Phase transition properties of ferroelectric thin films with two surface layers

The phase diagrams of ferroelectric thin films with two surface layers described by the transverse Ising model have been studied under the mean-field approximation. We discuss the effects of the exchange interaction and transverse field parameters on the phase diagrams. The results indicate that the phase transition properties of the phase diagrams can be greatly modified by changing the transverse Ising model parameters. In addition, the crossover features of the parameters from the ferroelectric dominant phase diagram to the paraelectric dominant phase diagram are determined for ferroelectric thin films with two surface layers.     

Simulation of thickness dependence in ferroelectric thin films

The thickness dependence of coercive field (E_C) and remanent polarization (P_r) in ferroelectric thin films has been numerically simulated using a two-dimensional four-state Potts model. In this model, each of the dipoles in the film is assigned to one of the four states corresponding to the four different mutually perpendicular orientations. Neighboring dipoles with the same orientation are then grouped together to form a domain. Four different kinds of domains exist. In the presence of the surface layer near the electrode/film interface, the thickness dependence of both coercive field and remanent polarization are simulated.     

Hydrophobic switching nature of methylcellulose ultra-thin films: thickness and annealing effects

We have studied the thermosensitive property of methylcellulose (MC) thin films supported on Si substrate by static sessile drop contact angle measurements, and their surface properties and thin film structure by x-ray reflectivity (XRR) and atomic force microscopy (AFM) techniques. From the static sessile drop contact angle measurements, the MC thin films showed the characteristic hydrophilic-to-hydrophobic transition at ～70?°C, which is the lower critical solution temperature of the bulk solution volume phase separation transition. For films with thickness d ≤ R(g), the onset of such a transition is affected by the film thickness while very thick films, d ? R(g), yielded higher contact angles. Annealing the MC thin films with thicknesses ～200 ? (near the radius of gyration, R(g), of the polymer) below the bulk glass transition temperature (T(g) ～ 195?° C) would not change the hydrophobic switch nature of the film but annealing 'at' and above the bulk T(g) would change its surface property. From surface topography images by AFM, there were no significant changes in either the roughness or the film texture before and after annealing. With XRR data, we were able to determine that such changes in the surface properties are highly correlated to the film thickness changes after the annealing process. This study, we believe, is the first to examine the thermal annealing affects on the thermal response function of a thermoresponsive polymer and is important for researching how to tailor the hydrophobic switching property of MC thin films for future sensing applications.     

Investigation of the seeding-layer effect for a ferroelectric thin film with the transverse Ising model

The transition feature of a ferroelectric thin film with a seeding layer is studied based on the transverse Ising model. The influence of the seeding layer on the transition behavior of a ferroelectric thin film is investigated systemically, and the effect of the interaction parameters for the seeding layer on the phase diagram is also obtained. Meanwhile, the polarization and Curie temperature of the ferroelectric thin film are calculated for different seeding-layer structures. The results show that the polarization and Curie temperature of the film will be obviously modified on adding a seeding layer.     

Renormalization group studies of phase diagrams of Ising and XY-model films of variable thickness

We compare the critical behavior of $\text{spin}\text{-}\text{1}\text{2}$ Ising model (ordinary phase transition in two dimensions) and classical XY-model (topological phase transition in two dimensions) films, with two flat surfaces and nearest neighbor couplings K_S between surface spins and K_B between all others, as a function of film thickness. We carry out a real space Migdal-style renormalization in two stages. In the bulk stage the film is first renormalized towards a double layer, with the renormalized parameters as inter- and intra-layer couplings. Then the double layer is renormalized with those couplings as initial parameters. From the RG-equations for the bulk stage we find a tricritical point, not only for the Ising model (in which case it is well known) but also for the XY-model. It signals the existence of distinct surface and bulk transitions for sufficiently large values of $\text{K}{}_{\mathrm{<mtext>S</mtext>}}\text{K}{}_{\mathrm{<mtext>B</mtext>}}$. For the Ising model the complete program can be carried out and the phase diagram for films of arbitrary thickness is constructed. For the double layer XY-model a sufficiently complex Migdal-style renormalization appears to be unfeasible, presumably due to the possible presence of strings between the layers. Therefore, in an alternative approach, two representations for the partition function of the double layer XY-model are given. The system can be described in terms of its topological excitations, i.e., vortices on each layer and strings, either closed or terminating in vortices, between them. The system is also written as three coupled Coulomb gases. Based on this representation a renormalization group is found, and used, together with a Griffiths inequality for the correlation functions, to obtain information on the phase diagram. If there is a single phase transition, there is one phase where the correlations exhibit power law behavior and another where they fall off exponentially. The transition temperature increases monotonously with interlayer coupling to twice its value in two dimensions, but the nature of the phase transition for any finite inter-layer coupling appears to be different from that at zero coupling. We suggest that this is associated with the behavior of the internal strings. These results should be relevant for the renormalization of the film with isotropic bulk couplings as well as for layered systems of finite thickness, with different inter- and intra-layer couplings.     

Stabilization of discotic liquid organic thin films by ITO surface treatment

Discotic liquid crystals (LCs) are promising materials in the field of electronic components and, in particular, to make efficient photovoltaic cells due to their good charge transport properties. These materials generally exhibit a mesophase in which the disk-shaped molecules can self-assemble into columns, which favorize charge displacement, and may align themselves uniformly on surfaces to form well-oriented thin films. In order to orientate such a columnar thin film on an indium tin oxide (ITO) substrate, the film is heated up to the temperature range of the isotropic liquid phase and subsequently cooled down again. This treatment may lead not only to the desired alignment, but also to dewetting, which leads to an appreciable inhomogeneity in film thickness and to short circuits during the realization of photovoltaic cells. In this article, we describe how this dewetting and the film morphology can be influenced by ITO surface treatments. The chemical modifications of the surface by these treatments were studied by X-ray photoelectron spectroscopy (XPS). Such ITO treatments are shown to be efficient to prevent thin film dewetting when combined with rapid cooling through the isotropic-to-LC phase transition.     

Structural and optical properties of ZnO thin films prepared by sol-gel method with different thickness

In this work, ZnO thin films with different thickness were prepared by sol-gel method on glass substrates and the structural and optical properties of these films were studied by X-ray diffractometer, atomic force microscope, UV-visible spectrophotometer, ellipsometer and fluorophotometer, respectively. The structural analyses show that all the samples have a wurtzite structure and are preferentially oriented along the c-axis perpendicular to the substrate surface. The growth process of highly c-axis oriented ZnO thin films derived from sol-gel method is a self-template process. With the increase of film thickness, the structural disorder decreases and the crystalline quality of the films is gradually improved. A transition of crystal growth mode from vertical growth to lateral growth is observed and the transition point is found between 270 and 360 nm thickness. The optical analyses show that with the increase of film thickness, both the refractive index and ultraviolet emission intensity are improved. However, the transmittance in the visible range is hardly influenced by the film thickness, and the averages are all above 80%.     

Surface chemical states of barium zirconate titanate thin films prepared by chemical solution deposition

Ba(Zr_0.05Ti_0.95)O₃ (BZT) thin films grown on Pt/Ti/SiO₂/Si(1 0 0) substrates were prepared by chemical solution deposition. The structural and surface morphology of BZT thin films has been studied by X-ray diffraction (XRD) and scanning electron microscope (SEM). The results showed that the random oriented BZT thin film grown on Pt/Ti/SiO₂/Si(1 0 0) substrate with a perovskite phase. The SEM surface image showed that the BZT thin film was crack-free. And the average grain size and thickness of the BZT film are 35 and 400 nm, respectively. Furthermore, the chemical states and chemical composition of the films were determined by X-ray photoelectron spectroscopy (XPS) near the surface. The XPS results show that Ba, Ti, and Zr exist mainly in the forms of BZT perovskite structure.     

Epitaxy surface effect on the first-order phase transition properties in a ferroelectric thin film

By modifying the interchange interactions and the transverse fields on the epitaxy surface layer,this paper studies the phase transition properties of an n-layer ferroelectric thin film by the Fermi-type Green’s function technique based on the transverse Ising model with a four-spin interaction.The special attention is given to the effect of the epitaxy surface layer on the first-order phase transition properties in the parameter space constructed by the ratios of the bulk transverse field and the bulk four-spin interaction to the bulk two-spin interaction with the framework of the higher-order decoupling approximation to the Fermi-type Green’s function.The results show that the first-order phase transition properties will be changed significantly due to the modification of interchange interaction and transverse field parameters on the epitaxy surface layer.The dependence of the first-order phase transition properties on the thickness of ferroelectric thin films is also discussed.     

The electrical properties and phase transformation of PLZST 2/85/13/2 antiferroelectric thin films on different bottom electrode

Pb_0.97La_0.02(Zr_0.85Sn_0.13Ti_0.02)O₃ (PLZST 2/85/13/2) antiferroelectric thin films were deposited on Pt(111)/Ti/SiO₂/Si and LaNiO₃(LNO)/SiO₂/Si substrates through a modified sol-gel process. The phase structure and microstructure of PLZST 2/85/13/2 antiferroelectric thin films were analysed by x-ray diffraction (XRD), scanning electron microcopy (SEM) and field-emission SEM (FE-SEM). The antiferroelectric nature of the PLZST 2/85/13/2 thin films on two electrodes was demonstrated by the C-V (capacitance-voltage) and P-E (polarization-electric field) measurement. The maximum polarizations for PLZST 2/85/13/2 films on Pt and LNO electrodes were 42 and 18 μC/cm², respectively. The temperature dependence of the dielectric property of the PLZST 2/85/13/2 films was measured under different dc electric fields. Also, the phase transformation of the PLZST 2/85/13/2 films was studied in detail as a function of temperature and dc electric field.     

Molecular dynamics investigation of the structural stability of body-centered cubic zirconium nanofilms

The influence of the film thickness and temperature on the phase stability of body-centered cubic (BCC) zirconium in infinite films with different crystallographic orientations has been investigated using the molecular dynamics method with a many-body interatomic interaction potential obtained within the embedded atom model. The calculations have been performed for BCC zirconium films with thicknesses ranging from 2 to 13 nm and with low Miller indices (001), (110), and (111). It has been shown that the BCC(001) zirconium nanofilms with thicknesses up to 6.1 nm, which are formed in the temperature range from 500 to 1300 K, undergo a reorientational phase transition through an intermediate metastable face-centered cubic (FCC) phase with the subsequent transformation into the hexagonal close-packed (HCP) structure (BCC(001)-FCC-BCC??(110)-HCP). When the temperature of initialization of the films is 500 K and below, the BCC-FCC transformation is observed and the FCC phase remains stable. The (110) films are characterized by a strong dependence of the temperature of the BCC-HCP phase transition on the film thickness up to values of 5.8 nm. In the (111) films, the amorphization of the initial BCC phase with the subsequent formation of the BCC phase with a twin structure is observed.     

Size-induced appearance of ferroelectricity in thin antiferroelectric films

In the paper we consider size effects on phase transitions and polar properties of thin antiferroelectric films. We extend the phenomenological approach proposed by Kittel for thin films allowing for gradient (correlation) energy and depolarization field energy. Surface piezoelectric effect as well as misfit strain appear due to lattice constants mismatch between the film and its substrate. Direct variational method is used to derive the free energy with renormalized coefficients depending on the film thickness. Obtained free energy expression allows the calculation of phase diagrams and all electro-physical properties by a conventional minimization procedure. Approximate analytical expressions for the paraelectric–antiferroelectric–ferroelectric transition temperature dependences on film thickness, polarization gradient coefficient, and extrapolation lengths were obtained. The thickness dependence of the electric field critical value that causes antiferroelectric–ferroelectric phase transition was calculated. Under favorable conditions the antiferroelectric phase at first transforms into ferroelectric one and then into paraelectric phase with the decrease of the film thickness. Proposed theoretical consideration explains the experimental results obtained in antiferroelectric PbZrO₃ thin films.     

Formation of the ferroelectric domains in epitaxial PbTiO3 thin films grown by metalorganic chemical vapor deposition

3 thin films have been prepared by metalorganic chemical vapor deposition under reduced pressure. The formation of ferroelectric domains in films grown on SrTiO₃ and LaAlO₃ substrates was investigated by synchrotron radiation and Rutherford backscattering spectroscopy. Single-domain (3000-Å thick) and multi-domain (4500-Å thick) PbTiO₃ films were produced on SrTiO₃. For multi-domain PbTiO₃ film, the c-domain presented epitaxial structure with its c-axis perpendicular to the substrate surface, while a-domains aligned four-fold symmetrically with c-domains by 2.79^° off the c-axis of c-domains. In the film, the measured lattice constants (a, b and c) of the a- and c-domains were different from each other, indicating that the films suffered a modulated strain during domain formation. In contrast, both the a and c domains of films on LaAlO₃ were alternatively aligned on substrate with the a-axis of the a-domain and the c-axis of c-domains perpendicular to the substrate surface. Two-dimensional distribution of these domains is proposed and the formation of these kinds of domains is discussed. The surface morphology and phase transition process of single and multi domain PbTiO₃ film on SrTiO₃ were studied by atomic force microscope (AFM) and high temperature X-ray diffraction, respectively. Received: 15 August 1996/Accepted: 21 January 1997     

SiO2和HfO2薄膜光学性能的椭偏光谱测量

结合XRD和原子力显微镜等方法,利用椭圆偏振光谱仪测试了单层SiO2薄膜（K9基片）和单层HfO2薄膜（K9基片）的椭偏参数,并用Sellmeier模型和Cauchy模型对两种薄膜进行拟合,获得了SiO2薄膜和HfO2薄膜在300-800nm波段内的色散关系。用X射线衍射仪确定薄膜结构,并用原子力显微镜观察薄膜的微观形貌,分析表明：SiO2薄膜晶相结构呈现无定型结构,HfO2薄膜的晶相结构呈现单斜相结构;薄膜光学常数的大小和薄膜的表面形貌有关;Sellmeier和Cauchy模型较好地描述了该波段内薄膜的光学性能,并得到薄膜的折射率和消光系数等光学常数随波长的变化规律。     

Influence of surface ordering on the wetting of structured liquids

The substrate is shown to induce substantial ordering in diblock copolymer thin films above the bulk order-disorder transition (ODT) where, thermodynamically, a phase mixed state is favored. Initially, uniform films reorganize to form a hierarchy of transient surface patterns and stable film thicknesses that depend on the initial film thickness and on the substrate. Self-consistent field calculations of the free energy of the system for different situations, depending on the relative tendency for the different block components to be attracted to the substrate and/or free surface, provide an explanation of the formation of the stable film thicknesses. A continuum picture proposed earlier by Brochard et al.rovides an explanation of the wetting characteristics of this system. In some cases the ordering destabilizes the film so that dewetting occurs (wetting autophobicity), whereas in other cases the surface ordering results in a kinetic stabilization of a film that would otherwise dewet. Received 3 August 2001 and Received in final form 1 November 2001     

参数修改对铁电薄膜相变性质的影响

在关联有效场理论的框架内, 利用微分算子技术, 详细地计算了基于横场伊辛模型描述的对称铁电薄膜系统的相变性质. 根据薄膜各层自旋平均值构成的一系列耦合方程, 推导出可以用来计算任意层的具有不同表面层的薄膜相图的解析通式方程, 讨论了参数修改对薄膜相互作用参数从FPD (铁电相占主导地位的相图)到PPD (顺电相占主导地位的相图)过渡值和参数空间中各相变区域的影响. 在与平均场近似进行比较的结果显示, 关联有效场理论所得到的铁电薄膜的铁电性在某种程度上比平均场近似下的结果减弱. 关键词： 铁电薄膜 横场伊辛模型 相图 居里温度     

Stability of thermoresponsive methylcellulose thin film: x‐ray reflectivity study

Methylcellulose (MC), a thermoreversible polymer, was fabricated as thin films into silicon substrates and characterized by x‐ray reflectivity (XRR) measurements for its stability with time and heating. XRR data from the as‐is thin films showed good agreement with the single‐layer model on top of a substrate from Parratt's formalism. Data fitting showed that the density of the thin films is slightly higher than the reported value by manufacturers. Interface roughness values indicate good wetting of the polymer onto the substrate. Heating the thin films at the phase transition temperatures and quenching them to room temperature showed no significant changes in the thin film parameters before and after heating. This showed the thermal stability and/or thermoreversibility of the film. Diffuse scattering measurements also showed no significant changes in the lateral structure of the film with heating and quenching. XRR measurements done on fabricated thin films stored for a month showed a slight increase in the film thickness which could be due to the hygroscopic nature of the polymer. Vacuum heating of the stored thin films at 100 °C for 1 h slightly decreased the thickness, but it has been found that other parameters such as density and surface/interface roughness show good thermal stability. Copyright © 2009 John Wiley & Sons, Ltd.     

Full X-ray pattern analysis of vacuum deposited pentacene thin films

Pentacene thin films with thicknesses ranging from 10 nm to 180 nm are investigated by specular X-ray diffraction in the reflectivity regime and in the wide angular regime. The results of the reflectivity measurements show a clear shift of the 001 reflection of the thin film phase depending on the layer thickness. It is shown that this shift can be explained by the dynamical scattering theory. The wide angular regime measurements show the 00L of the thin film phase. Williams-Hall plots are used to extract information on the crystallite size and mean micro strain of the thin film phase. The crystallite size is in good agreement with the results obtained by the reflectivity measurements. From this it can be concluded that the thin film phase crystallites are extended over the entire film thickness down to the substrate. Additionally an increase of the micro strain with increasing film thickness is observed.     

Piezoelectric evaluation of ion beam etched Pb(Zr,Ti)O3 thin films by piezoresponse force microscopy

The evolution of piezoelectric properties of Pb(Zr,Ti)O₃ (PZT) thin films after ion beam etching have been investigated at the nanoscale level by piezoelectric force microscopy. A comparison of the piezoelectric properties on etched and unetched films is realized. Piezoelectric contrasts imaging evidences a modification of the domain architecture at the film surface. Local piezoelectric hysteresis loops measurements on grains indicate that the coercive voltage for switching is much higher for the etched films (2.3 V) compared to the unetched ones (1.0 V) while the average piezoelectric activity is slightly lower. The results are explained in terms of grain-damaging during etching and domain-wall pinning.     

Study of relaxor-like behaviour of laser ablated (Pb, La)Tio3 thin films

Lanthanum modified lead titanate (PLT) thin films are one of the potential candidates for the pyroelectric and memory applications due to their excellent dielectric, pyroelectric and ferroelectric properties. PLT thin films with 25 at.% of La were deposited on platinum coated Si substrates by the laser ablation technique. The phase transition studies were done in the temperature range of −40 to 150 °C as a function of frequency and ac field. A diffused phase transition with the shifting of the maximum dielectric permittivity (?_max) to higher temperatures with the increase of frequency and dielectric dispersion with frequency at the lower temperatures were observed. The variation of the temperature corresponding to maximum dielectric constant T_m, with frequency follows the Vogel-Fulcher relation, which is the characteristic of the relaxor-like behavior of the material. With the increase of ac drive, the T_max was shifted to lower value.