Postannealing effect on physical and electrical characteristics of BTS thin films. Leakage densities are given for an applied voltage of 10V
\r\n\tIt is a relatively simple process and a standard tool in any industry. Because of the versatility of the titration techniques, nearly all aspects of society depend on various forms of titration to analyze key chemical compounds.
\r\n\tThe aims of this book is to provide the reader with an up-to-date coverage of experimental and theoretical aspects related to titration techniques used in environmental, pharmaceutical, biomedical and food sciences.
Since it was discovered in 1945, barium titanate (BT) attracted much attention to researchers, becoming one of the most investigated ferroelectric materials due to good electrical properties at room temperature, mechanical and chemical stability and the easiness in its preparation. It is known that above the Curie temperature, the crystalline barium titanate has a cubic, perovskite-like structure as shown in figure 1.
Crystalline structure of BT material above Curie temperature
Below the Curie temperature, the crystalline cell is suffering a series of changes: to tetragonal (at 120ºC), from tetragonal to orthorhombic (at 0ºC) and from orthorhombic to rhombohedral (at –90ºC) in which the material has ferroelectric properties.
Theories concerning the ferroelectric behavior of crystalline materials that have a perovskite structure pinpoint the important role played by the spatial oxygen arrangement having an ion in its center, to the ferroelectrical properties. Taking this into consideration it is easy to predict that a change in spatial alignment of the oxygen octahedra or a substitution of the central ion (B-site substitution) can modify the ferroelectric behavior of the material. Change in spatial alignment of the oxygen octahedra can be also made by (so called) A-site substitution, when an A-site ion is substituted with another ion. In the case of barium titanate, it has been found that substitutions can make the temperature of paraelectric to ferroelectric transition to shift towards lower or higher values and, in some conditions, the temperature of dielectric constant maxima will be affected by the frequency of the applied field (relaxor behavior). An A-site substitution, for example substituting Ba2+ with Sr2+ or Pb2+, is responsible for shifting the temperature region in which the ferroelectric properties are present while the values of permittivity remain relatively large. This is good from the applications viewpoint because the possibility of shifting Curie temperature and the selection of the sector for the temperature dependence for dielectric constant and dielectric loss broadens the application area of these BT-based materials. The representative material in this class is (Ba1-x,Srx)TiO3 (BST), one of the most studied solid solution due to its stability and the wide range of possible applications that can use its electrical properties.
A B-site substitution is also responsible of changing the degree of ordering in the solid solution resulting in a shift of Curie temperature and the appearance of the relaxor behavior when the local ordering of B-sites will make it favorable. In this category there is no widely studied BT-based material because their properties were comparable to other ferroelectric materials such as lead zirconate titanate (PZT), pure barium titanate, lead titanate or even barium strontium titanate. However, it has been found that small amounts of BaZrO3 or BaHfO3 included in BT can make it a candidate material for pyroelectric sensor, having electrical characteristics superior of those of lead lanthanum zirconate titanate (PLZT) or BST, materials that were commonly used for such applications.
As mentioned earlier, (Ba,Sr)TiO3 (BST) solid solutions are one of the most investigated ceramic materials because the shift of ferroelectric phase transition towards lower temperatures can easily be controlled by adjusting the Ba/Sr ratio while maintaining acceptable high dielectric constants coupled with good thermal stability. Ba (Ti,Sn)O3 (BTS) solid solutions are another subclass of materials that can be used for specific application. For a given application, to achieve the desired properties in the BST or BTS system, compositional control should be considered along with the preparation method and/or deposition method in the final device structure.
From many applications that can incorporate BT-based materials, here only optimization for two applications will be discussed in detail: dielectric bolometer mode of infrared sensor and embedded multilayered capacitor structures. Since the requirements for ferroelectric materials suitable for dielectric bolometer mode of infrared sensor and embedded multilayered capacitor structures are different, a good selection of ferroelectric material and fabrication method is necessary to ensure high quality ceramic layers for these applications. As a result, BTS thin films have been fabricated using metal-organic decomposition method as a suitable process to ensure good quality films for dielectric bolometer mode of infrared sensing applications. In the case of films for embedded multilayered capacitor applications, since the target require a low temperature fabrication technique, BST thick films have been fabricated using a relatively new deposition technique called aerosol deposition method, developed at National Institute of Advanced Industrial Science and Technology by Dr. Akedo, one of the coauthors of this paper, a fabrication method that allows fabrication of thick and dense ceramic layers at room temperature.
One important characteristic for a material to be suitable for dielectric bolometer (DB) mode of infrared sensor applications is to have a large Temperature Coefficient of Dielectric constant (TCD).
From 1990, Ba(Ti1-x,Snx)O3 solid solution captured the attention of the researchers because of his stable ferroelectric properties in the vicinity of the Curie point that makes it a good candidate for specific applications. Because it belongs to a class of ferroelectric materials that show a diffuse phase transition (DPT) who have promising properties behavior that can be used for various applications such as sensors, actuators or high permittivity dielectric devices, this solid solution captured the attention of many research groups as a suitable active material. Investigation made with bulk Ba(Ti1-x,Snx)O3 samples revealed that, if BaSnO3 content is 30% or more, the solid solutions of Ba(Ti1-x,Snx)O3 have relaxor behavior (Mueller et al., 2004; Lu et al., 2004; Yasuda et al., 1996; Xiaoyong et al., 2003). Moreover, Yasuda and al. observed a deviation of the dielectric constant from the Curie-Weiss law (that is specific for relaxor ferroelectrics) even when BaSnO3 content is between 10 and 20%, but only in a narrow temperature region above Curie point, and a relaxor behavior for samples in witch the BaSnO3 content is above 20%.
More recently, some authors see in Ba(Ti1-x,Snx)O3 a candidate to replace (Ba,Sr)TiO3 in microwave applications (Lu et al., 2004; Jiwei et al., 2004). Jiwei et al. showed that, in some conditions, tunability of a metal-ferroelectric-metal (MFM) structure could be as high as 54% at an applied field of 200 kV/cm and a frequency of 1 MHz.
A more important indirect result has shown by Tsukada et al. where, from the dielectric constant versus temperature for a Ba(Ti1-x,Snx)O3 (BaSnO3 content of 15%) thin film with a thickness of 400 nm deposited by PLD on Pt/Ti/SiO2/Si, a value close to 11% at 250C can be calculated.
In the processing of the thin films, the goal is not only to reduce the cost and time in fabrication process but, more important, is to optimize the film properties for specific applications. Metal-organic decomposition process (MOD) has some advantages in comparison with other widely used deposition techniques: precise control of stoichiometry, high homogeneity, large area of deposition and simple equipment and process flow. However, one of the biggest problems implying this technique is that is not possible to fabricate crystalline thin films with epitaxial or columnar structure and that the density of the material is lower than the one obtained by other technique. High quality films can still be obtained by this process comparing with other techniques and, along with the advantages offered by MOD convinced many researchers to use it in their investigations.
Liquid solution of BTS was prepared by mixing barium isopropoxide [Ba[OCH(CH3)2]2], titanium butoxide [Ti[O(CH2)3CH3]4] tin isopropoxide [Sn[OCH(CH3)2]4] and 1-methoxy-2-propanol supplied by Toshima MGF. CO.LTD.
The Ba(Ti0.85,Sn0.15)O3 (BTS) solution was deposited on Pt(240nm)/Ti(60nm) /SiO2(600nm)/Si substrates by spin-coating at 500 rpm for 5 seconds followed by another 20 seconds at 2200 rpm. This step was performed in enriched N2 atmosphere (1-5 l/min flow) to avoid moisture, because the solution is highly hygroscopic. After spin coating, the film was moved quickly on a hot plate and dried at 250ºC for one minute followed by 10 minutes drying into an oven at the same temperature in air. After drying, the BTS films were pyrolyzed at 450ºC for 10 minutes into an oven in enriched O2 atmosphere (1 l/min
Process flow of the BTS thin films prepared by MOD
TG-DTA analysis results of the BTS MOD-solution
flow). Spin-coating / drying / pyrolyzing sequence was repeated another 4 times before annealing in enriched O2 atmosphere (1 l/min flow) for 10 minutes was performed. The BST15 thin films were annealed at 600ºC, 700ºC, 750ºC or 800ºC. The deposition and heat treatment were repeated 20 times before a final annealing was performed for 20 minutes in O2 enriched atmosphere. The schematic representation of the deposition steps is shown in Figure 2. Differential thermal analysis (DTA) and thermo-gravimetric analysis (TG) (Figure 3) were used to determine the thermal decomposition behavior of the BTS solution and to select the appropriate temperatures for drying and baking. DTA curve shows an endothermic peak at 103ºC corresponding to solvent evaporation point and two exothermic peaks at 350 and 370ºC, temperatures that correspond to precursor decomposition and formation of BTS compound. The TG curve showed that the total mass of the investigated liquid decreases rapidly at the beginning, the solution loosing almost 94% of its mass at 180ºC and slowly loosing more, reaching -97% at 380ºC. The weight loss is insignificant above 380ºC.
According to TG-DTA results, a drying temperature over 180ºC and a baking temperature over 370ºC are necessary. A drying temperature of 250ºC and baking temperature of 450ºC were selected to ensure full solvent evaporation in short time and to minimize as much as possible the stress and defects caused by a further weight reduction during annealing and a rapid complete precursor decomposition and BTS formation.
The thickness of the BTS15 films obtained by this process was about 360nm.
After BTS thin films preparation was completed, Pt/Ti electrodes were formed on the film by RF sputtering to make BTS capacitors. After completion of BTS capacitor fabrication, for films annealed at 700ºC, a post electrode-forming annealing was performed at temperature varying from 200 to 350ºC in air and at 300ºC in high vacuum for 60 minutes.
In order to obtain high quality films suitable for DB-mode of infrared sensing applications (high values of TCD), the BTS thin film properties have been studied for different fabrication conditions and the results were used to optimize the deposition conditions for improved BTS thin films. The influence of annealing temperature and postannealing treatment on physical and electrical properties of the fabricated BTS thin films was investigated aiming an increase in TCD values near room temperature. The temperature of maximum permittivity for the fabricated BTS thin films was found to be near 13ºC.
The annealing effect on the properties of the fabricated BTS thin films has been checked first in order to optimize the fabrication conditions.
XRD patterns of the BTS thin films annealed at different annealing temperatures
In Figure 4, XRD patterns of the films annealed at temperature ranging from 600ºC to 800ºC are showed. The films annealed at 600ºC are still amorphous but for films annealed at 700ºC and higher, crystal structure has been detected. The films have strong (110) peaks suggesting that the crystalline BTS films have a preferential orientation along (110) direction. The other peaks, assignable to a cubic perovskite type structure, are also present but their intensities are much smaller than the intensity of (110) peak. The preferred orientation and intensity ratios among the peaks revealed little distinct differences among these films as a function of annealing temperature. The average grain size was estimated from the half-width of the x-ray diffraction peak using Scherrer’s formula to be in the 33.3 – 50 nm range.
For films fabricated at annealing temperatures of 700, 750 and 800ºC, leakage currents, C-V and temperature dependence of capacity (and through it, the permittivity dependence) were measured and analyzed. Except the temperature dependence of capacity, the other electrical measurements were performed at room temperature, well above the temperature of maximum permittivity.
The leakage current measurements showed that the films annealed at 750ºC have a higher leakage current than films annealed at 700ºC and 800ºC (Figure 5). The reason for this behavior is still not clearly understood. Because films with small leakage currents are desired the films annealed at 750ºC cannot be considered suitable for DB-mode infrared sensing applications. For this reason the attention was focused on the films annealed at 700ºC and 800ºC.
Leakage current for BTS films annealed at different temperatures
The investigations of the temperature influence on the dielectric loss (Figure 6) revealed that the dielectric loss increases with increase in annealing temperature. Moreover, the dielectric loss for films annealed at 800ºC shows large temperature dependence compared with films annealed at 700 and 750ºC. On the other hand, the films annealed at 700ºC have the dielectric loss very little affected by the increase in the annealing temperature.
In Figure 7, temperature dependence of capacitance for films annealed at 700ºC and 800ºC has been plotted. The variation of capacitance for BTS samples annealed at 700ºC is more pronounced than for the samples annealed at 800ºC.
Reviewing the results obtained after physical and electrical properties in becomes clear that annealing at 700ºC is more suitable in obtaining BTS thin films with good properties for DB-mode of infrared sensor applications.
Dielectric loss vs. sample temperature for BTS films annealed at different temperatures
Capacitance vs. sample temperature for BTS films annealed at 7000C and 8000C
The effect of postannealing temperatures on physical and electrical properties of BTS thin films was investigated keeping in mind that the films should be suitable for DB-mode of infrared sensor. The annealing temperature has been set to 700ºC as a result of annealing temperature effect investigations performed earlier. After the top-electrode deposition, a postannealing treatment has been performed at temperatures of 200, 300 and 350ºC in air and at 300ºC, in vacuum for 60 minutes. The results of the investigations made on BTS samples are summarized in Table 1.
Postannealing effect on physical and electrical characteristics of BTS thin films. Leakage densities are given for an applied voltage of 10V
Only some electrical properties are affected by the treatment. Polarization in P-E hysteresis loops is increasing with the increase in postannealing temperature (not shown here). This can be explained considering the fact that a postannealing treatment is improving the metal-ferroelectric interface. The effect of oxygen diffusion during postannealing treatment should not be neglected while considering improvement in polarization. However, as we will show below, increase in polarization due only to improvement in film surface due to reduction in oxygen vacancies by oxygen diffusion from air cannot fully explain the tendency.
Analyzing the results summarized in Table 1 it can be seen that the current leakage of the BTS samples is the most affected by postannealing temperature being smaller for films postannealed at 200ºC. It can be observed that increase in postannealing temperature will not further improve the leakage currents of the samples. Y. Fukuda et al. (Fukuda et al., 1997) reported that, by increasing the postannealing temperature in the case of (Ba,Sr)TiO3 thin films deposited on Pt/SiO2/Si or SrTiO3 substrates, the diffusion of the oxygen from the postannealing atmosphere is decreasing. Our results suggest the same effect by increasing the postannealing temperature because the leakage current, even if it is better than that for as-deposited samples, is increasing by increasing the annealing temperature.
Figure 8 is showing the I-E1/2 characteristics of the leakage current for BTS samples postannealed at 200ºC and 350ºC along leakage current for samples that were not postannealed. The leakage behavior for samples postannealed at 300ºC is not shown to avoid overlay in the graphic because it shows almost the same behavior as samples annealed at 350ºC. It can be seen in the figure that postannealing treatment decreases Schottky leakage currents. The Schottky currents can be described by (Sze, 1981; Fukuda et al., 1998):
where
J-E1/2 characteristics of the leakage current for BTS samples, as-deposited and postannealed at 200ºC and 350ºC (Schottky currents)
In figure 8 it can be observed that the first part of the I-E1/2 characteristics can be plotted with a straight line, suggesting that the leakage is mainly due to Schottky currents. Moreover, the plotted lines seem to be almost parallel to each other. Similar result has been obtained by Fukuda while investigating the effects of postannealing in oxygen ambient on leakage properties of (Ba,Sr)TiO3 thin film capacitors (Fukuda et al., 1998). Because the plotted lines are parallel, all parameters except
Focusing the attention back to table 1, it can be seen that TCD is highest for samples postannealed at 300ºC reaching 5.6% at 25ºC. Even if the leakage behavior for samples postannealed at 300ºC and 350ºC is almost similar, we expect a difference in oxygen vacancy concentration due to different oxygen diffusion coefficients.
In order to understand how postannealing at 300ºC is improving the value of TCD, the postannealing treatment has been performed in air as well as in high vacuum conditions. In this way the effect of presence of oxygen in the postannealing atmosphere can be better understood. Physical and electrical properties (especially leakage current and TCD versus sample temperature) were again investigated but this time the attention has been focused into noticing any particular differences among samples.
Post-annealing after electrode deposition in air or vacuum was found to have little effect on the BTS XRD peaks, indicating that the crystalline structure is not changed after the post-annealing. AFM observation (not shown here) revealed a root-mean-square (RMS) roughness of 1 to 3 nm.
The chemical change induced by the postannealing in films was obtained after XPS investigations (Figure 9). The attention was focused upon the chemical shifts that were clearly visible in the samples. The peaks were carefully calibrated using the Pt peaks and viewing the carbon peaks for confirmation.
XPS spectra for BTS thin films as-deposited and postannealed at 300ºC for 1 hour in vacuum and air.
TCD vs.film temperature for BTS thin films as-deposited and postannealed at 300ºC for 1 hour in vacuum and air
The exact binding energy of an electron depends upon the formal oxidation state of the atom from which it was extracted and local chemical and physical environment. The postannealing after electrode deposition was performed in air as well in vacuum to study the influence of diffused oxygen to the chemical properties of the near-surface layer of the BTS thin films. For postannealed films in vacuum or air, the Ti peaks are shifting towards higher binding energies than Ti peaks for as-deposited films. The presence of O2 in the air can explain why the Ti peaks for the sample postannealed in air are shifting more than the Ti peaks for the sample postannealed in vacuum. Chemically speaking, the presence of O2 in postannealing atmosphere causes oxygen diffusion into the BTS thin films that will be responsible for the reduction in concentration of the oxygen vacancies near the surface, increasing the oxidation state of the Ti, causing the shift of the Ti peaks position towards higher binding energies in XPS investigations.
An important electrical measurement is the investigation of the temperature dependence of the capacitance (i.e. dielectric constant). Figure 10 shows the TCD behavior for BTS thin films as-deposited and postannealed in air and vacuum. The films post-annealed at 300ºC in air have TCD values reaching more than 5.4 %/K at 25ºC and 11 %/K at 20ºC, which is very high compared with similar reported values for TCD. The improvement in TCD values makes the BTS thin film very promising for realizing highly sensitive dielectric-bolometer mode of infrared sensor.
Because of the principle of operation, a dielectric-bolometer mode is expected to offer high sensitivity compared with other detectors (Noda et al., 1999; Balcerak, 1999; Radford et al., 1999; Noda et al., 1999). This aspect, along with other advantages offered, such as chopper free device and low operation voltages are good reasons to consider the DB-mode a good choice in fabricating an infrared sensor.
Following the results obtained for ferroelectric BTS thin films, integration into a simple infrared sensing structure will confirm that the BTS can be considered a good candidate for DB-mode of infrared sensing applications.
Picture view of the infrared sensor cell
In order to investigate what are the sensor capabilities of a structure containing BTS thin film as detecting layer, a simple structure was made, containing a simple capacitance ratio sensor that will sense any capacitance difference between detector and reference capacitors. A picture view of the fabricated structure is shown in Figure11.
Fabrication of the structure on silicon was made with the use of silicon micro machining process. The fabrication steps are shown in Figure 12. Only the detector-capacitor is constructed on a membrane, the reference capacitor will stay on SiO2/Si3N4/SiO2/Si substrate.
Process of infrared sensor fabrication
Detection circuit for infrared measurement
Schematically, an infrared sensing cell can be represented as in Figure 13. A sensing cell is composed of serially connected capacitors. This sensor cell is operating on the principle of sensing the change in the capacitance of the detector-capacitance relative to reference capacitance. Because of the construction, when the sensing cell is exposed to infrared radiation, the temperature at the ferroelectric BTS material site for the detecting capacitor is higher compared with the one for the reference capacitor. Different temperatures are responsible for different dielectric constant values at the detector and reference capacitors that translate into different capacitance values. The variation of the capacitance of the detector-capacitor relative to the value of the capacitance in reference capacitor is detected as a voltage change. Because this voltage signal is very small, amplification is required for the detection.
The infrared response evaluation system is showed schematically in Figure 14. In infrared response evaluation, the temperature of a black body radiator (600ºC to room temperature range) is used as source of infrared rays. The infrared rays were focused with germanium lens so that the radiation will fall mainly on the single element sensor. A function generator was used to apply sinusoidal waves with voltage amplitude of 3V, offset of 1.5V and frequency of 1kHz to both capacitors. An almost 180 degree reversal of the phase was used in the capacitors in order to minimize the output signal. When infrared radiation will fall on the detecting capacitor, heating will cause a change in the value of capacitance. This change will affect the “equilibrium” state in the circuit and a Vout signal will be detected. The output voltage is then amplified through the band-pass filter of 1 kHz for which lock-in amplifier was substituted and observed as an output waveform with an oscilloscope. Furthermore, using the high-speed Fourier transform (FFT) function built in the oscilloscope, the output signal is extracted.
Infrared response evaluation system
The optimization of the DB operation conditions has to be made before making any comment about the sensing properties of the ferroelectric BTS thin films. Running a set of experiments such as DB output voltage behavior at different applied voltages considering the low leakage behavior of the films at low applied voltages or DB output voltage behavior at different applied frequencies are essential in increasing device sensitivity.
Blackbody temperature dependence of DB output as a parameter of the operation amplitude of supply voltage is showed in Figure 15. For the same sensing cell structure and the same applied frequency, DB output signal is increased by increase in applied voltage amplitude.
Blackbody temperature dependence of DB output as a parameter of the applied frequency of supply voltage is shown in Figure 16.
It can be seen that the DB output level increases with decreasing the frequency of the supplied voltage. The reason for this behavior is considered to be the fact that not the entire voltage amplitude is applied to the series capacitor structure while the frequency is increased.
It can be concluded now that the optimal DB operation conditions are:
Larger amplitude of supply voltage. The amplitude should be, however, small enough to ensure small leakage currents through the BTS thin film. 3 to 5 V amplitude for the applied voltage is considered here;
Low operation frequency for the applied voltage. 10 or 100Hz is considered in this experiment.
DB output as a parameter of the operation amplitude of supply voltage
DB output as a parameter of the operation frequency of supply voltage
As a result of optimization, sensing properties of the BTS ferroelectric thin film can be investigated. The output voltage for infrared sensing cells containing BTS thin films as deposited and postannealed at 300ºC in air for 60 minutes is shown in Figure 17.
Output voltage vs. blackbody temperature for sensing cells containing BTS thin films as deposited and postannealed at 300ºC in air
Output voltage for blackbody temperatures below 100ºC for sensing cells containing BTS thin films as deposited and postannealed at 300ºC in air
The importance of postannealing can be clearly seen from this figure. Moreover, a closer look at the response while exposing to the infrared radiations emitted by the black body when its temperature was below 100ºC (Figure 18) revealed that a stable detection of infrared radiation emitted by a blackbody when its temperature was 27ºC was successfully obtained. However the output signal is less than expected because 75% of the incident radiation is reflected by the top electrode; only a maximum of 25% of incident radiation will cause the heating in the sensing cell. Voltage responsivity (Rv) and specific detectivity (D٭) were calculated to be 0.1 KV/W and 3x108 cmHz1/2W, respectively, being in the same range as thin metal oxide film bolometers.
BTS obtained by metal-organic decomposition process can be successfully used as active material in fabrication of DB-mode of infrared sensor. As demonstrated above, temperatures lower than the temperature of a human body can be successfully detected by this type of infrared sensor cell using BTS deposited by metal-organic decomposition process as active material.
The demand of miniaturization and increased functionality in electronic devices trigered the need of finding ways to increase densification of components on electronic boards and 3D packing. There is a need to improve current technologies or develop new ones in order to cope with the problems that arise with miniaturization and 3D packing. The use of high temperatures during fabrication are not desirable since can trigger unwanted chemical reactions, interdiffusion, shrinkage and/or alteration of electrical properties for the component already present on the circuit board. A relatively new deposition method called the Aerosol Deposition (AD) technique based on room temperature impact consolidation (RTIC) phenomena can be a good alternative in film formation at room temperature (Akedo & Lebedev, 1999; Akedo et al., 1999; Akedo & Lebedev, 2001; Akedo, 2004; Akedo, 2006). In this way, the problems linked with relatively high temperatures needed for film formation using the current (more popular) technologies can be avoided and embedding of dense ceramics into low temperature substrate becomes possible.
As mentioned earlier, barium strontium titanate is an extensively investigated ferroelectric material due to its good electrical properties in bulk and thin film form being a leading candidate for applications in many electronic devices. Barium strontium titanate is currently considered as an attractive material in sensing, memory, capacitor and RF and microwave applications (Kirchoefer et al., 2002; Acikel et al., 2002; Hwang et al., 1995; Zhu et al., 2004; Tissot, 2003). But many important issues, such as improving dielectric constant values, dielectric loss and leakage, still need further attention in order to improve film quality and device performance. Regarding the AD-deposited (Ba0.6,Sr0.4)TiO3 (BST) films, there are few reports regarding the film particularities. The logical ways to improve film properties are by tempering with film chemical composition, deposition conditions and post-film-formation treatments, and metallization. However, preliminary results have shown that post-film formation annealing is not helpful to improve the properties of the AD-fabricated BST films (Popovici et al., 2009). The substrate is also playing an important role in improving the AD-fabricated BST film properties since a soft substrate is suitable in ensuring that the films are less stressed (Popovici et al., 2008).
For AD process, powder condition is one of the most important factors since humidity, physical characteristics of the particle and particle aggregation are affecting the deposition rate and film properties.
Below, only the results on the investigation regarding the quality of commercially available (raw) powder used in the AD-deposition and improvement by heat treatments to allow the fabrication of (Ba0.6,Sr0.4)TiO3 (BST60) layers with higher dielectric constants will be discussed due to space constrains in writing this article.
BST60 thick films were grown by the AD technique on Cu substrates using raw and thermally treated powders. To investigate the effect of powder thermal treatment on AD-fabricated BST60 thick films properties, powder from the same lot has been thermally treated for 1 h at 800 or 900ºC in O2 atmosphere.
The AD system used in film fabrication is represented schematically in figure 19. Powder aerosols are formed by oxygen flowing in the vacuum powder chamber at a rate of 4 l/min and transported through connecting tubes to the vacuum deposition chamber where the particle are ejected through the nozzle toward a moving substrate for deposition. A schematic representation of the consolidation process by AD is shown in figure 20. During AD deposition, the particles will suffer a plastic like deformation and fracture upon impact with the substrate. This plastic like deformation and the fracture of the impacting particles are essential to ensure the formation of very dense AD films.
Schematic representation of AD system
Schematics of consolidation process by AD
Before being used in AD, the powder is optimized by ball milling to allow fabrication of high quality films at high deposition rates and with minimum consumption of powder. The average particle size after ball milling should fall within the optimum range (considered to be 0.7-1.4 μm for the BST powder). The thickness of the fabricated BST60 films was around 3 μm and their density was estimated to be in the 92-93% range from the theoretical density, being independent of the powder condition. To examine the electrical properties of the films, Pt/Ti electrodes were deposited by RF sputtering on BST60 thick films to form capacitor structures.
In BST powder synthesis, there are a number of reports that suggest that the presence of BaCO3 in BT and BST powders is difficult to prevent whatever the fabrication route is used (Henningh & Mayr, 1978; Coutures et al., 1992; Hennings & Schreinemacher, 1992; Stockenhuber et al., 1993; Lemoine et al., 1994; Ries et al.,2003). Moreover, there are reports that suggest that BT is thermodynamically unstable in H2O having a pH below 12 (Lencka & Riman, 1993; Abicht et al., 1997; Voltzke et al.,1999). The BST is expected to show a similar problem since it is a BT-based material. The most probable chemical reaction with water is shown below:
The formed solid TiO2 (amorphous) will remain in the outer shell of the initial BT (or BST) particle and will act as a barrier in the further removal of Ba by water (Voltzke et al., 1999). Upon air exposure, Ba(OH)2 will react as follows:
The instability of strontium titanate (STO) material in water is not confirmed, therefore, only, only the instability of Ba2+ ions in H2O is considered here.
Whatever the reasons for the presence of BaCO3 as a secondary phase in BST and BT powders, BaCO3 formation must be controlled to ensure the fabrication of BST or BT films with the desired properties since AD is a room temperature process and post-film-formation thermal treatments at elevated temperatures are not reccomended.
X-ray photoelectron spectroscopy (XPS) has been used to clarify the presence of the secondary phase in the powder and films and the effect of powder annealing. The powder specimens were prepared on Al plate using a commercial double-sided adhesive tape on which the powder adhered. The tape was well covered with powder to avoid the occurrence of tape-related peaks in the XPS spectra. For calibration purpose and to avoid charging due to electron photoemission, a very thin layer of Au was deposited on the surface of the samples by RF sputtering. Six elements were detected on the surface of the investigated samples: C, Au, O, Ba, Sr and Ti. The Au peaks were used to calibrate the XPS profiles.
The XPS profiles of the C 1s peaks of raw powder, the AD-fabricated film obtained from this powder, and powder recovered from the deposition chamber are shown in figure 21. The C 1s peak located near 284.8 eV is commonly attributed to C-C and C-H bonds. The C 1s peak located near 288.45 eV is assumed to be correlated with the C state in CO32- of BaCO3 (Viviani et al, 1999) since the other possible chemical states for carbon, C-O and CO2, should reveal peaks located at binding energies that are higher with approximately 2 eV (Viviani et al, 1999) and 7 eV (Wagner et al.,1979), respectively, than those of the reference C 1s peak. Comparing the relative intensities of the CO32--related C 1s peak (relative to Sr 3p3/2 peak) for the raw powder, AD-fabricated BST60 film, and powder recovered from the deposition chamber it can be concluded that the relative intensity of the carbonate phase is higher in the AD-fabricated film than in the powder.
XPS C1s peak profile for raw and annealed powders
XRD profiles of BST raw and thermally treated powders
XRD profiles of 900ºC treated powder immediately after treatment and after one year
The XRD profiles of the as-received and 800 and 900ºC thermally treated powders show that the crystallinity is retained in all films. However, a closer observation of the XRD pattern near 2theta=24º revealed the presence of an additional peak that can be assigned to the orthorhombic BaCO3 phase (figure 22). Since the concentraton of BaCO3 second phase is high enough to surpass the sensitivity limit of the X-ray diffraction system, it can be also assumed that a peak related to this phase will also appear in XPS results. On this ground, it has been assumed that the BaCO3 second phase will be responsible for the appearance of a relatively high intensity peak in the C 1s XPS peak profile of the BST60 powder, peak that should be located near 289 eV.
This is another reason for linking the peak located at 288.45 eV in C 1s XPS profile to the C state in CO32- of the BaCO3 second phase. It should be notted that for powders thermally treated at 900ºC for 1 h, peaks generated by the presence of the second carbonate phase were not observed in the XRD profile, suggesting that this temperature is suitable for the removal of the secondary phase in the BST60 powders. To further test the BST powder instability against humidity and CO2 in air some treated powder was intentionally placed in atmospheric conditions for 1 year. In figure 23, the XRD patterns near 2theta=24º are shown for freshly treated powder and powder aged in air for 1 year away from dust. The carbonate peak becomes visible again suggesting that humidity and CO2 from air were sufficient to trigger Ba2+ ion removal from BST60 powders and formation of BaCO3 in the outershell of BST particles.
The effect of powder thermal treatment on the physical and electrical properties of the AD-fabricated BST60 films was also analyzed. As shown in figure 24, the dielectric constant of AD-fabricated films using 900ºC treated powders is highest among the investigated films being close to 200 for a wide frequency range. The dielectric loss in all samples was below 0.06 and no marked changes in this parameter were observed. Since the grain size is similar in all the films, the difference in dielectric constant is not due to its dependence on grain size.
Frequency dependence of dielectric constant for AD BST thick films deposited from raw and thermally treated powders
Due to the unique way deposition of films take place in AD, the material in the outershell of the crystalline particles participating in the consolidation process will always be found to form grain boundaries in the as-deposited AD films. The increase in dielectric constant can be correlated with the improvement of the grain boundary regions since, by minimizing the ammount of the secondary phase, the low dielectric constant carbonate phase will be less present at the grain boundary. Moreover, the leakage in AD films is improved by annealing the powder at 900ºC (figure 24).
Leakage of BST films deposited from raw and 900ºC thermally treated powders
For the AD-fabricated BST60 thick films obtained from 900ºC treated powders, the leakage currents stay below 10-7 A/cm2 for applied electric fields up to 500 kV/cm. A reduction in leakage current of one or two orders of magnitude is observed for the AD-fabricated films obtained from 900ºC treated powders as compared with the films fabricated from raw powders. This is another indication that the grain boundaries of the BST60 films were modified following the thermal treatment of the powders at 900ºC prior to deposition. The removal of the secondary phase from the grain boundary regions by thermally treating the powder at 900ºC increases the resistivity of the grain boundary regions, reducing the leakage currents through the grain boundary.
Thermal treatment of commercially available BST powder at 900ºC is a good approach to increase the overall performance of the AD-fabricated BST thick films deposited at room temperature and to make them more attractive for embedded multilayer capacitor applications.
BT-based materials represent a class of materials with a wide range of applications. Here, we showed how substitution in A or B site can make these materials suitable for different applications. Two examples of how BT-based materials can show potential in specific applications are discussed.
Ba(Ti0.85,Sn0.15) (BTS) ferroelectric thin films have been prepared by metal-organic decomposition (MOD) technique. Annealing and postannealing temperatures were optimized to obtain films with suitable electrical properties for application in DB-mode of infrared sensing. Annealing at 700ºC has as the result the minimization of the leakage current and the dielectric loss. Also, the capacitance of a capacitor containing BTS thin film crystallized at this temperature will decrease more rapidly with an increase in film temperature than on a similar capacitor made with BTS thin films annealed at 800ºC. Considering the results, annealing at 700ºCis suitable to fabricate with good properties for application to DB-mode of infrared sensing. Applying a postannealing treatment to the capacitors after top-electrode deposition can improve further the electrical properties of the BTS thin films. It has been found that, postannealing at 300ºC in air for 60 minutes, even if the leakage is higher than in the case of postannealing at 200ºC, will increase the value of the temperature coefficient of dielectric constant (TCD) from 1 %/K to 5.6 %/K at 25ºC comparing with only 1.3 %/K for films postannealed at 200ºC. A closer look on the leakage current behavior on BTS films postannealed in air reveals that an increase in postannealing temperature will reduce the oxygen diffusion from the air into the films that translates as higher leakage currents for samples postannealed at temperatures higher than 200ºC than on the samples postannealed at 200ºC. However these values are still smaller than that of as-deposited BTS thin films. TCD values are higher for samples postannealed at 300ºC suggesting that some degree of oxygen deficiency in the film is needed in order to obtain satisfactory values for TCD. A close investigation regarding the importance of postannealing at 300ºC revealed the important role played by the oxygen vacancies to the value of TCD. Postannealing in air-free environment will not do much improvement to the electrical properties of the film except a relatively small increase in polarization observed in P-E hysteresis loops. On the other hand, postannealing in air will promote oxygen diffusion into the film and, as a result, a change in electrical properties of the dead-layer and a change in the lattice parameters of the crystalline BTS thin films. It can be observed that postannealing at 300ºC for 60 minutes is an important condition in order to fabricate BTS thin films suitable for DB-mode of infrared sensing. The results obtained after BTS film investigations were used in the fabrication of a simple-structures infrared sensing cell. The cell consist in a series of two capacitors, one used as reference capacitor and the other, fabricated on a membrane to reduce the thermal loss, used as detector-capacitor.After optimization of the BD operation mode (application of sinusoidal waves with a voltage amplitude of 3 to 5V and a frequency between 10Hz and 100Hz) sensing properties of the films were revealed. A stable infrared detection was possible even for objects (in this case a black body) heated at temperatures of 27ºC. Good figures-of-merit such as voltage responsivity (Rv) of 0.1 KV/W and specific detectivity (D٭) of 3x108 cmHz1/2W were also calculated making BTS material a strong candidate for application in DB-mode of infrared sensing.
(Ba0.6,Sr0.4)TiO3 (BST60) thick films were fabricated on Cu substrates by Aerosol Deposition (AD) method. The quality of the raw powder has been checked and optimized in order to increase the dielectric constant of the fabricated films without the need of post-film-formation annealing procedure. Carbonate phase has been observed in the raw powders and it was successfully reduced by thermally treating the powder at 900ºC. The AD-fabricated films obtained from the 900ºC treated powder show a dielectric constant of 200 being much higher that the dielectric constant of the AD-films obtained from the as-received powders. The leakage currents in the films fabricated from 900ºC treated powders stay below 10-7 A/cm2 when the applied electric filed is less than 500 kV/cm and it is at least one order of magnitude smaller than for films obtained from as-received powders. The above results indicate that thermally treating the powder at 900ºC is a good way to improve the AD-fabricated BST60 thick films electrical properties. This results represent a step forward in our goal of ceramic fabrication at room temperature aiming integration into embedded multilayered ceramic capacitor structures in electronic devices.
The first author acknowledge the support of Japanese Government Scholarship (Monbukagakusho) program in making possible his research and study at Osaka University.This research has also been partially supported by the NEDO project on “The next generation MEMS (Fine MEMS) project” in Japan.
The sense of beauty, its development and improvement, depends on many factors. Modern human society is trying to make people’s lives more beautiful, comfortable, and technological. The artificial beauty created by some people is presented in various forms and offered for understanding and acceptance by other people. There is the sphere in which a person is invited to understand the beauty and somehow transform this understanding into the environment of his life, in choosing those forms of beauty that will bring him the greatest joy and well-being. A modern person needs to develop a sense of beauty in himself. Professional activity often requires ingenuity which is connected with the sense of beauty also. The influence of the sense of beauty on ingenuity, on the ability to create beautiful things with one’s intellect, is undeniable. Therefore, let us try to understand what factors determine the development of a sense of natural and artificial beauty and what can become the basis for a harmonious transition from the perception of the beautiful to the creation of the beautiful. Readers are invited to become familiar with the analysis of such human properties as contemplation and observation. The relationship of the factors that create a transition from the process of perception of the beautiful to the creative principle and ingenuity is also considered.
When I hear the word beauty I ask myself—what is it? Is this a certain feeling or is it a way of thinking or is it an algorithm for perceiving phenomena? Does beauty make a person move along a creative path? Are all people equally able to perceive different beauties? Does the sense of beauty affect the development of human ingenuity in the technical field? We will try to consider these issues in this chapter.
When we raise our heads to the sky and see how a plane gracefully flies at a high altitude, it seems to us beautiful, majestic, and ingenious, especially from the point of view of what we can create with the human’s mind and hands.
It happened in my life that I was lucky enough to be born and grew up in a very beautiful place. The nature was connected to mountains, valleys, the sea, and good and beautiful people. From my birth I have been surrounded by natural beauty and harmony of human life. This fact predetermined all my further perceptions of life and movement along it, as well as my attitude to beauty.
I became a technical specialist after graduation, and at a certain point of my life, my feelings of natural beauty and creativity began to combine inside me, including in the field of technical ingenuity.
There are many different opinions and scientific approaches to developing a person’s ability to be creative and to invent.
Creativity as the ingenuity is given to any of us, but many lose it as adults. Further development of these abilities depends mainly on the atmosphere in which the person was raised. I think that nature has the primacy role in this environment. It is the natural harmony of power and energy that determine for a child the very sense of beauty that will accompany him throughout his life. This feeling will also allow a person the ability to create something beautiful, regardless of what people do in a professional sphere.
It is very important to observe the diversity of natural wealth in childhood such as mountain topography, sunset and sunrise, the elements of rain and thunderstorms, sea storms and calm, and so on. Observing such phenomena, the child learns to feel and analyze, which is an essential necessity for the further development of inventiveness [1]. Natural playscapes offer sensory stimulation and physical diversity which is critical for childhood experiences [2].
It is in natural phenomena that the foundations of human behavior and abilities are developed, and in childhood a feeling of enthusiasm is formed. However, at this age, this feeling is still specific, not completely formed, and differs from the enthusiasm of adults, who, as we know can be admired in different ways. For example, a 3-year-old child is more likely to enjoy some toy than a beautiful sunset. This happens because in childhood, the brain of the child still accumulates information and pictures of the world in order, to build subsequently on this basis, its own unique algorithm of perception and behavior in the world around it. Therefore, those pictures of the world that a child observed in the first 5–7 years of his life determine the development of human abilities, the level of his susceptibility. That is why we observe such a variety of degrees and levels of perception, the ability to see and create beauty around ourselves in adulthood among different people and nations [3, 4].
The level of the perfection and development of our life has reached today is interrelated from nature. People continue to learn from nature. We copy natural phenomena, creations, and even in such a form as “ourselves.” Natural beauty is in everything—these are colors and shapes; these are sequences of changing seasons, weather phenomena; these are life cycles; and so on. Thanks to the vision of this beauty, the human’s brain is transformed through the process of observation, discovery, and development of new areas of science [5].
Technical devices that people created have allowed us to see a grandiose beauty that has been hidden until recently from humanity in the depths of space—the beauty of the universe and its breath [6]. So how wonderful it is that the perception of beauty on our own planet has expanded the scope of thinking and expanded the possibilities of seeing extraterrestrial beauty.
The study of human nature and world is associated with sequences and algorithms. From primitive actions to the highest complexity of engineering structures, a person in his thinking and behavior is based on algorithms and therefore on sequences. This ability has made it possible to create mathematics, physics, and other sciences that have become the basis of our prosperity. In all developmental processes, there is the beauty of discoveries, research, definitions, and relationships.
The development of a person’s ingenuity is invariably associated with his observation, and the process of developing ingenuity can be presented as the following scheme:
Beauty → Contemplation → Observation → Creativity
From generation to generation, people pass on to each other knowledge, as perhaps the most precious legacy. The stratification of observations in different epochs during the existence of humanity has allowed us today to create very complex technical systems that surround us everywhere and give us a certain degree of freedom. Remember how many millennia people have watched the flight of birds, dreaming to rise in the sky and fly as well. Today, an airplane flying overhead seems to us to be the norm. However, in order to understand how to take off the earth and fly, humanity had to observe, observe, and observe.
How does the desire for observation appear? By the author’s opinion, the natural beauty creates and develops in us this gift and ability to see the essence of beauty, since natural beauty was the first and natural call for a person to embark on a developmental path. When we meet natural phenomena or new places on our way where we are going, we sometimes cannot take our eyes off the beauty we see, and we want to look at it repeatedly. People do not get tired of natural beauty. Therefore, observation can be defined as the ability to learn from the beauties of nature.
In some discussions about the character of a person, his nature, one can trace the opinion that contemplation is a negative property. In some dictionaries, contemplative person is defined as a passive observer. Has someone ever considered how contemplation and beauty are connected? After all, if you analyze what a person is looking at more, then this is something beautiful, especially at a young age. So what is wrong with a person enjoying vision of beauty? Could it be the other way around? Those people who spend their life energy and time searching for something vital and do not have time to see the beauty of the world around them, their own beauty—maybe these people lose much more than contemplators do.
Of course, it is not impossible to be a one-sided person in the modern world, but a reasonable balance between the ability to contemplate and the ability to succeed in a profession can give a person more joy in life.
Creativity, as a way of self-expression of a person, is a companion for human society probably from the moment when people realized themselves. Nature has shown people the algorithms for the development of creativity. For example, there are algorithms of movements, algorithms of temperature and shape changes, algorithms of fire appearance, and so on. However, how could one know these algorithms without contemplation and observation? If we consider that contemplation is the ability to see for a long time and observation is the ability to see deeply, then these two properties become absolutely necessary for the development of inventiveness, as a process of manifestation of the abilities to create.
The invention of the wheel, which allowed humanity to race along the path of technological progress, was probably interrelated in nature from observations of how stones or logs roll, and natural fires made it possible for people to feel the heat and the benefits of using it on an ongoing basis.
Observations of nature gave a person an understanding of how to use forms in mathematics, architecture and engineering [7], and various colors in almost all areas of production and life. The beauty of natural sounds is transformed by a man in musical instruments. Finally, we observe the endless desire of engineers to create beautiful designs.
At the beginning of engineering, ingenuity lies in functionality, but soon engineers also focused on the appearance of their creations. Of course, it often happens that the beauty of structures is determined immediately during their design, but in the long term, the substantial part of the appearance always strives for new beauties, those that can only be born in the human’s mind.
So why do not all people perceive the same phenomena equally and adults do not always associate beauty with the possibility of its subsequent transformation into ingenuity or creativity? Perhaps the reason lies in the ability to perceive beauty as a system of values.
If we look at what objects and natural phenomena surround us, then they will seem beautiful to us. Almost everyone agrees that we like beautiful landscapes, buildings, cars, ships, clothes, dishes, meal, paintings, music, and graceful movement. We love flowers, fruits of plants, natural stones, and in general, everything that can cause a feeling of delight. However, not everyone knows how to admire.
A person of a creative warehouse is able to see and hear beauty in almost everything as a rule. Persons, who do not have creativity, need additional environmental factors and perceptions of the world to delight them. Therefore, such people subconsciously strive to approach creative people to adopt the ability to admire from them [8]. In these cases, an additional responsibility lies with creative people—not to reject those who do not know how to create and be inventive and not to blame them for this but rather try to involve and teach them how to see true beauty, to be beautiful and enjoy beauty in life.
For many years, while working with students, I have observed how their worldview changes when they meet not only inventive teachers but also inventive students. The exchange of technical and cultural knowledge and skills during learning is the second stage in the formation of the ability to move from ingenuity to the perception of beauty, after the childhood period of life. It was during this period that the algorithms finally formed and what can make it possible to create something new on their basis.
When I was at school, my physics teacher read his poems to us in the classroom. Sometimes I wondered why he was doing this. However, when I began teaching students, I realized that many people could understand things that are difficult only if they have a broad outlook. Moreover, the expansion of our horizons is influenced by everything that carries a beautiful content—the sounds of music, poetry, travel, nature with its phenomena and riddles, the process of cognition, the discovery of oneself, and the creation of new ideas and objects with your brain. In addition, all this is interconnected.
It is not in vain, when something pleases us, especially something new, we enthusiastically pronounce the word “beauty”! But beauty requires thought [9].
The life of humanity is developing in such a way that more and more technical objects begin to surround us. Especially in modern big cities, people actually live in an industrial environment. On the one hand, this fact is a direct result of human ingenuity, and on the other hand, in recent decades, we are increasingly beginning to see beauty through a technical lens of perception.
A transformation occurs—the perception of beauty affects ingenuity, and vice versa, ingenuity affects the perception of beauty. Sometimes this transformation proceeds in a dangerous direction, for example, the creation of computer technology more and more involves people in a virtual way of perceiving beauty. The time has come to find balance.
The last century has shown how structural elements in technology affect the development and the life of all humanity. Many technical objects were invented over the entire twentieth century and the beginning of the current century. After the creation of internal combustion engines, people began to gladly produce on an industrial scale and use these devices to solve economic and other problems. However, when a certain level of development was achieved, humanity began to realize the danger that these devices carry in for the environment. So today, humanity is looking for ways to abandon internal combustion engines or, in any case, minimize their use. At the beginning of the twenty-first century with similar enthusiasm, computer technology was received. Seeing in these devices a new stage in the possibility of accelerating industrial and economic growth, we began to use them as extensively as internal combustion engines.
Calculations and organizational capabilities of computer technology, no doubt, allow you to create countless possible models, conduct research and analysis, and develop new programs. However, I like to ask—does the human brain need as much information as can be obtained by computer technology? Alternatively, being energized by computer technology, is our brain capable of harmoniously functioning, fulfilling its natural purpose?
Saturating our brain with a lot of information, there is a danger for people to lose the natural gift to see beauty [10]. Where is the border that technology impairs our ability to perceive and replicate natural beauty? In the author’s opinion, computer technology with its extensive capabilities must first study and determine the possibility of a person losing the perception of natural harmony and beauty. Creating a virtual world around him and becoming more and more immersed in it, a person ceases to hear the birdsong and to notice the momentary subtleties of natural phenomena. This narrows his natural visual vision and finally stifles his creativity. A study at the University of Kansas found that young people who backpacked for 3 days showed higher creativity and cognitive abilities [11].
There is a saying that “beauty will save our world.” I would add from myself that natural beauty might save the world.
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The Corresponding Author (acting on behalf of all Authors) and INTECHOPEN LIMITED, incorporated and registered in England and Wales with company number 11086078 and a registered office at 5 Princes Gate Court, London, United Kingdom, SW7 2QJ conclude the following Agreement regarding the publication of a Book Chapter:
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\n\n2.1 Subject to the following Article, the Corresponding Author grants and shall ensure that each Co-Author grants, to IntechOpen, during the full term of copyright and any extensions or renewals of that term the following:
\n\nThe aforementioned licenses shall survive the expiry or termination of this Agreement for any reason.
\n\n2.2 The Corresponding Author (on their own behalf and on behalf of any Co-Author) reserves the following rights to the Chapter but agrees not to exercise them in such a way as to adversely affect IntechOpen's ability to utilize the full benefit of this Publication Agreement: (i) reprographic rights worldwide, other than those which subsist in the typographical arrangement of the Chapter as published by IntechOpen; and (ii) public lending rights arising under the Public Lending Right Act 1979, as amended from time to time, and any similar rights arising in any part of the world.
\n\nThe Corresponding Author confirms that they (and any Co-Author) are and will remain a member of any applicable licensing and collecting society and any successor to that body responsible for administering royalties for the reprographic reproduction of copyright works.
\n\nSubject to the license granted above, copyright in the Chapter and all versions of it created during IntechOpen's editing process (including the published version) is retained by the Corresponding Author and any Co-Author.
\n\nSubject to the license granted above, the Corresponding Author and any Co-Author retains patent, trademark and other intellectual property rights to the Chapter.
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\n\n2.4 The Corresponding Author (on their own behalf and on behalf of each Co-Author) will not assert any rights under the Copyright, Designs and Patents Act 1988 to object to derogatory treatment of the Chapter as a consequence of IntechOpen's changes to the Chapter arising from translation of it, corrections and edits for house style, removal of problematic material and other reasonable edits.
\n\n3. CORRESPONDING AUTHOR'S DUTIES
\n\n3.1 When distributing or re-publishing the Chapter, the Corresponding Author agrees to credit the Book in which the Chapter has been published as the source of first publication, as well as IntechOpen. The Corresponding Author warrants that each Co-Author will also credit the Book in which the Chapter has been published as the source of first publication, as well as IntechOpen, when they are distributing or re-publishing the Chapter.
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\n\nThe Corresponding Author will be held responsible for the payment of the Open Access Publishing Fees.
\n\nAll payments shall be due 30 days from the date of the issued invoice. The Corresponding Author or the payer on the Corresponding Author's and Co-Authors' behalf will bear all banking and similar charges incurred.
\n\n3.3 The Corresponding Author shall obtain in writing all consents necessary for the reproduction of any material in which a third-party right exists, including quotations, photographs and illustrations, in all editions of the Chapter worldwide for the full term of the above licenses, and shall provide to IntechOpen upon request the original copies of such consents for inspection (at IntechOpen's option) or photocopies of such consents.
\n\nThe Corresponding Author shall obtain written informed consent for publication from people who might recognize themselves or be identified by others (e.g. from case reports or photographs).
\n\n3.4 The Corresponding Author and any Co-Author shall respect confidentiality rights during and after the termination of this Agreement. The information contained in all correspondence and documents as part of the publishing activity between IntechOpen and the Corresponding Author and any Co-Author are confidential and are intended only for the recipient. The contents may not be disclosed publicly and are not intended for unauthorized use or distribution. Any use, disclosure, copying, or distribution is prohibited and may be unlawful.
\n\n4. CORRESPONDING AUTHOR'S WARRANTY
\n\n4.1 The Corresponding Author represents and warrants that the Chapter does not and will not breach any applicable law or the rights of any third party and, specifically, that the Chapter contains no matter that is defamatory or that infringes any literary or proprietary rights, intellectual property rights, or any rights of privacy. The Corresponding Author warrants and represents that: (i) the Chapter is the original work of themselves and any Co-Author and is not copied wholly or substantially from any other work or material or any other source; (ii) the Chapter has not been formally published in any other peer-reviewed journal or in a book or edited collection, and is not under consideration for any such publication; (iii) they themselves and any Co-Author are qualifying persons under section 154 of the Copyright, Designs and Patents Act 1988; (iv) they themselves and any Co-Author have not assigned and will not during the term of this Publication Agreement purport to assign any of the rights granted to IntechOpen under this Publication Agreement; and (v) the rights granted by this Publication Agreement are free from any security interest, option, mortgage, charge or lien.
\n\nThe Corresponding Author also warrants and represents that: (i) they have the full power to enter into this Publication Agreement on their own behalf and on behalf of each Co-Author; and (ii) they have the necessary rights and/or title in and to the Chapter to grant IntechOpen, on behalf of themselves and any Co-Author, the rights and licenses expressed to be granted in this Publication Agreement. If the Chapter was prepared jointly by the Corresponding Author and any Co-Author, the Corresponding Author warrants and represents that: (i) each Co-Author agrees to the submission, license and publication of the Chapter on the terms of this Publication Agreement; and (ii) they have the authority to enter into this Publication Agreement on behalf of and bind each Co-Author. The Corresponding Author shall: (i) ensure each Co-Author complies with all relevant provisions of this Publication Agreement, including those relating to confidentiality, performance and standards, as if a party to this Publication Agreement; and (ii) remain primarily liable for all acts and/or omissions of each such Co-Author.
\n\nThe Corresponding Author agrees to indemnify and hold IntechOpen harmless against all liabilities, costs, expenses, damages and losses and all reasonable legal costs and expenses suffered or incurred by IntechOpen arising out of or in connection with any breach of the aforementioned representations and warranties. This indemnity shall not cover IntechOpen to the extent that a claim under it results from IntechOpen's negligence or willful misconduct.
\n\n4.2 Nothing in this Publication Agreement shall have the effect of excluding or limiting any liability for death or personal injury caused by negligence or any other liability that cannot be excluded or limited by applicable law.
\n\n5. TERMINATION
\n\n5.1 IntechOpen has a right to terminate this Publication Agreement for quality, program, technical or other reasons with immediate effect, including without limitation (i) if the Corresponding Author or any Co-Author commits a material breach of this Publication Agreement; (ii) if the Corresponding Author or any Co-Author (being an individual) is the subject of a bankruptcy petition, application or order; or (iii) if the Corresponding Author or any Co-Author (being a company) commences negotiations with all or any class of its creditors with a view to rescheduling any of its debts, or makes a proposal for or enters into any compromise or arrangement with any of its creditors.
\n\nIn case of termination, IntechOpen will notify the Corresponding Author, in writing, of the decision.
\n\n6. INTECHOPEN’S DUTIES AND RIGHTS
\n\n6.1 Unless prevented from doing so by events outside its reasonable control, IntechOpen, in its discretion, agrees to publish the Chapter attributing it to the Corresponding Author and any Co-Author.
\n\n6.2 IntechOpen has the right to use the Corresponding Author’s and any Co-Author’s names and likeness in connection with scientific dissemination, retrieval, archiving, web hosting and promotion and marketing of the Chapter and has the right to contact the Corresponding Author and any Co-Author until the Chapter is publicly available on any platform owned and/or operated by IntechOpen.
\n\n6.3 IntechOpen is granted the authority to enforce the rights from this Publication Agreement, on behalf of the Corresponding Author and any Co-Author, against third parties (for example in cases of plagiarism or copyright infringements). In respect of any such infringement or suspected infringement of the copyright in the Chapter, IntechOpen shall have absolute discretion in addressing any such infringement which is likely to affect IntechOpen's rights under this Publication Agreement, including issuing and conducting proceedings against the suspected infringer.
\n\n7. MISCELLANEOUS
\n\n7.1 Further Assurance: The Corresponding Author shall and will ensure that any relevant third party (including any Co-Author) shall, execute and deliver whatever further documents or deeds and perform such acts as IntechOpen reasonably requires from time to time for the purpose of giving IntechOpen the full benefit of the provisions of this Publication Agreement.
\n\n7.2 Third Party Rights: A person who is not a party to this Publication Agreement may not enforce any of its provisions under the Contracts (Rights of Third Parties) Act 1999.
\n\n7.3 Entire Agreement: This Publication Agreement constitutes the entire agreement between the parties in relation to its subject matter. It replaces and extinguishes all prior agreements, draft agreements, arrangements, collateral warranties, collateral contracts, statements, assurances, representations and undertakings of any nature made by or on behalf of the parties, whether oral or written, in relation to that subject matter. Each party acknowledges that in entering into this Publication Agreement it has not relied upon any oral or written statements, collateral or other warranties, assurances, representations or undertakings which were made by or on behalf of the other party in relation to the subject matter of this Publication Agreement at any time before its signature (together "Pre-Contractual Statements"), other than those which are set out in this Publication Agreement. Each party hereby waives all rights and remedies which might otherwise be available to it in relation to such Pre-Contractual Statements. Nothing in this clause shall exclude or restrict the liability of either party arising out of its pre-contract fraudulent misrepresentation or fraudulent concealment.
\n\n7.4 Waiver: No failure or delay by a party to exercise any right or remedy provided under this Publication Agreement or by law shall constitute a waiver of that or any other right or remedy, nor shall it preclude or restrict the further exercise of that or any other right or remedy. No single or partial exercise of such right or remedy shall preclude or restrict the further exercise of that or any other right or remedy.
\n\n7.5 Variation: No variation of this Publication Agreement shall be effective unless it is in writing and signed by the parties (or their duly authorized representatives).
\n\n7.6 Severance: If any provision or part-provision of this Publication Agreement is or becomes invalid, illegal or unenforceable, it shall be deemed modified to the minimum extent necessary to make it valid, legal and enforceable. If such modification is not possible, the relevant provision or part-provision shall be deemed deleted.
\n\nAny modification to or deletion of a provision or part-provision under this clause shall not affect the validity and enforceability of the rest of this Publication Agreement.
\n\n7.7 No partnership: Nothing in this Publication Agreement is intended to, or shall be deemed to, establish or create any partnership or joint venture or the relationship of principal and agent or employer and employee between IntechOpen and the Corresponding Author or any Co-Author, nor authorize any party to make or enter into any commitments for or on behalf of any other party.
\n\n7.8 Governing law: This Publication Agreement and any dispute or claim (including non-contractual disputes or claims) arising out of or in connection with it or its subject matter or formation shall be governed by and construed in accordance with the law of England and Wales. The parties submit to the exclusive jurisdiction of the English courts to settle any dispute or claim arising out of or in connection with this Publication Agreement (including any non-contractual disputes or claims).
\n\nLast updated: 2020-11-27
\n\n\n\n
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