Synthesis and characterization of PLZT thin films obtained by pulsed laser deposition

Thin films of Pb_1-xLa_x(Zr_0.65Ti_0.35)_1-x/4O₃ with x=0.09 (PLZT 9/65/35) have been grown by pulsed laser deposition (PLD) and by PLD assisted by radio frequency (RF) discharge in oxygen which increases the plasma reactivity and reduces the oxygen vacancies in films and at the film-bottom electrode interface. Significant compositional, structural and dielectric differences have been found among samples grown in the same deposition conditions excepting for RF power. Films grown by RF-assisted PLD have less pyrochlore and are more oriented. For these films dielectric permittivity vs. temperature variation was typical of relaxor ferroelectrics and the temperature of the dielectric maximum was close to that obtained in bulk, but the permittivity value was much lower. This was attributed mainly to the influence of a low permittivity interface layer and to the detrimental effect of pyrochlore phase, still present in small quantities even in the films obtained by RF-PLD. The dielectric behavior of films grown without RF discharge was very different: no dielectric anomaly was observed, only a step increase above 180 °C. Moreover much higher dielectric loss was measured for these films. PACS 84.15.Fg; 77.84.-s; 77.22.Gm     

The power of in situ pulsed laser deposition synchrotron characterization for the detection of domain formation during growth of Ba0.5Sr0.5TiO3 on MgO

A highly sophisticated pulsed laser deposition (PLD) chamber has recently been installed at the NANO beamline at the synchrotron facility ANKA (Karlsruhe, Germany), which allows for comprehensive studies on the PLD growth process of dielectric, ferroelectric and ferromagnetic thin films in epitaxial oxide heterostructures or even multilayer systems by combining in situ reflective high‐energy diffraction with the in situ synchrotron high‐resolution X‐ray diffraction and surface diffraction methods. The modularity of the in situ PLD chamber offers the opportunity to explore the microstructure of the grown thin films as a function of the substrate temperature, gas pressure, laser fluence and target–substrate separation distance. Ba_0.5Sr_0.5TiO₃ grown on MgO represents the first system that is grown in this in situ PLD chamber and studied by in situ X‐ray reflectivity, in situ two‐dimensional reciprocal space mapping of symmetric X‐ray diffraction and acquisition of time‐resolved diffraction profiles during the ablation process. In situ PLD synchrotron investigation has revealed the occurrence of structural distortion as well as domain formation and misfit dislocation which all depend strongly on the film thickness. The microstructure transformation has been accurately detected with a time resolution of 1 s. The acquisition of two‐dimensional reciprocal space maps during the PLD growth has the advantage of simultaneously monitoring the changes of the crystalline structure as well as the formation of defects. The stability of the morphology during the PLD growth is demonstrated to be remarkably affected by the film thickness. A critical thickness for the domain formation in Ba_0.5Sr_0.5TiO₃ grown on MgO could be determined from the acquisition of time‐resolved diffraction profiles during the PLD growth. A splitting of the diffraction peak into two distinguishable peaks has revealed a morphology change due to modification of the internal strain during growth.     

Structure and dielectric properties of ultra-thin ZrO<Subscript>2</Subscript> films for high-<Emphasis Type="Italic">k</Emphasis> gate dielectric application prepared by pulsed laser deposition

ZrO₂ thin films have been prepared on Pt-coated silicon substrates and directly on n-Si(100) substrates by the pulsed laser deposition (PLD) technique using a ZrO₂ ceramic target under different deposition conditions. X-ray diffraction showed that the films prepared at 400 °C in 20 Pa oxygen ambient remained amorphous. Differential thermal analysis was carried out to study the crystallization behavior of ZrO₂. The dielectric constant of ZrO₂ was determined to be around 24 by measuring a Pt/ZrO₂/Pt capacitor structure. Sputtering depth profile X-ray photoelectron spectroscopy was used to investigate the interfacial characteristics of ZrO₂/n-Si stacks. A Zr silicate interfacial layer was formed between the ZrO₂ layer and the silicon substrate. The equivalent oxide thickness (EOT) and leakage current densities of the films with 6.6 nm physical thickness post-annealed in O₂ and N₂ ambient were investigated. An EOT of 1.65 nm with a leakage current of 36.2 mA/cm² at 1 V gate voltage for the film post-annealed in N₂ has been obtained. ZrO₂ thin films prepared by PLD have acceptable structure and dielectric properties required by a candidate material of high-k gate dielectrics. PACS 77.55.+f; 81.15.Fg; 73.40.Qv     

PLD and RF-PLD synthesis of Ba<Subscript>0.6</Subscript>Sr<Subscript>0.4</Subscript>TiO<Subscript>3</Subscript> ferroelectric thin films for electrically controlled devices

Ba_0.6Sr_0.4TiO₃ (BST) bulk ceramic synthesized by solid state reaction was used as target for thin films grown by pulsed laser deposition (PLD) and radiofrequency beam assisted PLD (RF-PLD). The X-ray diffraction patterns indicate that the films exhibit a polycrystalline cubic structure with a distorted unit cell. Scanning Electron Microscopy investigations showed a columnar microstructure with size of spherical grains up to 150 nm. The capacitance–voltage (C–V) characteristics of the BST films were performed by applying a DC voltage up to 5 V. A value of 280 for dielectric constant and 12.5% electrical tunability of the BST capacitor have been measured at room temperature.     

Effect of growth defects on microwave properties in epitaxial Ba0.5Sr0.5TiO3 thin films grown on (001) MgO by pulsed laser deposition

Ba_0.5Sr_0.5TiO₃ (BSTO) films have been grown heteroepitaxially on (001) MgO substrates by pulsed laser deposition (PLD) to fabricate microwave phase shifters for the wide frequency range 45 MHz–50 GHz. Both as-grown and ex situ annealed films have a cube on cube epitaxial relationship with ?100?BSTO//?100?MgO. Threading dislocations are the dominant defects, mostly with Burgers vectors b = ?101?. Growth at 10^?1 mbar oxygen pressure, compared to 10^?4 mbar, resulted in significantly better properties. Ex situ annealing of the film grown at 0.1 mbar resulted in a reduction of 40% in threading dislocation density and a 40% increase in dielectric tunability.     

Effect of process parameters and post-deposition annealing on the microwave dielectric and optical properties of pulsed laser deposited Bi<Subscript>1.5</Subscript>Zn<Subscript>1.0</Subscript>Nb<Subscript>1.5</Subscript>O<Subscript>7</Subscript> thin films

Bismuth Zinc niobate (Bi_1.5Zn_1.0Nb_1.5O₇) thin films were deposited by pulsed laser deposition (PLD) method on fused silica substrates at different oxygen pressures. The structural, microwave dielectric and optical properties of these thin films were systematically studied for both the as-deposited and the annealed films at 600°C. The as-deposited films were all amorphous in nature but crystallized on annealing at 600°C in air. The surface morphology as studied by atomic force microscopy (AFM) reveals ultra-fine grains in the case of as-deposited thin films and cluster grain morphology on annealing. The as-deposited films exhibit refractive index in the range of 2.36–2.53 (at a wavelength of 750 nm) with an optical absorption edge value of 3.30–3.52 eV and a maximum dielectric constant of 11 at 12.15 GHz. On annealing the films at 600°C they crystallize to the cubic pyrochlore structure accompanied by an increase in band gap, refractive index and microwave dielectric constant.     

Pulsed laser deposition of PZT/Pt composite thin films with high dielectric constants

PbZr_0.53Ti_0.47O₃ (PZT) thin films containing nanoparticles of Pt (3–10 nm) were produced using pulsed laser deposition (PLD). The Pt content can be tuned by varying the energy density of the laser beam. Phase and microstructure analysis of the thin films was performed using XRD, SEM, TEM and AFM. The electrical properties were investigated by C–V and I–V measurements. The effective dielectric constant of the composite films increased substantially through the Pt dispersion. These films are promising candidates, for instance, for high-density dynamic random access memory (DRAM) devices. PACS 77.22.Ch; 77.84.Lf; 81.15.Fg     

Effect of Bi substitution on the magnetic and dielectric properties of epitaxially grown BaFe0.3Zr0.7O3−δ thin films on SrTiO3 substrates

The structural, dielectric and magnetic properties of single crystalline Ba_1−xBi_xFe_0.3Zr_0.7O_3−δ (x=0.0-0.29) thin films have been studied. The pseudotetragonal epitaxial thin films were obtained by pulsed laser-beam deposition (PLD) on (0 0 1) SrTiO₃ (STO) single-crystal substrates. The Bi substitution for the Ba ions up to an extent of x=0.18 caused a slight improvement in the leakage current properties, as well as an enhancement of the apparent dielectric constant. The saturation magnetization of the films was significantly decreased following Bi substitution. These changes were thought to be related to the increase in oxygen deficiencies in the films. The effect of the Bi substitution on the dielectric and magnetic properties was analyzed in conjunction with the change in valence value of the Fe ions.     

Optical parameters of In–Se and In–Se–Te thin amorphous films prepared by pulsed laser deposition

The thin films of materials based on In–Se are under study for their applicability in photovoltaic devices, solid-state batteries and phase-change memories.The amorphous thin films of In₂Se_3−xTe_x (x=0–1.5) and InSe were prepared by pulsed laser deposition method (PLD) using a KrF excimer laser beam (λ=248 nm, 0.5 J cm⁻²) from polycrystalline bulk targets. The compositions of films verified by energy-dispersive X-ray analysis (EDX) were close to the compositions of targets. The surfaces of PLD films containing small amount of droplets were viewed by optical and scanning electron microscopy (SEM).The optical properties (transmittance and reflectance spectra, spectral dependence of index of refraction, optical gap, single-oscillator energy, dispersion energy, dielectric constant) of the films were determined.The values of index of refraction increased with increasing substitution of Te for Se in In₂Se₃ films, the values of the optical gap decreased with increasing substitution of Te for Se in In₂Se₃ films.     

Temperature-dependent characteristics of pulse-laser-deposited (Pb,Sr)TiO<Subscript>3</Subscript> films at low temperatures

Pulsed laser deposition (PLD) of (Pb,Sr)TiO₃ (PSrT) film on Pt/SiO₂/Si at low substrate temperatures (T_s), ranging from 300–450 °C, has been investigated. As T_s increases, the films reveal coarsening clusters, improved crystallization of the perovskite phase, distinct capacitance–electric field (C–E) hysteretic loops and a larger dielectric constant. The 350 °C-deposited film shows strong (100) preferred orientation and optimum dielectric properties with the dielectric constant of ∼620. The current density increases as the measurement temperature and the electric field increase. Moreover, PSrT films exhibit a strong negative temperature coefficient of resistance (NTCR) behavior at temperatures ranging from 100 to 390 °C. PACS 81.15.Fg; 77.22.Ch; 68.60.Dv     

The coexistence of ferroelectricity and ferromagnetism in Mn-doped BaTiO3 thin films

Due to the fault of the first author, this article entitled “The coexistence of ferroelectricity and ferromagnetism in Mn-doped BaTiO3 thin films”, published in “Chinese Physics B”, 2011,Vol.20, Issue 12, Article No. 127701, has been found to copy from the article entitled“Decisive role of oxygen vacancy in ferroelectric versus ferromagnetic Mn-doped BaTiO3 thin films”, published in “Journal of Applied Physics”, 2011,Vol.109, Issue 8, article No. 084105. So the above article in “Chinese Physics B” has been withdrawn from the publication.<     

Film structure and ferroelectric properties of in situ grown SrBi2Ta2O9 films

Ferroelectric SrBi₂Ta₂O₉ (SBT) films were grown by pulsed-laser deposition (PLD) at different substrate temperatures and fluences. A correlation between film structure and ferroelectric properties is established. The dielectric function ε^′ of thin SBT films shows a Curie–Weiss behavior well below the peak temperature T_max and relaxor-like behavior in the vicinity of T_max. Domain walls have a strong influence on the dielectric and ferroelectric properties and on the polarization fatigue of SBT films below 100 °C. The formation of ferroelectric phases is favored at lower substrate temperatures by incorporating Bi₂O₃ template layers into the structure. Received: 18 March 1999 / Accepted: 19 March 1999 / Published online: 5 May 1999     

SBN thin films growth by RF plasma beam assisted pulsed laser deposition

SBN thin films were grown on MgO and Silicon substrates by PLD and RF-PLD (radiofrequency assisted PLD) starting from single crystal Sr_0.6Ba_0.4Nb₂O₆ and ceramic Sr_0.5Ba_0.5Nb₂O₆ stoichiometric targets. Morphological and structural analyses were performed on the SBN layers by AFM and XRD and optical properties were measured by spectroellipsometry. The films composition was determined by Rutherford Backscattering Spectrometry. The best set of experimental conditions for obtaining crystalline, c-axis preferential texture and with dominant 31° in-plane orientation relative to the MgO (100) axis is identified.     

Mössbauer Studies of Nanosize CuFe2O4 Particles

⁵⁷Fe Mössbauer spectra of pulsed-laser deposited (PLD) films of CoFe₂O₄ of 0.3 µm thickness is investigated using transmission geometry is reported. Mössbauer parameters were determined for the tetrahedral (A) and octahedral (B) sites. The PLD processed films gave measurable spectra with no visible evidence of clustering or multiple phases present. Results on the films agreed with those of the bulk material. The films exhibited magnetic hyperfine and quadruple splittings similar to that of bulk CoFe₂O₄. This work demonstrates that measurable transmission Mössbauer spectra may be obtained for PLD deposited CoFe₂O₄ thick films.     

两种不同(Ba,Sr)TiO3薄膜介电-温度特性的研究

研究并比较了两种不同(Ba_0.5,Sr_0.5)TiO₃(BSTO)薄膜介电-温度特性.采用脉冲激光沉积技术在Pt/Ti/SiO₂/Si(100)衬底上制备BSTO薄膜，发现制备条件的不同，可以得到介电性质完全不同的BSTO薄膜.在550℃和氮气氛下制备的BSTO薄膜在常温下具有很高的介电常数，在10kHz下，超过2500，并在200K温度以上介电常数基本不变.它的一些电学性质不同于在正常条件(650℃和氧气氛下)制得的BSTO薄膜，而类似于目前广泛报道的巨介电常数材料如CaCu_３Ti_４O₁₂.两种薄膜介电性质测试结果表明: 氧气氛下制备的BSTO薄膜呈现铁电-顺电相变，符合居里-外斯定律；低温氮气氛下制备的BSTO薄膜，介电弛豫时间和温度的关系符合德拜模型，是热激发弛豫.文中给出了产生这种介电特性的初步解释. 关键词： 薄膜 脉冲激光沉积 介电弛豫     

Pulsed laser deposition of ZnO grown on glass substrates for realizing high-performance thin-film transistors

We report characterization of ZnO thin-film transistors (TFTs) on glass substrates fabricated by pulsed laser deposition (PLD). ZnO films were characterized by X-ray diffraction (XRD), atomic force microscopy and Hall effect measurements. The XRD results showed high c-axis-oriented ZnO(0002) diffraction corresponding to the wurtzite phase. Moreover, the crystallization and the electrical properties of ZnO thin films grown at room temperature are controllable by PLD growth conditions such as oxygen gas pressure. The ZnO films are very smooth, with a root-mean-square roughness of 1 nm. From the Hall effect measurements, we have succeeded in fabricating ZnO films on glass substrates with an electron mobility of 21.7 cm²/V s. By using the ZnO thin film grown by two-step PLD and a HfO₂ high-k gate insulator, a transconductance of 24.1 mS/mm, a drain current on/off ratio of 4.4×10⁶ and a subthreshold gate swing of 0.26 V/decade were obtained for the ZnO TFT.     

Thermal stability and electrical properties of Zr silicate films for high-k gate-dielectric applications, as prepared by pulsed laser deposition

Zirconium silicate films with high thermal stability and good electrical properties have been prepared on n-Si(100) substrates and commercially available Pt-coated Si substrates to fabricate metal–insulator–metal (MIM) structures by the pulsed laser deposition (PLD) technique using a Zr_0.69Si_0.31O_2- ceramic target. Rapid thermal annealing (RTA) in N₂ was performed. X-ray diffraction indicated that the films annealed at 800 °C remained amorphous. Differential thermal analysis revealed that amorphous Zr silicate crystallized at 830 °C. X-ray photoelectron spectroscopy showed that RTA annealing of Zr silicate films at 900 °C led to phase separation. The dielectric constant has been determined to be about 18.6 at 1 MHz by measuring the Pt/Zr silicate/Pt MIM structure. The equivalent oxide thicknesses (EOTs) and the leakage-current densities of films with 6-nm physical thickness deposited in O₂ and N₂ ambient were investigated. An EOT of 1.65 nm and a leakage current of 31.4 mA/cm² at 1-V gate voltage for the films prepared in N₂ and RTA annealed in N₂ at 800 °C were obtained. An amorphous Zr-rich Zr silicate film fabricated by PLD looks to be a promising candidate for future high-k gate-dielectric applications. PACS 77.55.+f; 81.15.Fg; 73.40.Qv     

Lead-free ferroelectric BaTiO3 doped-(Na0.5Bi0.5)TiO3 thin films processed by pulsed laser deposition technique

The difficulties in synthesizing phase pure BaTiO₃ doped-(Na_0.5Bi_0.5)TiO₃ are known. In this work, we reporting the optimized pulsed laser deposition (PLD) conditions for obtaining pure phase 0.92(Na_0.5Bi_0.5)TiO₃-0.08BaTiO₃, (BNT-BT_0.08), thin films. Dielectric, ferroelectric and piezoelectric properties of BNT-BT_0.08, thin films deposited by PLD on Pt/TiO₂/SiO₂/Si substrates are investigated in this paper. Perovskite structure of BNT-BT_0.08 thin films with random orientation of nanocrystallites has been obtained by deposition at 600 °C. The relative dielectric constant and loss tangent at 100 kHz, of BNT-BT_0.08 thin film with 530 nm thickness, were 820 and 0.13, respectively. Ferroelectric hysteresis measurements indicated a remnant polarization value of 22 μC/cm² and a coercive field of 120 kV/cm. The piezoresponse force microscopy (PFM) data showed that most of the grains seem to be constituted of single ferroelectric domain. The as-deposited BNT-BT_0.08 thin film is ferroelectric at the nanoscale level and piezoelectric.     

Structural and optical properties of Ba(Zn1/3Ta2/3)O3 thin films deposited by pulsed laser deposition

Ba(Zn_1/3Ta_2/3)O₃, (BZT), is a high-k and low loss dielectric resonator material which finds applications in the area of microwave communication and related areas. While there are reports on its bulk properties, there is hardly any report on its thin films. We report here preparation of thin films of BZT deposited on to borosilicate and quartz substrates using the pulsed laser deposition (PLD) technique under different oxygen mixing percentage (OMP) and preliminary studies on their structural and optical properties. The EDAX spectra show that the deposited films exhibit the composition of the target. As-deposited films, whether on a glass or quartz substrate, were found to be amorphous. The refractive index and energy bandgap of the films were found to be around 1.5 in the dispersion free region (500–1500 nm) and 5.2–5.5 eV, respectively. The Dynamic Force Microscopy (DFM) study of the BZT films exhibited columnar growth and films deposited at higher OMPs showed the smaller grain size.     

Structure, thermally and optically induced effects in amorphous As2Se3 films prepared by pulsed laser deposition

Thin amorphous As-Se films were prepared by pulsed laser deposition (PLD) and by classical thermal evaporation techniques. Raman spectra and optical properties (optical gap, E_g^opt, index of refraction, n, third-order non-linear susceptibility, χ⁽³⁾) of prepared films and their photo- and thermally induced changes were studied. The structure of laser deposited films was close to the corresponding bulk glasses contrary to thermal evaporated films. The composition of PLD films was practically unchanged during the process of deposition. The optically and thermally induced changes of n and of E_g^opt in PLD films are different from the changes in thermally deposited films. The differences are discussed.