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.     

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.     

Study of amorphous Ta2O5 thin films by DC magnetron reactive sputtering

The dc magnetron reactive sputtering deposition of tantalum pentoxide (Ta₂O₅) thin films was investigated. By combining Schiller's criterion and Reith’s “target preoxidation” procedure, high quality Ta₂O₅ thin films were prepared at a high deposition rate of about lOOÅ;/min. The deposited films were amorphous, with a refractive index around 2.07 and a dielectric constant of 20. An optical transmit-tance of 98.6% was obtained for a 4500Â thick film. The leakage current density is 5 × 10^?9 A/cm² at an electric field strength of 1 MV/cm and its breakdown field strength is above 2 MV/cm. The temperature coefficient of capacitance for capacitors fabricated using the deposited films is approximately +230 ppm/°C. X-ray photoelectron spectroscopy shows that the films are stoichiometric tantalum pentoxide, Ta₂O₅, and exhibit good stability.     

Deposition of tantalum oxide films by dual spectral source assisted metalorganic chemical vapor deposition (MOCVD)

Dual spectral source assisted metalorganic chemical vapor deposition (MOCVD) is an ideal technique for the deposition of high dielectric constant materials. Tungsten halogen lamps and a deuterium lamp are used as the sources of optical and thermal energy. In this paper, we have reported the deposition and characterization of tantalum penta oxide films. Ta₂O₅ films were deposited at 660°C for 15 min and annealed at 400°C for 1 h. The leakage current densities of 10.6 nm thick films are as low as 10₋₁₀ A/cm² for gate voltage under 4V. To the best of our knowledge, these are the best results reported to date by any researcher. The high energy photons used in the in-situ cleaning and deposition process play an important role in obtaining high quality films of Ta₂O₅.     

Effect of a silicon nitride buffer layer on the electrical properties of tantalum pentoxide films

Ta₂O₅ films with a buffer layer of silicon nitride of various thicknesses were deposited on Si substrate by reactive sputtering and submitted to annealing at 700 °C in nitrogen atmosphere. The microstructure and the electrical properties of thin films were studied. It was found that with a buffer layer of silicon nitride the electrical properties of Si_xN_y/Ta₂O₅ film can be improved than Ta₂O₅ film. When the thickness of the buffer layer was 3 nm, the Si_xN_y/Ta₂O₅ film has the highest dielectric constant of 27.4 and the lowest leakage current density of 4.61 × 10⁻⁵ A/cm² (at −1 V). For the Si_xN_y (3 nm)/Ta₂O₅ film, the conduction mechanism of leakage current was also analyzed and showed four types of conduction mechanisms at different applied voltages.     

Effects of annealing in O2 and N2 on the electrical properties of tantalum oxide thin films prepared by electron cyclotron resonance plasma enhanced chemical vapor deposition

The tantalum oxide thin films with a thickness of 14 nm were deposited at 95°C by electron cyclotron resonance plasma enhanced chemical vapor deposition (ECRPECVD), and annealed at various temperatures (700∼850°C) in O₂ and N₂ ambients. The microstructure and composition of the tantalum oxide thin films and the growth of interfacial silicon oxide layer were investigated and were related to the electrical characteristics of the film. Annealing in an O₂ ambient led to a high dielectric constant (ε_r(Ta₂O₅) = 24) as well as a small leakage current (E_bd = 2.3 MV/cm), which were due to the improved stoichiometry and the decreased impurity carbon content. Annealing in an N₂ ambient resulted in poor and nonuniform leakage current characteristics. The as-deposited tantalum oxide films were crystallized into δ-Ta₂O₅ after annealing at above 750°C regardless of the ambient. The leakage current of the film abruptly increased after annealing at 850°C probably because of the stress caused by thermal expansion or contraction.     

Effects of annealing conditions on the properties of tantalum oxide films on silicon substrates

The formation of a SiO₂ layer at the Ta₂O₅/Si interface is observed by annealing in dry O₂ or N₂ and the thickness of this layer increases with an increase in annealing temperature. Leakage current of thin (less than 40 nm thick) Ta₂O₅ films decreases as the annealing temperature increases when annealed in dry O₂ or N₂. The dielectric constant vs annealing temperature curve shows a maximum peak at 750 or 800° C resulting from the crystallization of Ta₂O₅. The effect is larger in thicker Ta₂O₅ films. But the dielectric constant decreases when annealed at higher temperature due to the formation and growth of a SiO₂ layer at the interface. The flat band voltage and gate voltage instability as a function of annealing temperature can be explained in terms of the growth of interfacial SiO₂. The electrical properties of Ta₂O₅ as a function of annealing conditions do not depend on the fabrication method of Ta₂O₅ but strongly depend on the thickness of Ta₂O₅ layer.     

Breakdown fields and conduction mechanisms in thin Ta2O5 layers on Si for high density DRAMs

The conduction mechanisms and the microstructure of rf sputtered Ta₂O₅ on Si, before and after oxygen annealing at high temperatures (873, 1123 K; 30 min) have been investigated. The as-deposited and annealed at 873 K layers are amorphous whereas crystalline Ta₂O₅ (orthorhombic β-Ta₂O₅ phase) was obtained after O₂ treatment at 1123 K. The results (electrical, X-ray diffraction, transmission electron microscopy) reveal the formation of an interfacial ultrathin SiO₂ layer under all technological regimes used. The higher (493 K) substrate temperature during deposition stimulates the formation of amorphous rather than crystalline SiO₂. It is found that the oxygen heating significantly reduces the oxide charge (Q_f<10¹⁰ cm⁻²) and improves the breakdown characteristics (the effect is more pronounced for the higher annealing temperature). It is accompanied by an increase of the effective dielectric constant (up to 37 after 1123 K treatment). It is established that the influence of the oxygen treatment on the leakage current is different depending on the film thickness, namely: a beneficial effect for the thinner and a deterioration of leakage characteristics for thicker (80 nm) films. A leakage current density as low as 10⁻⁷ A/cm² at 1 MV/cm applied field for 26 nm annealed layers has been obtained. The current reduction is considered to be due to a removal by annealing of certain structural nonperfections present in the initial layers. Generally, the results are discussed in terms of simultaneous action of two opposite and competing processes taking place at high temperatures––a real annealing of defects and an appearance of a crystal phase and/or a neutral traps generation. The contribution of the neutral traps also is involved to explain the observed weaker charge trapping in the as-fabricated films compared to the annealed ones.The conduction mechanism of the as-deposited films is found to be of Poole–Frenkel (PF) type for a wide range of applied fields. A change of the conduction mechanism for the annealed films at medium fields (0.8–1.3 MV/cm) is established. This transition from PF process to the Schottky emission limited current is explained with an annealing of bulk traps (oxygen vacancies and nonperfect bonds). It is concluded that the dominant conduction mechanism in the intermediate fields can be effectively controlled by appropriate technological steps.     

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.     

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.     

Atomic - vapour - deposited HfO2 and Sr4Ta2O9 layers for metal-insulator-metal applications

Sr₄Ta₂O₉ and HfO₂ films were prepared on 200 mm TiN/Si(100) substrates by Atomic Vapour Deposition (AVD). Depositions were carried out within a thermal budget of CMOS back end of line. Electrical properties have been investigated in metal-insulator-metal capacitors after sputter deposition of Au top electrodes. Both Sr₄Ta₂O₉ and HfO₂ dielectrics show excellent electrical performances. Oxides possess high capacitance densities of 3.5 fF/μm²(HfO₂) and 4.5 fF/μm² (Sr₄Ta₂O₉) in combination with high voltage linearity (α < 100ppm/V²). Sr₄Ta₂O₉ MIM capacitors provide lower leakage currents at 2 V, while HfO₂ MIMs offer higher operating voltage values for 10 years lifetime than Sr₄Ta₂O₉ based capacitors. The dielectric breakdown fields of HfO₂ (5.8 MV/cm) and Sr₄Ta₂O₉ (3.2 MV/cm) were obtained from I(V) characteristics.     

Reduction of defect states of tantalum oxide thin films with additive elements

Electrical properties of tantalum oxide (Ta₂O₅) thin films formed by metalorganic decomposition have been studied with respect to their defect states. A shallow band of defect states, which are the origin of hole traps, is detected by thermally stimulated current. The defect states in the Ta₂O₅ films are fully suppressed with additive elements such as TiO₂ and WO₃. It is considered that oxygen vacancies are fully compensated by Ti⁴⁺ ions or W⁶⁺ ions that are substitutionally incorporated into Ta⁵⁺ sites.     

Structural and Electrical Properties of Ta ax La(1−a)x O y Thin Films

Effect of annealing temperature on the characteristics of sol–gel-driven Ta _ax La_(1?a)x O _y thin film spin-coated on Si substrate as a high-k gate dielectric was studied. Ta _ax La_(1?a)x O _y thin films with different amounts of a were prepared (as-prepared samples). X-ray diffraction measurements of the as-prepared samples indicated that Ta_0.3x La_0.7x O_y film had an amorphous structure. Therefore, Ta_0.3x La_0.7x O _y film was chosen to continue the present studies. The morphology of Ta_0.3x La_0.7x O _y films was studied using scanning electron microscopy and atomic force microscopy techniques. The obtained results showed that the size of grain boundaries on Ta_0.3x La_0.7x O _y film surfaces was increased with increasing annealing temperature. Electrical and optical characterizations of the as-prepared and annealed films were investigated as a function of annealing temperature using capacitance–voltage (C–V) and current density–voltage (J–V) measurements and the Tauc method. The obtained results demonstrated that Ta_0.3x La_0.7x O _y films had high dielectric constant (≈27), wide band gap (≈4.5 eV), and low leakage current density (≈10^?6 A/cm² at 1 V).     

High dielectric constant TiO2 film grown on polysilicon by liquid phase deposition

In this study, titanium dioxide (TiO₂) films were grown on polycrystalline silicon by liquid phase deposition (LPD) with ammonium hexafluoro-titanate and boric acid as sources. The film structure is amorphous as examined by X-ray diffraction (XRD). A uniform composition of LPD-TiO₂ was observed by SIMS examination. The leakage current density of an Al/LPD-TiO₂/poly-Si/p-type Si metal–oxide–semiconductor (MOS) structure is 1.9 A/cm² at the negative electric field of 0.7 MV/cm. The dielectric constant is 29.5 after O₂ annealing at 450 °C. The leakage current densities can be improved effectively with a thermal oxidized SiO₂ added at the interface of LPD-TiO₂/poly-Si. The leakage current density can reach 3.1×10⁻⁴ A/cm² at the negative electric field of 0.7 MV/cm and the dielectric constant is 9.8.     

Effect of oxygen plasma on the properties of tantalum oxide films

The effect of oxygen plasma on the leakage current, permittivity, and the dielectric loss tangent of Ta₂O₅ thin layers (300–400 nm) is studied. It is suggested to treat tantalum oxide films in oxygen plasma to control their electrical and dielectric characteristics.     

Zr‐Doped Indium Oxide (IZRO) Transparent Electrodes for Perovskite‐Based Tandem Solar Cells

Parasitic absorption in transparent electrodes is one of the main roadblocks to enabling power conversion efficiencies (PCEs) for perovskite‐based tandem solar cells beyond 30%. To reduce such losses and maximize light coupling, the broadband transparency of such electrodes should be improved, especially at the front of the device. Here, the excellent properties of Zr‐doped indium oxide (IZRO) transparent electrodes for such applications, with improved near‐infrared (NIR) response, compared to conventional tin‐doped indium oxide (ITO) electrodes, are shown. Optimized IZRO films feature a very high electron mobility (up to ≈77 cm² V^?1 s^?1), enabling highly infrared transparent films with a very low sheet resistance (≈18 Ω □^?1 for annealed 100 nm films). For devices, this translates in a parasitic absorption of only ≈5% for IZRO within the solar spectrum (250–2500 nm range), to be compared with ≈10% for commercial ITO. Fundamentally, it is found that the high conductivity of annealed IZRO films is directly linked to promoted crystallinity of the indium oxide (In₂O₃) films due to Zr‐doping. Overall, on a four‐terminal perovskite/silicon tandem device level, an absolute 3.5 mA cm^?2 short‐circuit current improvement in silicon bottom cells is obtained by replacing commercial ITO electrodes with IZRO, resulting in improving the PCE from 23.3% to 26.2%.     

Implementation of Low‐Power Electronic Devices Using Solution‐Processed Tantalum Pentoxide Dielectric

The development of solution‐processed field effect transistors (FETs) based on organic and hybrid materials over the past two decades has demonstrated the incredible potential in these technologies. However, solution processed FETs generally require impracticably high voltages to switch on and off, which precludes their application in low‐power devices and prevent their integration with standard logic circuitry. Here, a universal and environmentally benign solution‐processing method for the preparation of Ta₂O₅, HfO₂ and ZrO₂ amorphous dielectric thin films is demonstrated. High mobility CdS FETs are fabricated on such high‐κ dielectric substrates entirely via solution‐processing. The highest mobility, 2.97 cm² V^?1 s^?1 is achieved in the device with Ta₂O₅ dielectric with a low threshold voltage of 1.00 V, which is higher than the mobility of the reference CdS FET with SiO₂ dielectric with an order of magnitude decrease in threshold voltage as well. Because these FETs can be operated at less than 5 V, they may potentially be integrated with existing logic and display circuitry without significant signal amplification. This report demonstrates high‐mobility FETs using solution‐processed Ta₂O₅ dielectrics with drastically reduced power consumption; ≈95% reduction compared to that of the device with a conventional SiO₂ gate dielectric.     

Effects of Growth Temperature and Annealing on Properties of Zn3Sn2O7 Thin Films and Application in TFTs

The effects of growth temperature and annealing on the physical properties of Zn₃Sn₂O₇ thin films were investigated in this work. The Zn₃Sn₂O₇ thin films were deposited on glass substrates by radio frequency (rf) magnetron sputtering. It is found that the films are amorphous regardless of the growth temperature. The film grown at room temperature shows the highest mobility of 8.1 cm² V^?1 s^?1 and the lowest carrier concentration of 2.0 × 10¹⁵ cm^?3. The highest carrier concentration of 1.6 × 10¹⁹ cm^?3 is obtained at the growth temperature of 250°C. Annealing treatment of the Zn₃Sn₂O₇ thin films resulted in increases of carrier concentration and mobility. The average transmittance of the as-deposited and annealed films reaches 80%. By using a Zn₃Sn₂O₇ thin film as the channel and a Ta₂O₅ thin film as the insulating layer, we fabricated transparent Zn₃Sn₂O₇ thin-film transistors with field-effect mobility of 21.2 cm² V^?1 s^?1, on/off current ratio of 10⁵, threshold voltage of 0.8 V, and subthreshold swing of 0.8 V/decade.     

Effect of Rapid Thermal Annealing on Sputtered CaCu<Subscript>3</Subscript>Ti<Subscript>4</Subscript>O<Subscript>12</Subscript> Thin Films

Calcium copper titanium oxide (CaCu₃Ti₄O₁₂, abbreviated to CCTO) films were deposited on Pt/Ti/SiO₂/Si substrates at room temperature (RT) by radiofrequency magnetron sputtering. As-deposited CCTO films were treated by rapid thermal annealing (RTA) at various temperatures and in various atmospheres. X-ray diffraction patterns and scanning electron microscope (SEM) images demonstrated that the crystalline structures and surface morphologies of CCTO thin films were sensitive to the annealing temperature and ambient atmosphere. Polycrystalline CCTO films could be obtained when the annealing temperature was 700°C in air, and the grain size increased signifi- cantly with annealing in O₂. The 0.8-μm CCTO thin film that was deposited at RT for 2 h and then annealed at 700°C in O₂ exhibited a high dielectric constant (ε′) of 410, a dielectric loss (tan δ) of 0.17 (at 10 kHz), and a leakage current density (J) of 1.28 × 10⁻⁵ A/cm² (at 25 kV/cm).     

Biosensor properties of SOI nanowire transistors with a PEALD Al<Subscript>2</Subscript>O<Subscript>3</Subscript> dielectric protective layer

The properties of protective dielectric layers of aluminum oxide Al₂O₃ applied to prefabricated silicon-nanowire transistor biochips by the plasma enhanced atomic layer deposition (PEALD) method before being housed are studied depending on the deposition and annealing modes. Coating the natural silicon oxide with a nanometer Al₂O₃ layer insignificantly decreases the femtomole sensitivity of biosensors, but provides their stability in bioliquids. In deionized water, transistors with annealed aluminum oxide are closed due to the trapping of negative charges of <(1–10) × 10¹¹ cm^?2 at surface states. The application of a positive potential to the substrate (V_sub > 25 V) makes it possible to eliminate the negative charge and to perform multiple measurements in liquid at least for half a year.