposition on the electrical properties of sputtered (Ba,Sr)TiO₃ thin films was investigated. BST thin films with thickness 40 nm were deposited by a simple two-step radio frequency-magnetron sputtering technique, where the BST thin film consisted of a seed layer and a main layer. The dielectric constant was strongly dependent on the thickness of seed layer, but there was no dependence on deposition temperature of the seed layer. For a 2 nm seed layer, the dielectric constants were higher by about 29% than those of single-step BST thin films due to higher crystallinity and the leakage current was nearly the same as that of a single-step sample in bias voltage from −2 to 2.5 V. However, an improvement of the dielectric constant was not observed for samples having above 4 nm thick seed layers. A 40 nm thick BST film with 2 nm thick seed layer deposited by a two-step method exhibited a SiO₂ equivalent thickness of 0.385 nm and a leakage current density of 2.74 × 10⁻⁸A/cm²at+1.5V after post-annealing under an atmosphere of flowing N₂ for 30 min at 750°C.     

Pentacene thin-film transistors with sol-gel derived amorphous Ba0.6Sr0.4TiO3 gate dielectric

An amorphous Ba_0.6Sr_0.4TiO₃ (BST) film with the thickness of 200 nm was deposited on indium-tin-oxide (ITO)-coated glass substrate through sol-gel route and post-annealing at 500 °C. The dielectric constant of the BST film was determined to be 20.6 at 100 kHz by measuring the Ag/BST/ITO parallel plate capacitor, and no dielectric tunability was observed with the bias voltage varying from −5 to 5 V. The BST film shows a dense and uniform microstructure as well as a smooth surface with the root-mean-square (RMS) roughness of about 1.4 nm. The leakage current density was found to be 3.5 × 10⁻⁸ A/cm² at an applied voltage of −5 V. The transmittance of the BST/ITO/glass structure is more than 70% in the visible region. Pentacene based transistor using the as-prepared BST film as gate insulator exhibits a low threshold voltage of −1.3 V, the saturation field-effect mobility of 0.68 cm²/Vs, and the current on/off ratio of 3.6 × 10⁵. The results indicate that the sol-gel derived BST film is a promising high-k gate dielectric for large-area transparent organic transistor arrays on glass substrate.     

Effect of bottom electrode materials on the electrical andreliability characteristics of (Ba, Sr)TiO3 capacitors

The dielectric constant and the leakage current density of (Ba, Sr)TiO₃ (BST) thin films deposited on various bottom electrode materials (Pt, Ir, IrO₂/Ir, Ru, RuO₂/Ru) before and after annealing in O₂ ambient were investigated. The improvement of crystallinity of BST films deposited on various bottom electrodes was observed after the postannealing process. The dielectric constant and leakage current of the films mere also strongly dependent on the postannealing conditions. BST thin film deposited on Ir bottom electrode at 500°C, after 700°C annealing in O₂ for 20 min, has the dielectric constant of 593, a loss tangent of 0.019 at 100 kHz, a leakage current density of 1.9×10 ^-8 A/cm² at an electric field of 200 kV/cm with a delay time of 30 s, and a charge storage density of 53 fC/μm² at an applied field of 100 kV/cm. The BST films deposited on Ir with post-annealing can obtain better dielectric properties than on other bottom electrodes in our experiments. And Ru electrode is unstable because the interdiffusion of Ru and Ti occurs at the interface between the BST and Ru after postannealing. The ten year lifetime of time-dependent dielectric breakdown (TDDB) studies indicate that BST on Pt, Ir, IrO₂/Ir, Ru, and RuO₂/Ru have long lifetimes over ten gears on operation at the voltage bias of 2 V     

Examination and evaluation of La2O3 as gate dielectric for sub-100 nm CMOS and DRAM technology

High-k gate dielectric La₂O₃ thin films have been deposited on Si(1 0 0) substrates by molecular beam epitaxy (MBE). Al/La₂O₃/Si metal-oxide–semiconductor capacitor structures were fabricated and measured. A leakage current of 3 × 10⁻⁹ A/cm² and dielectric constant between 20 and 25 has been measured for samples having an equivalent oxide thickness (EOT) 2.2 nm. The estimated interface state density D_it is around 1 × 10¹¹ eV⁻¹ cm⁻². EOT and flat-band voltage were calculated using the NCSU CVC program. The chemical composition of the La₂O₃ films was measured using X-ray photoelectron spectrometry and Rutherford backscattering. Current density vs. voltage curves show that the La₂O₃ films have a leakage current several orders of magnitude lower than SiO₂ at the same EOT. Thin La₂O₃ layers survive anneals of up to 900 °C for 30 s with no degradation in electrical properties.     

Reducing Cu diffusion in SiCOH low-k films by O2 plasma treatment

This work investigates the Cu diffusion in SiCOH low dielectric constant films treated by O₂ plasma. By capacitance–voltage and current-voltage measurement, and thermal stress analysis, it is found that the O₂ plasma surface treatment of SiCOH films can lead to the decrease of flatband voltage shift ΔV_FB, the increase of activation energy E_a, and the decrease of leakage current. The small ΔV_FB and lower leakage current indicate the weak Cu diffusion. The increase of active energy means the reducing of fast Cu ions surface diffusion through the interconnected pores structure of the film. Hence, the Cu diffusion in SiCOH films can be reduced by O₂ plasma treatment. By FTIR and AFM analysis on the bonding configuration and microstructure, the reduce of Cu diffusion is related to the increase of Si-O cages and networks, which makes more open pores sealed at the surface of SiCOH films.     

Thin RF sputtered and thermal Ta2O5 on Si for high density DRAM application

Tantalum pentoxide thin films on Si prepared by two conventional for modern microelectronics methods (RF sputtering of Ta in Ar + O₂ mixture and thermal oxidation of tantalum layer on Si) have been investigated with respect to their dielectric, structural and electric properties. It has been found that the formation of ultra thin SiO₂ film at the interface with Si, during fabrication implementing the methods used, is unavoidable as both, X-ray photoelectron spectroscopy and electrical measurements, have indicated. The initial films (as-deposited and as-grown) are not perfect and contain suboxides of tantalum and silicon which act as electrical active centers in the form of oxide charges and interface states. Conditions which guarantee obtaining high quality tantalum oxide with dielectric constant of 32–37 and leakage current density less than 10⁻⁷ A/cm² at 1.5 V applied voltage (Ta₂O₅ thickness equivalent to about 3.5 nm of SiO₂) have been established. These specifications make the layers obtained suitable alternative to SiO₂ for high density DRAM application.     

New TIT capacitor with ZrO2/Al2O3/ZrO2 dielectrics for 60 nm and below DRAMs

New ZrO₂/Al₂O₃/ZrO₂ (ZAZ) dielectric film was successfully developed for DRAM capacitor dielectrics of 60 nm and below technologies. ZAZ dielectric film grown by ALD has a mixture structure of crystalline phase ZrO₂ and amorphous phase Al₂O₃ in order to optimize dielectric properties. ZAZ TIT capacitor showed small Tox.eq of 8.5 Å and a low leakage current density of 0.35 fA/cell, which meet leakage current criteria of 0.5 fA/cell for mass production. ZAZ TIT capacitor showed a smaller cap leak fail bit than HAH capacitor and stable leakage current up to 550 °C anneal. TDDB (time dependent dielectric breakdown) behavior reliably satisfied the 10-year lifetime criteria within operation voltage range.     

Thermal Ta2O5––alternative to SiO2 for storage capacitor application

Tantalum pentoxide thin layers (10–100 nm) obtained by thermal oxidation of rf sputtered Ta films on Si have been investigated with respect of their dielectric, structural and electric properties. It is established that stoichiometric Ta₂O₅ detected at the surface of the layers is reduced to tantalum suboxides in their depth. The oxide parameters are discussed in terms of a presence of an unavoidable ultrathin SiO₂ between Si and Ta₂O₅ and bond defects in both the oxide and the interface transition region. Conditions which guarantee obtaining high quality tantalum oxide with a dielectric constant of 32–35 and a leakage current less than 10⁻⁷–10⁻⁸ A/cm² at 1.5 V (SiO₂ equivalent thickness of 2.5–3 nm) are established. These specifications make the layers obtained suitable alternative to SiO₂ for high density DRAMs application.     

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.     

Characteristics of metal-ferroelectric-insulator-semiconductor structure using Sr0.8Bi2.2Ta2O9 and Sr0.8Bi2.2Ta2O9-BaZrO3 for ferroelectric gates

Characteristics of BaZrO₃ (BZO) modified Sr_0.8Bi_2.2Ta₂O₉ (SBT) thin films fabricated by sol-gel method on HfO₂ coated Si substrates have been investigated in a metal-ferroelectric-insulator-semiconductor (MFIS) structure for potential use in a ferroelectric field effect transistor (FeFET) type memory. MFIS structures consisting of pure SBT and doped with 5 and 7 mol% BZO exhibited memory windows of 0.81, 0.82 and 0.95 V with gate voltage sweeps between −5 and +5 V, respectively. Leakage current density levels of 10⁻⁸ A/cm² for BZO doped SBT gate materials were observed and attributed to the metallic Bi on the surface as well as intrinsic defects and a porous film microstructure. The higher than expected leakage current is attributed to electron trapping/de-trapping, which reduces the data retention time and memory window. Further process improvements are expected to enhance the electronic properties of doped SBT for FeFET.     

Selective etching of (Ba,Sr)TiO3 thin films over silicon in an inductively coupled plasma

In this work, we investigated etching characteristics of BST thin films and higher selectivity of BST over Si using inductive coupled O₂/Cl₂/Ar plasma (ICP) system. The maximum etch rate of BST thin films and selectivity of BST over Si were 61.5 nm/min at a O₂ addition of 1 sccm, 9.52 at a O₂ addition of 4 sccm into the Cl₂(30%)/Ar(70%) plasma, respectively. Plasma diagnostics was performed by Langmuir probe (LP), optical emission spectroscopy (OES) and quadrupole mass spectrometry (QMS). These results confirm that the increased etch rates at O₂ addition of 1 sccm is the result of the enhanced chemical reaction between BST and Cl radicals and an ion bombardment effect.     

快速退火对Pt/BST/Pt电容器结构和性能的影响

采用脉冲激光沉积(PLD)法在Pt/Ti/SiO2/Si(001)基片上制备了Ba0.6Sr0.4TiO3(BST)薄膜,对Pt/BST/Pt电容器在空气中进行400℃快速退火(RTA)处理,研究了快速退火对Pt/BST/Pt电容器的结构和性能的影响。结果表明:快速退火虽然对BST薄膜的结晶质量影响较小,但却极大改善了Pt/BST/Pt电容器的电学性能。当测试频率为100kHz、直流偏压为0V时,介电损耗从快速退火前的0.07减小到0.03,介电常数和调谐率略有增加。快速退火后负向漏电流过大现象得到了明显抑制,正负向漏电流趋于对称,在300×103V/cm电场强度下,漏电流密度为4.83×10–5A/cm2。     

Time-dependent-dielectric-breakdown characteristics of Hf-doped Ta2O5/SiO2 stack

The Time-Dependent-Dielectric Breakdown (TDDB) characteristics of MOS capacitors with Hf-doped Ta₂O₅ films (8 nm) have been analyzed. The devices were investigated by applying a constant voltage stress at gate injection, at room and elevated temperatures. Stress voltage and temperature dependences of hard breakdown of undoped and Hf-doped Ta₂O₅ were compared. The doped Ta₂O₅ exhibits improved TDDB characteristics in regard to the pure one. The maximum voltage projected for a 10 years lifetime at room temperature is −2.4 V. The presence of Hf into the matrix of Ta₂O₅ modifies the dielectric breakdown mechanism making it more adequate to the percolation model. The peculiarities of Weibull distribution of dielectric breakdown are discussed in terms of effect of three factors: nature of pre-existing traps and trapping phenomena; stress-induced new traps generation; interface layer degradation.     

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.     

Structural and electrical characteristics of RF-sputtered HfO2 high-k based MOS capacitors

The HfO₂ high-k thin films have been deposited on p-type (1 0 0) silicon wafer using RF magnetron sputtering technique. The XRD, AFM and Ellipsometric characterizations have been performed for crystal structure, surface morphology and thickness measurements respectively. The monoclinic structured, smooth surface HfO₂ thin films with 9.45 nm thickness have been used for Al/HfO₂/p-Si metal-oxide-semiconductor (MOS) structures fabrication. The fabricated Al/HfO2/Si structure have been used for extracting electrical properties viz dielectric constant, EOT, barrier height, doping concentration and interface trap density through capacitance voltage and current-voltage measurements. The dielectric constant, EOT, barrier height, effective charge carriers, interface trap density and leakage current density are determined are 22.47, 1.64 nm, 1.28 eV, 0.93 × 10¹⁰, 9.25 × 10¹¹ cm⁻² eV⁻¹ and 9.12 × 10⁻⁶ A/cm² respectively for annealed HfO₂ thin films.     

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.     

Electrical properties of thin Ta2O5 films obtained by thermal oxidation of Ta on Si

Tantalum pentoxide films (13–260 nm) on p-type Si have been prepared by thermal oxidation at 673–873 K of rf sputtered Ta films and have been studied using Al–Ta₂O₅–Si capacitors. Both dielectric constant and refractive index were found to depend on the thickness of the Ta₂O₅ layers. Layers with a dielectric constant of 25–32 were obtained. A decreasing trend in the leakage current was found upon increasing oxidation temperature from 673 to 873 K. Leakage current density of (10⁻⁸ to 3×10⁻⁷) A cm⁻² at 1 MV cm⁻¹ effective field was achieved.     

Effect of bottom electrodes on resistance degradation and breakdownof (Ba,Sr)TiO3 thin films

The influence of bottom electrodes (Pt, Ir, Ru) on the degradation of (Ba,Sr)TiO₃ (BST) thin films under dc stress conditions was investigated. The current-time (I-t) and current-voltage (I-V) measurement results indicated that the BST thin films deposited on Ru have faster degradation than those deposited on Pt and Ir. The degradation was considered to be caused by the deterioration of the Schottky-barrier. Under dc stress conditions, the dielectric relaxation current in the BST dielectric films probably enhances the deterioration. The breakdown time was found to be approximated by an exponential function of an electric field [t_B=α exp(-βE)] for dc stress. The value of the exponential factor β for BST deposited on Pt and Ir was about a quarter of that for BST deposited on Ru. The different value of β observed under dc stress indicates that the degradation of BST on Ru would be more serious than on Pt and Ir. The ten years lifetime of time-dependent dielectric breakdown (TDDB) studies indicate that BST on Pt, Ir and Ru have longer lifetime over ten years for operation at the voltage bias of 1 V