Microstructure and dielectric properties of La2O3 doped amorphous SiO2 films as gate dielectric material

As a potential gate dielectric material, the La₂O₃ doped SiO₂ (LSO, the mole ratio is about 1:5) films were fabricated on n-Si (0 0 1) substrates by using pulsed laser deposition technique. By virtue of several measurements, the microstructure and electrical properties of the LSO films were characterized. The LSO films keep the amorphous state up to a high annealing temperature of 800 °C. From HRTEM and XPS results, these La atoms of the LSO films do not react with silicon substrate to form any La-compound at interfacial layer. However, these O atoms of the LSO films diffuse from the film toward the silicon substrate so as to form a SiO₂ interfacial layer. The thickness of SiO₂ layer is only about two atomic layers. A possible explanation for interfacial reaction has been proposed. The scanning electron microscope image shows the surface of the amorphous LSO film very flat. The LSO film shows a dielectric constant of 12.8 at 1 MHz. For the LSO film with thickness of 3 nm, a small equivalent oxide thickness of 1.2 nm is obtained. The leakage current density of the LSO film is 1.54 × 10⁻⁴ A/cm² at a gate bias voltage of 1 V.     

Characteristics of sandwich-structured Al2O3/HfO2/Al2O3 gate dielectric films on ultra-thin silicon-on-insulator substrates

Sandwich-structure Al₂O₃/HfO₂/Al₂O₃ gate dielectric films were grown on ultra-thin silicon-on-insulator (SOI) substrates by vacuum electron beam evaporation (EB-PVD) method. AFM and TEM observations showed that the films remained amorphous even after post-annealing treatment at 950 °C with smooth surface and clean silicon interface. EDX- and XPS-analysis results revealed no silicate or silicide at the silicon interface. The equivalent oxide thickness was 3 nm and the dielectric constant was around 7.2, as determined by electrical measurements. A fixed charge density of 3 × 10¹⁰ cm⁻² and a leakage current of 5 × 10⁻⁷A/cm² at 2 V gate bias were achieved for Au/gate stack /Si/SiO₂/Si/Au MIS capacitors. Post-annealing treatment was found to effectively reduce trap density, but increase in annealing temperature did not made any significant difference in the electrical performance.     

Growth of highly-oriented CaCu3Ti4O12 thin films on SrTiO3 (1 0 0) substrates by a chemical solution route

Highly-oriented CaCu₃Ti₄O₁₂ (CCTO) thin films deposited directly on SrTiO₃ (1 0 0) substrates have been developed successfully using a chemical solution coating method. X-ray diffraction (XRD), scanning electron microscopy (SEM), and atomic force microscopy (AFM) were employed to characterize the structure and the morphology. It was observed that the CCTO thin films had the 1 μm × 1 μm domain-like microstructure that consists of compact grains of about 0.1 μm in size. The cross sectional SEM image shows that the CCTO grains grow regularly close to the clear interface between the CCTO film and the SrTiO₃ substrate. The result was discussed in terms of lattice mismatch between CCTO and SrTiO₃.     

Microstructure and interfacial properties of HfO2-Al2O3 nanolaminate films

High-k HfO₂-Al₂O₃ composite gate dielectric thin films on Si(1 0 0) have been deposited by means of magnetron sputtering. The microstructure and interfacial characteristics of the HfO₂-Al₂O₃ films have been investigated by using X-ray diffraction (XRD), Fourier transform infrared spectroscopy (FTIR) and spectroscopic ellipsometry (SE). Analysis by XRD has confirmed that an amorphous structure of the HfO₂-Al₂O₃ composite films is maintained up to an annealing temperature of 800 °C, which is much higher than that of pure HfO₂ thin films. FTIR characterization indicates that the growth of the interfacial SiO₂ layer is effectively suppressed when the annealing temperature is as low as 800 °C, which is also confirmed by spectroscopy ellipsometry measurement. These results clearly show that the crystallization temperature of the nanolaminate HfO₂-Al₂O₃ composite films has been increased compared to pure HfO₂ films. Al₂O₃ as a passivation barrier for HfO₂ high-k dielectrics prevents oxygen diffusion and the interfacial layer growth effectively.     

Chemical vapor deposition of ZrxTi1−xO2 and HfxTi1−xO2 thin films using the composite anhydrous nitrate precursors

Zr-Ti and Hf-Ti composite nitrates were successfully developed as single-source precursors for the chemical vapor deposition (CVD) of Zr_xTi_1−xO₂ and Hf_xTi_1−xO₂ thin films. The Zr-Ti nitrate can be assumed as a solid solution of the individual Zr and Ti nitrates, and the Zr/Ti molar ratio in the deposited Zr_xTi_1−xO₂ films is consistent with that in the precursor. The Hf-Ti nitrate appears to be a mixture of the Hf and Ti nitrates and the composition of the deposited Hf_xTi_1−xO₂ films depends remarkably on the heating time of precursor. Both Zr_xTi_1−xO₂ and Hf_xTi_1−xO₂ films exhibit trade-off properties between band gap and dielectric constant. The obtained results suggest that Zr_xTi_1−xO₂ and Hf_xTi_1−xO₂ films are promising candidates for gate dielectric application to improve the scalability and reduce the leakage current of the future complementary metal-oxide-semiconductor (CMOS) devices.     

Oxygen-defects-related dielectric response in CaCu3Ti4O12 ceramics

A 10 mm thickness columned CaCu₃Ti₄O₁₂ ceramic was fabricated by the conventional solid-state reaction method and the dielectric properties of different parts in ceramic had been investigated. For the sample close to the surface, only one Debye-type relaxation around 10⁷ Hz was observed at room temperature. However, for the sample close to the core, another relaxation peak was observed at about 10⁴ Hz. The results were explained in terms of the equivalent circuit model by showing in the impedance spectroscopy. Moreover, it was introduced that the low-frequency dielectric relaxation is associated with the electrode-sample contact effect based on varying sample thickness and an annealing treatment in the nitrogen atmospheres.     

Effect of incorporating nonlanthanoidal indium on optical properties of ferroelectric Bi4Ti3O12 thin films

Bi₄Ti₃O₁₂ (BTO) and Bi_3.25In_0.75Ti₃O₁₂ (BTO:In) thin films were prepared on fused quartz and LaNiO₃/Si (LNO) substrates by chemical solution deposition (CSD). Their microstructures, ferroelectric and optical properties were investigated by X-ray diffraction, scanning electron microscope, ferroelectric tester and UV-visible-NIR spectrophotometer, respectively. The optical band-gaps of the films were found to be 3.64 and 3.45 eV for the BTO and BTO:In films, respectively. Optical constants (refractive indexes and extinction coefficients) were determined from the optical transmittance spectra using the envelope method. Following the single electronic oscillator model, the single oscillator energy E₀, the dispersion energy E_d, the average interband oscillator wavelength λ₀, the average oscillator strength S₀, the refractive index dispersion parameter (E₀/S₀), the chemical bonding quantity β, and the long wavelength refractive index n_∞ were obtained and analyzed. Both the refractive index and extinction coefficient of the BTO:In films are smaller than those of the BTO films. Furthermore, the refractive index dispersion parameter (E₀/S₀) increases and the chemical bonding quantity β decreases in the BTO and BTO:In films compared with those of bulk.     

Electrical behavior of BaZr0.1Ti0.9O3 and BaZr0.2Ti0.8O3 thin films

BaZr_0.1Ti_0.9O₃ and BaZr_0.2Ti_0.8O₃ (BZT) thin films were deposited on Pt/Ti/LaAlO₃ (1 0 0) substrates by radio-frequency magnetron sputtering, respectively. The films were further annealed at 800 °C for 30 min in oxygen. X-ray diffraction θ-2θ and Φ-scans showed that BaZr_0.1Ti_0.9O₃ films displayed a highly (h 0 0) preferred orientation and a good cube-on-cube epitaxial growth on the LaAlO₃ (1 0 0) substrate, while there are no obvious preferential orientation in BaZr_0.2Ti_0.8O₃ thin films. The BaZr_0.1Ti_0.9O₃ films possess larger grain size, higher dielectric constant, larger tunability, larger remanent polarization and coercive electric field than that of BaZr_0.2Ti_0.8O₃ films. Whereas, BaZr_0.1Ti_0.9O₃ films have larger dielectric losses and leakage current density. The results suggest that Zr⁴⁺ ion can decrease dielectric constant and restrain non-linearity. Moreover, the enhancement in dielectric properties of BaZr_0.1Ti_0.9O₃ films may be attributed to (1 0 0) preferred orientation.     

Microstructure-dependent giant dielectric response in CaCu3Ti4O12 ceramics

CaCu₃Ti₄O₁₂ ceramics were prepared at the sintering temperatures ranged from 1025 to 1125 °C, and the dielectric characteristics were evaluated together with the microstructures. The giant dielectric constant with the maximum of 53,120 was obtained in CaCu₃Ti₄O₁₂ ceramics at room temperature and 10 kHz, and strong processing and microstructure dependence of dielectric characteristics of the present ceramics was determined. The precipitation of the dispersed Cu-rich secondary phases of CuO and/or Cu₂O and their network structure provided the extrinsic origins of the enhanced giant dielectric response, and the present findings would offer the greater potential for enhancing the giant dielectric constant and controlling the dielectric loss in CaCu₃Ti₄O₁₂ ceramics by optimizing the microstructures.     

Band bending measurement of HfO2/SiO2/Si capacitor with ultra-thin La2O3 insertion by XPS

The flat band voltage shifts of HfO₂/SiO₂/nSi capacitors with ultra-thin La₂O₃ insertion at HfO₂/SiO₂ interface have been confirmed using hard X-ray photoelectron spectroscopy (HX-PES). By increasing the amount of La₂O₃ insertion, the binding energy of Si 1s core spectra increases, which means that the surface potential of Si substrate also increases. A voltage drop difference of HfO₂ and La₂O₃ at SiO₂ interface can be estimated to be 0.40 V.     

CaCu3Ti4O12块材和薄膜的巨介电常数

用固相反应法和脉冲激光沉积(PLD)制备了CaCu₃Ti₄O₁₂块材和薄膜，获得了相对介电常数ε′（1kHz,300K)高于14000的介电特性，是目前该体系最好的结果.报道了(00l)取向高质量CaCu₃Ti₄O₁₂外延薄膜及其介电性质.C aCu₃Ti₄O₁₂相对介电常数ε′在100—300K温度范围 内 关键词： 3Ti₄O₁₂')" href="#">CaCu₃Ti₄O₁₂ 巨介电常数 PLD     

Ti deficiency effect on the dielectric response of CaCu3Ti4O12 ceramics

Single phase ceramics CaCu₃Ti_4.0O₁₂ and CaCu₃Ti_3.9O₁₂ have been prepared using the traditional solid-state reaction method. Compared with the stoichiometric ceramics CaCu₃Ti_4.0O₁₂, Ti-deficient ceramics CaCu₃Ti_3.9O₁₂ have the larger lattice parameter, the higher force constant, and smaller dielectric constant and the lower dissipation factor, although their fundamental characters of dielectric response are similar. Their characteristic relaxation frequencies are not well fitted with the Arrhenius Law but a tentatively supposed relation. With the Cole-Cole Law, the fitted broadened factors of dissipation peaks are 0.5433 and 0.8651 for CaCu₃Ti_3.9O₁₂ and CaCu₃Ti_4.0O₁₂, respectively. All facts mentioned above imply that mutually correlated motion of Ti ions or defects may be expected to be responsible for the giant dielectric constant and high dissipation factor of CaCu₃Ti_4.0O₁₂.     

Effect of Cu-stoichiometry on the dielectric and electric properties in CaCu3Ti4O12 ceramics

CaCu_3+yTi₄O₁₂ (y=0, ±0.025, ±0.05, ±0.1 and −0.15) ceramics are prepared by the conventional solid-state reaction technique under sintering condition of 1050 ^°C, 10 h. X-ray diffraction shows that they all have the good crystalline structure. Cu-deficient ceramics exhibit the microstructures of uniform grain size distribution, whereas both Cu-stoichiometric and Cu-rich ceramics display microstructures of bimodal grain size distribution. The largeness of low-frequency dielectric permittivity at room temperature is found to be very sensitive to the Cu-stoichiometry. Upon raising the measuring temperature, all of the ceramics present commonly three semicircles in the complex impedance plane. It indicates that there exist three distinct contributions, which are ascribed to arising from domains, grain boundaries and domain boundaries. In addition, the influence of CuO segregation on the dielectric and electrical properties is also discussed.     

First principles study of the electron structures of CaCu3Mn4O12 and CaCu3Ti4O12

The electronic structures of CaCu₃Mn₄O₁₂ and CaCu₃Ti₄O₁₂ are investigated from HF SCF LCAO calculation. In CaCu₃Mn₄O_12, the band and the density of states show a spin asymmetric ferrimagnetic character with a small energy gap. The Mn spin is anti-aligned with the Cu spin, and the total spin moment is 9 μ_B. Our calculation correctly reproduces the observed antiferromagnetic insulating character of CaCu₃Ti₄O₁₂. The gap in the band structure, which is 2.15 eV, reasonably agrees with the experimental value 1.5 eV. The electron density populations at different planes show clearly that the electron density has symmetric character. A tilted Mn(Ti) orbital implies a typical tilted three-dimensional network of MnO₆ (TiO₆) octahedra due to doping of the Jahn–Teller ion Cu. There is no covalency between Ca, Cu and Mn(Ti) atoms. In contrast, there are stronger bonds and somewhat likely covalency between Cu and O atoms, and also between Mn(Ti) and O atoms.     

Field electron emission from HfNxOy thin films deposited by direct current sputtering

HfN_xO_y thin films were deposited on Si substrates by direct current sputtering at room temperature. The samples were characterized by scanning electron microscopy (SEM), atomic force microscopy (AFM) and X-ray diffraction (XRD). SEM indicates that the film is composed of nanoparticles. AFM indicates that there are no sharp protrusions on the surface of the film. XRD pattern shows that the films are amorphous. The field electron emission properties of the film were also characterized. The turn-on electric field is about 14 V/μm at the current density of 10 μA/cm², and at the electric field of 24 V/μm, the current density is up to 1 mA/cm². The field electron emission mechanism of the HfN_xO_y thin film is also discussed.     

Dependence of excess bismuth content in precursor sols on ferroelectric and dielectric properties of Bi3.25La0.75Ti3O12 thin films fabricated by chemical solution deposition

Bi_3.25La_0.75Ti₃O₁₂ (BLT) thin films were fabricated on Pt/Ti/SiO₂/Si(1 0 0) substrates by chemical solution deposition (CSD), and the dependence of ferroelectric and dielectric properties of the as-deposited BLT thin films on excess Bi content in precursor sols was studied. It is found that the prepared BLT thin film shows the best polarization-electric field, capacitance-voltage and dielectric constant (?_r)-frequency characteristics, when the value of excess Bi content in precursor sols is 10%. In detail, its remnant polarization (2P_r) value is 40 μC/cm², the capacitance tunability is 21% measured at room temperature under conditions of an applied voltage of 8 V and measurement frequency of 10 kHz, and the ?_r is 696 at 100 kHz frequency.     

Optical and structural studies on Ba(Mg1/3Ta2/3)O3 thin films obtained by radiofrequency assisted pulsed plasma deposition

Single-phase Ba(Mg_1/3Ta_2/3)O₃ thin films were prepared by radiofrequency plasma beam assisted pulsed laser deposition (RF-PLD) starting from a bulk ceramic target synthesized by solid state reaction. Atomic force microscopy, X-ray diffraction and spectroscopic ellipsometry were used for morphological, structural and optical characterization of the BMT thin films. The X-ray diffraction spectra show that the films exhibit a polycrystalline cubic structure. From spectroscopic ellipsometry analysis, the refractive index varies with the thin films deposition parameters. By using the transmission spectra and assuming a direct band to band transition a band gap value of ≈4.72 eV has been obtained.     

直流老化对CaCu3Ti4O12陶瓷介电性能的影响

在电场为3.5 kV/cm的条件下, 对CaCu₃Ti₄O₁₂陶瓷进行了60 h的直流老化, 研究了老化过程对CaCu₃Ti₄O₁₂陶瓷介电性能和电气特性的影响. J-E特性测试结果表明, 直流老化导致CaCu₃Ti₄O₁₂陶瓷击穿场强、非线性系数和势垒高度明显降低. 介电性能测试结果表明, 低频介电常数和介电损耗明显增大, 并且介电损耗随频率的变化遵从Debye弛豫理论, 可分解为直流电导损耗和弛豫损耗, 直流老化主要导致了电导损耗的增加. 在低温233 K, 介电损耗谱中出现两个弛豫峰, 其活化能分别为0.10, 0.50 eV, 认为对应着晶粒和畴界的弛豫过程, 且不随直流老化而变化. 通过电模量谱对CaCu₃Ti₄O₁₂陶瓷的弛豫过程进行了表征, 发现直流老化导致的界面空间电荷在外施交变电场的作用下符合Maxwell-Wagner极化效应, 并在低频区形成新的弛豫峰. 在高温323-473 K的阻抗谱中, 晶界弛豫峰在直流老化后明显向高频移动, 其对应的活化能从1.23 eV 下降到0.72 eV, 晶界阻抗值下降了约两个数量级. 最后, 建立了CaCu₃Ti₄O₁₂陶瓷的阻容电路模型, 分析了介电弛豫过程与电性能之间的关联.     

Nanoparticles of the giant dielectric material, CaCu3Ti4O12 from a precursor route

A method of preparing the nanoparticles of CaCu₃Ti₄O₁₂ (CCTO) with the crystallite size varying from 30 to 200 nm is optimized at a temperature as low as 680 °C from the exothermic thermal decomposition of an oxalate precursor, CaCu₃(TiO)₄(C₂O₄)₈·9H₂O. The phase singularity of the complex oxalate precursor is confirmed by the wet chemical analyses, X-ray diffraction, FT-IR and TGA/DTA analyses. The UV-vis reflectance and ESR spectra of CCTO powders indicate that the Cu(II) coordination changes from distorted octahedra to nearly flattened tetrahedra (squashed) to square-planar geometry with increasing annealing temperature. The HRTEM images have revealed that the evolution of the microstructure in nanoscale is related to the change in Cu(II) coordination around the surface regions for the chemically prepared powder specimens. The nearly flattened tetrahedral geometry prevails for CuO₄ in the near surface regions of the particles, whereas square-planar CuO₄ groups are dominant in the interior regions of the nanoparticles. The powders derived from the oxalate precursor have excellent sinterability, resulting in high-density ceramics which exhibited giant dielectric constants upto 40,000 (1 kHz) at 25 °C, accompanied by low dielectric loss <0.07.     

Microstructures and dielectric properties of compositionally graded (Ba1-xSrx) TiO3 thin films prepared by pulsed laser deposition

Compositionally graded (Ba_1-xSr_x)TiO₃ (BST) (x:0.0∼0.25) thin films were grown on Pt (111)/TiO₂/SiO₂/Si (100) substrates using layer-by-layer pulsed laser deposition in the temperature range 550–650 °C. Both downgraded (Ba/Sr ratio varying from 100/0 at the bottom surface to 75/25 at the top surface) and upgraded (Ba/Sr ratio varying from 75/25 at the bottom surface to 100/0 at the top surface) BST films were prepared. Their microstructures were systematically studied by X-ray diffractometry and scanning electron microscopy. A grain morphology transition from large ‘rosettes’ (>0.30 μm) to small compact grains (70–110 nm) was observed in the downgraded BST films as the deposition temperature was increased from 550 to 650 °C. No such grain morphology transition was detected in the upgraded BST films. Dielectric measurements with metal electrodes revealed an enhanced dielectric behavior in the downgraded films. This enhancement is mainly attributed to the large compressive stress field built up near the interface between the downgraded film and substrate. Furthermore, the BaTiO₃ layer in the downgraded BST films not only serves as a bottom layer but also as an excellent seeding layer for enhancing the crystallization of the subsequent film layers in the downgraded films. Received: 10 December 2001 / Accepted: 12 March 2002 / Published online: 19 July 2002 RID="*" ID="*"Corresponding author. Fax: 86-25/359-5535, E-mail: xhzhu@public1.ptt.js.cn