METHOD FOR THE PREPARATION OF A LEAD-FREE PIEZOELECTRIC MATERIAL AND PRECURSOR SOLUTION

Abstract

The present disclosure relates to a method for the preparation of a precursor solution for a ceramic of the BZT-aBXT type wherein X is selected from Ca, Sn, Mn and Nb and a is a molar fraction selected in the range between 0.10 and 0.90 comprising the steps of: a) dissolving at least one barium precursor compound and at least one precursor compound selected from the group consisting of a calcium precursor compound, a tin precursor compound, a manganese precursor compound and a niobium precursor compound in a linear or branched anhydrous alkyl alcohol containing from 2 to 6 carbon atoms and, after dissolution, dehydrating by stripping, to obtain a first solution; b) dissolving at least one zirconium precursor compound and at least one titanium precursor compound in a linear or branched anhydrous alkyl alcohol containing from 2 to 6 carbon atoms in the presence of an anhydrous chelating agent to obtain a second solution; c) joining said first and second solutions in an anhydrous environment and dehydrating by stripping to obtain said precursor solution. It also relates to a precursor solution, to a method for the preparation of a film of a piezoelectric material, to a piezoelectric material and to an electronic device comprising this piezoelectric material.

Claims

1. A method, comprising: preparing a precursor solution for a ceramic of a BZT-αBXT type wherein X is selected from Ca, Sn, Mn and Nb and a is a molar fraction selected in the range between 0.10 and 0.90 comprising: obtaining a first solution by dissolving at least one barium precursor compound and at least one precursor compound selected from the group consisting of a calcium precursor compound, a tin precursor compound, a manganese precursor compound and a niobium precursor compound in a linear or branched anhydrous alkyl alcohol containing from 2 to 6 carbon atoms and, after dissolution, dehydrating by stripping; obtaining a second solution by dissolving at least one zirconium precursor compound and at least one titanium precursor compound in a linear or branched anhydrous alkyl alcohol containing from 2 to 6 carbon atoms in the presence of an anhydrous chelating agent; joining said first and said second solutions in an anhydrous environment and dehydrating by stripping.

2. The method according to claim 1 wherein obtaining a second solution includes the presence of at least one niobium or tungsten precursor compound.

3. The method according to claim 1 wherein said precursor of calcium, barium, tin, manganese, niobium, zirconium, titanium and tungsten are selected from the group consisting of metal alkoxides, their partial hydrolysates and metal carboxylates, metal-diol complexes, metal-thiol complexes, metal carb oxylates, metal-3-diketonate complexes, metal-3-diketoester complexes, metal-3-iminoketo complexes, metal-amine complexes.

4. The method according to claim 1 wherein said barium precursor compound is barium acetate.

5. The method according to claim 1 wherein said calcium precursor compound is calcium acetate.

6. The method according to claim 1 wherein said titanium precursor compound is selected from the group consisting of titanium tetraethoxide, titanium tetraisopropoxide, titanium tetra-n-butoxide, titanium tetraisobutoxide, titanium tetra-t-butoxide, and titanium dimethoxy diisopropoxide.

7. The method according to claim 1 wherein said zirconium precursor compound is selected from the group consisting of zirconium n-propoxide, zirconium tetraethoxide, zirconium tetraisopropoxide, zirconium tetra-n-butoxide, zirconium tetraisobutoxide, zirconium tetra-t-butoxide, and zirconium dimethoxy diisopropoxide.

8. The method according to claim 1 wherein said niobium precursor compound is selected from the group consisting of niobium alkoxides.

9. The method according to claim 1 wherein said tungsten precursor compound is selected from the group consisting of tungsten alkoxides.

10. The method according to claim 1 wherein said chelating agent is selected from the group consisting of glacial acetic acid and anhydrous ethylene glycol.

11. The method according to claim 1 wherein obtaining the first solution and joining the first and second solutions are carried out in a rotary evaporator.

12. A precursor solution for a ceramic of the BZT-αBXT type wherein X is selected from Ca, Sn, Mn and Nb and a is a molar fraction selected in the range between 0.10 and 0.90 obtained with the method according to claim 1.

13. A method, comprising: preparing a film of piezoelectric material made of a ceramic of the BZT-αBXT type wherein X is selected from Ca, Sn, Mn and Nb and a is a molar fraction selected in the range between 0.10 and 0.90 comprising a step of depositing on a substrate a precursor solution according to claim 12, a calcining step and a sintering step.

14. A piezoelectric material made of a ceramic of the BZT-αBXT type wherein X is selected from Ca, Sn, Mn and Nb and a is a molar fraction selected in the range between 0.10 and 0.90 obtained from a precursor solution of claim 12.

15. The piezoelectric material according to claim 14, in the form of a film or powder.

16. An electronic device comprising an active region configured to deform under the action of an external quantity or of a polarization electrical quantity, comprising a layer of piezoelectric material according to claim 14.

Description

BRIEF DESCRIPTION OF THE SEVERAL VIEWS OF THE DRAWINGS

[0031] The present disclosure will now be described in detail with reference to the annexed drawings, wherein:

[0032] FIG. 1 illustrates the unit of the cell of an ideal cubic perovskite of the ABO.sub.3 type;

[0033] FIG. 2 illustrates the tetragonal ferroelectric distortion of the perovskite structure in the two polarization states;

[0034] FIG. 3 illustrates the piezoelectric properties d.sub.33 of piezoelectric materials in MPB composition;

[0035] FIG. 4 shows a block diagram of an electronic apparatus including a device having a piezoelectric region;

[0036] FIGS. 5A and 5B are respectively a top view and a cross-section view of an operating region of the device of FIG. 4, according to an embodiment;

[0037] FIGS. 6A and 6B are respectively a top view and a cross-section view of an operating region of the device of FIG. 4, according to a different embodiment;

[0038] FIG. 7A illustrates the diffraction pattern of the powders dried at 120° C. of the solution prepared according to standard methods present in the literature and FIG. 7B illustrates the diffraction pattern of the powders dried at 120° C. of the solution prepared according to the present disclosure;

[0039] FIG. 8 illustrates the thermogravimetric analysis for a solution prepared by the method of the present disclosure;

[0040] FIG. 9 illustrates a typical ferroelectric hysteresis curve (P-E) wherein the Residual Polarization is indicated with Pr and the coercive field with Ec;

[0041] FIG. 10A illustrates the P-E curves measured at a frequency of 5 kHz for a device according to FIGS. 6A, 6B and FIG. 10B illustrates the P-E curves measured at a frequency of 5 kHZ for a device according to FIGS. 5A, 5B;

[0042] FIG. 11 illustrates the comparison between the curves of capacitance as the frequency varies measured for a device according to FIGS. 5A, 5B and according to FIGS. 6A, 6B;

[0043] FIG. 12 illustrates the comparison between the diffraction spectra of the BNZT-BCNT and BZT-BCT tablets;

[0044] FIG. 13 is a cross-section of a test structure for the evaluation of the electrical characteristics of BNZT-BCNT and BZT-BCT tablets; and

[0045] FIG. 14 illustrates the comparison of the ferroelectric curves measured at the frequency of 1 kHz for a BNZT-BCNT and BZT-BCT disc.

DETAILED DESCRIPTION

[0046] According to the present description, a method is provided for the preparation of a precursor solution for a ceramic of the BZT-αBXT type wherein X is selected from Ca, Sn, Mn and Nb and α is a molar fraction selected in the range between 0.10 and 0.90 comprising the steps of: [0047] a) dissolving at least one barium precursor compound and at least one precursor compound selected from the group consisting of a calcium precursor compound, a tin precursor compound, a manganese precursor compound and a niobium precursor compound in a linear or branched anhydrous alkyl alcohol containing from 2 to 6 carbon atoms and, after dissolution, dehydrating by stripping, to obtain a first solution; [0048] b) dissolving at least one zirconium precursor compound and at least one titanium precursor compound in a linear or branched anhydrous alkyl alcohol containing from 2 to 6 carbon atoms in the presence of an anhydrous chelating agent to obtain a second solution; [0049] c) joining said first and said second solutions in an anhydrous environment and dehydrating by stripping to obtain said precursor solution.

[0050] By the term “precursor solution” is understood a mixture containing all the necessary components used to form a BZT-BXT ceramic following a suitable treatment.

[0051] Advantageously, the method described above allows the preparation of a substantially water-free and homogeneous precursor solution. The precursor solution obtained with the described method allows the crystallization temperature to be reduced and a dense and well crystallized thin film to be obtained with a consequent improvement of its electrical properties in terms of resistance, dielectric and ferroelectric properties both in planar and vertical configuration.

[0052] In particular, step a) and step c) are carried out in a rotary evaporator.

[0053] In one embodiment, step b) is further carried out in the presence of at least one niobium or tungsten precursor compound.

[0054] The addition of niobium or tungsten in the preparation of the precursor solution allows to obtain doped BZT-BCT ceramics that have higher piezoelectric coefficients, dielectric losses and dielectric constants in the face of a reduction in the coercive field.

Metal Compounds

[0055] In the present text, by “barium precursor compound,” “calcium precursor compound,” “tin precursor compound,” “manganese precursor compound,” “niobium precursor compound,” “zirconium precursor compound,” “titanium precursor compound” and “tungsten precursor compound” are understood compounds wherein an organic group is bonded, respectively, to the metal element Ba, Ca, Sn, Mn, Nb, and Zr, Ti and W through an oxygen or nitrogen atom of the organic group. The choice of the metal precursors determines the nature of the cations of the sites A and B of the perovskite structure.

[0056] In particular, the precursor compounds of Ca, Ba, Zr, Ti, Sn, Nb, Mn and W may be chosen in the group consisting of metal alkoxides, metal-diol complexes, metal-thiol complexes, metal carboxylates, metal-3-diketonate complexes, metal-3-diketoester complexes, metal-3-iminoketo complexes, metal-amine complexes, more in particular, metal alkoxides, their partial hydrolysates and metal carboxylates.

[0057] Examples of a precursor compound of Ca include acetates, such as calcium acetate (Ca(OAc).sub.2).

[0058] Examples of a precursor compound of Ba include acetates, such as barium acetate (Ba(OAc).sub.2).

[0059] Examples of a precursor compound of Ti comprise alkoxides, such as titanium tetraethoxide (Ti(OEt).sub.4), titanium tetraisopropoxide (Ti(OiPr).sub.4), titanium tetra-n-butoxide (Ti(OnBu).sub.4), titanium tetraisobutoxide (Ti(OiBu).sub.4), titanium tetra-t-butoxide (Ti(OtBu).sub.4), or titanium dimethoxy diisopropoxide (Ti(OMe).sub.2(OiPr).sub.2), more in particular titanium tetrabutoxide and titanium isopropoxide.

[0060] Examples of precursor compounds of Zr are zirconium n-propoxide, zirconium tetraethoxide (Zr(OEt).sub.4), zirconium tetraisopropoxide (Zr(OiPr).sub.4), zirconium tetra-n-butoxide (Zr(OnBu).sub.4), zirconium tetraisobutoxide (Zr(OiBu).sub.4), zirconium tetra-t-butoxide (Zr(OtBu).sub.4), or zirconium dimethoxy diisopropoxide (Zr(OMe).sub.2(OiPr).sub.2), more in particular zirconium n-propoxide. Examples of a precursor compound of Mn include manganese acetate.

[0061] Furthermore, examples of precursor compounds of Nb include niobium alkoxides, in particular niobium pentaethoxide.

[0062] Examples of precursor compounds of W include tungsten alkoxides, in particular tungsten pentaethoxide and 1,2-dimethoxyethane tungsten ethoxide.

[0063] Among the precursor compounds of Ti and Zr particularly indicated are the alkoxides that are favored on account of their high reactivity and capacity of forming the desired phases at low reaction temperatures, whereas among the compounds of Ba and Ca carboxylates are favored.

Solvent

[0064] The choice of the solvent is linked to the desire to identify a means in which the compounds of Ba, Ca, Sn, Mn, Nb, Zr, Ti and W are mutually compatible, but above all to obtain a clear and stable sol solution.

[0065] It has been found that the presence of residual water deriving from hydration of the metal compounds, from environmental humidity, or from residue in the solvents leads to precipitation of the gel in the sol solution, thus determining the instability of the same. Furthermore, the presence of both hygroscopic and structural water substantially reduces the homogeneity of the precursor solution.

[0066] It is therefore desired to remove the presence of residual water during the preparation of the gel solution.

[0067] This result is achieved due to the use of anhydrous solvents and the dehydration of organic salts.

[0068] It has been observed that the use of a linear or branched anhydrous alkyl alcohol containing from 2 to 6 carbon atoms, preferably selected from the group consisting of ethanol, 1-butanol, 1-propanol, 2-propanol, 2-butanol, isobutyl alcohol, 1-pentanol, 2-pentanol and 2-methyl-2-pentanol, allows sol solutions to be obtained that remain clear and stable over time.

Chelating Agent

[0069] To stabilize the metal compounds upon decomposition, in particular the titanium and zirconium compounds, chelating agents are to be used.

[0070] The chelating agents act both by physically surrounding the cation in solution (steric hindrance) and by binding directly thereto in order to reduce its chemical reactivity (inductive effect).

[0071] Examples of anhydrous chelating agents are acetylacetone (2,2-pentanedione, or AcAc), glacial acetic acid (HAc), glycerol, propylene glycol, anhydrous ethylene glycol, diethanolamine, EDTA (ethylenediaminetetraacetic acid), triethanolamine, preferably glacial acetic acid and anhydrous ethylene glycol.

[0072] Acetic acid (HAc) may be used for reducing the reactivity of titanium alkoxides. Gelling and precipitation in sols containing titanium alkoxides may be suppressed with the addition of moderate amounts of acetic acid.

[0073] According to the present disclosure, a precursor solution is also provided for a ceramic of the BZT-αBXT type, where X is selected from Ca, Sn, Mn, and Nb, and a is a molar fraction selected in the range between 0.10 and 0.90 obtained according to the method described above.

[0074] Furthermore, according to the present disclosure, a piezoelectric material is made of a ceramic of the BZT-αBXT type where X is selected from Ca, Sn, Mn, and Nb, and a is a molar fraction selected in the range between 0.10 and 0.90 obtained from the precursor solution obtained with the method described above. This material is preferable in the form of film or powder.

[0075] This material may be used instead of conventional PZTs, for example in applications such as sensors for airbags, fuel piezo-injectors, ignition sources for gas lighters, detonation sensors, angle sensors for motor vehicles, hard disks, ink-jet print heads, touch sensors for PC monitors, atomization sources for humidifiers and inhalers, smoke detectors, devices for cleaning jewelry and contact lenses, accelerometers, pollution detectors, flow meters, detectors of air bubbles in tubes, impact sensors, level indicators, micropositioning equipment, pressure sensors, non-destructive ultrasound cleaning devices, ultrasound degreasers, ultrasound grinders, welders, ultrasound apparatuses, dental appliances, nebulizers, ultrasound therapy, sonars, orientation systems, optical and acoustic microphones, speakers, tweeters, resonators, filters, microactuators for scanning electron microscopes and cameras, non-volatile memories.

[0076] FIG. 4 schematically shows an electronic apparatus 1 which uses a device 2 including an operating region 6 including the piezoelectric material discussed above.

[0077] The electronic apparatus 1 comprises, in addition to the device 2, a signal conditioning circuit 3, for example an ASIC (“Application Specific Integrated Circuit”) connected to the device 2; a processing unit 4, for example a microprocessor, connected to the ASIC 5; a memory 5, connected to the processing unit 4; a battery 8 for supplying the various blocks of the electronic apparatus 1; and an input/output interface 9, which is also connected to the processing unit 4.

[0078] The device 2 may be a MEMS sensor; in this case the operating region 6 is a sensitive region including a layer consisting of the piezoelectric material discussed above. The sensitive region may be suspended, for example formed by a membrane or may be clamped (so-called “clamped” region); in both cases, the sensitive region 6 is configured to deform upon detection of an external physical quantity.

[0079] The ASIC 3 is electrically coupled to the device 2 so as to receive the electrical sensing signals generated by the latter and supply processed signals to the processing unit 4. The processing unit 4 receives the processed signals and supplies to the outside world the values of the detected physical quantities and/or information correlated thereto.

[0080] Alternatively, the device 2 may be a MEMS actuator, instead of a MEMS sensor. In this case, the operating region 6 forms an actuation region and the device 2 is connected to a driving unit (again indicated with 3). The driving unit 3 generates electrical signals for driving the device 2 on the basis of command signals received by the processing unit 4, to suitably polarize the operating region 6 and cause the actuation deformation thereof, in a per se known manner.

[0081] In both cases, the operating region 6 may have electrodes arranged in a planar or vertical manner.

[0082] For example, in FIGS. 5A and 5B an operating region 6 having electrodes with planar structure is shown.

[0083] In detail, the operating region 6 of FIGS. 5A and 5B has a support 10; a piezoelectric region 11 and electrodes 12.

[0084] The support 10 is here formed by a stack of layers of silicon/silicon oxide/titanium oxide/platinum (Si/SiO.sub.2/TiO.sub.2/Pt). The support 10 has a thickness linked to the intended application, for example equal to 100 nm; the silicon layer may be in contact with the piezoelectric region 11 and the platinum layer may be arranged facing outwards, to allow the electrical connection, if desired.

[0085] The piezoelectric region 10 is formed by a layer of ceramic of the BZT-αBXT type, where X is selected from Ca, Sn, Mn and Nb and a is a molar fraction selected in the range between 0.10 and 0.90 obtained from the precursor solution obtained with the method described above. The piezoelectric region 10 may have a thickness linked to the specific application and comprised between 100 nm and 10 um, for example of 500 nm.

[0086] The electrodes 12 are made for example of platinum (Pt) and are used for the polarization of the piezoelectric region 10, that is the detection of electrical signals. The electrodes 12 may have a thickness of, for example, 100 nm; they may have a rectangular shape, as visible in the top view of FIG. 5A, with a short side of 1.1 mm and a long side of 2 mm; and they may be arranged at a distance linked to the application, for example of 100 μm.

[0087] FIGS. 6A and 6B show an operating region 6 having electrodes with a vertical structure. In detail, the operating region 6 of FIGS. 5A and 5B also comprises a support 10; a piezoelectric region 11 and at least one top electrode 12; the support 10, the piezoelectric region 11 and the at least one top electrode 12′ are made of the same materials as the structures of the same name described above for FIGS. 5a, 5B.

[0088] In FIG. 6B, the platinum layer (indicated with 15), which is a bottom electrode, has been represented dashed in the support 10; FIG. 6A shows two top electrodes 12′. The at least one top electrode 12′ may have a square shape in top view, with a side of, for example, 0.5 mm; however, the number, arrangement and spacing of the top electrodes 12′ may vary according to the application and design considerations.

[0089] The operating region 6 is then polarized by applying a suitable voltage to the electrodes 12′, 15, that is the electrodes 12′, 15 are used for detecting electrical signals indicative of the strains and deformations of the piezoelectric region 11.

[0090] According to the present disclosure, there is also provided a method for the preparation of a film of a piezoelectric material made of a ceramic of the BZT-αBXT type, where X is selected from Ca, Sn, Mn, and Nb, and a is a molar fraction selected in the range between 0.10 and 0.90, comprising a step of depositing on a substrate the precursor solution described above, a calcining step, and a sintering step.

[0091] In particular, the precursor solution may be applied by spin-coating on a suitable substrate, for example a silicon substrate coated with platinum. Next, the solution is calcined and sintered (annealing) at high temperatures in the presence of oxygen to obtain a homogeneous crystalline film.

[0092] In particular, the calcining step may be conducted at a temperature comprised between 300° C. and 450° C., and the sintering step at a temperature of 550-730° C. This allows thin films to be obtained that are dense and without cracks. This cycle of deposition, calcining, and sintering may be repeated a number of times to obtain films of different thicknesses stacked on one another.

[0093] Possibly, prior to the calcining step, a drying step may be carried out to remove the solvent, in particular at a temperature comprised between 100° C. and 200° C.

[0094] Where it is instead necessary to obtain a piezoelectric material in the form of powder, the precursor solution is first calcined at a temperature comprised between 300° C. and 450° C., and subsequently sintered at a temperature of 700-1200° C.

[0095] Further characteristics will emerge from the ensuing description of some merely illustrative and non-limiting examples.

Example 1

BZT-BCT—Preparation and Characterization

[0096] The salts of barium and calcium, barium acetate and calcium acetate monohydrate are dissolved in 50 ml of butanol in a 1-liter glass flask connected to a rotary evaporator by setting an oil bath temperature of 85° C. for about 1 h. Then the oil bath temperature is raised to 125° C. to completely dehydrate the salts.

[0097] At the same time, in a nitrogen atmosphere the titanium butoxide and zirconium butoxide with suitable stoichiometric concentrations are stabilized: in detail, the titanium butoxide is dissolved in 10 ml of acetic acid and stirred and after 15 minutes the zirconium butoxide is also added and about 1 h is awaited for the complete stabilization.

[0098] Once the alkoxides have been stabilized, 50 ml of anhydrous butanol and 10 ml of glacial acetic acid are added. This solution is added to the dehydrated salts in the evaporator with 10 ml of anhydrous ethylene glycol, inside the flask to dissolve the dehydrated salts. The volume of any lost solvent is added to achieve the desired molarity. A precursor solution is thus obtained.

[0099] The powder obtained by drying the precursor solution prepared by a rotary evaporator is amorphous compared to the powder obtained with the precursor solution prepared with the standard procedure reported in IT 102015000078953.

[0100] FIGS. 7A and 7B respectively show the diffraction pattern of the powders dried at 120° C. of the solution prepared according to the method illustrated in IT 102015000078953 (7A), and the diffraction pattern of the powders dried at 120° C. of the solution prepared according to the present disclosure (7B).

[0101] FIG. 7A highlights a wealth of peaks due to the presence of multiple crystalline structures: from the comparison with the crystallographic databases, the structures of barium acetate and hydrated calcium acetate may be identified.

[0102] FIG. 7B highlights how the represented pattern is more amorphous than the previous one; however, minor peaks remain due to the presence of barium acetate.

[0103] The thermal behaviors of the powders of the precursor solution were analyzed by differential thermal analysis (DTA) and differential thermogravimetric analysis (DTG) in nitrogen. The temperature was acquired from an environmental temperature of 1200° C. at a heating rate of 10° C./min.

[0104] The TGA-DTG curve (FIG. 8) reveals the main thermal events related to the mass variation for a sample of dried powders from a solution prepared by the present disclosure as a function of the temperature, due to evaporation of the residual solvent, pyrolysis of the organic material and decomposition of the carbonates with simultaneous crystallization of BZT-BCT.

[0105] The ferroelectric properties of a thin film made with the method described above, both in planar and vertical configuration (FIGS. 5A-5B and 6A-6B), were observed with an Aixact TFA2000 by measuring the polarization as a function of the electric field curve.

[0106] The results are reported in Table 1.

TABLE-US-00002 TABLE 1 Freq. ΔEc ΔPr Tested device [kHz] [kV/cm] [uC/cm.sup.2] Vertical 5 20.6  0.5 Planar 5 1.2 1650    Vertical 1 43.0  1.2 Planar 1 5   2553   

[0107] FIG. 9 shows a typical ferroelectric hysteresis curve (P-E) wherein the points corresponding to the Residual Polarization are indicated with Pr and —Pr and those corresponding to the coercive field with Ec and −Ec.

[0108] The values of ΔPr and ΔEc reported in Table 1 were obtained from the measured experimental ferroelectric curves.

[0109] FIGS. 10A and 10B show the ferroelectric curves measured at the frequency of 5 kHz for a vertical device and for a planar device, respectively.

[0110] Comparison with the Precursor Solutions of IT 102015000078953 Due to the formation of cracks, it was not possible to test the materials of the prior art (IT 102015000078953) with electric fields greater than 600 kV/cm. On the contrary, the thin films obtained according to what has been described above were tested at electric field values up to 1 MV/cm without any alterations being detectable.

[0111] The performance of the film is also stable and reproducible over several test cycles.

[0112] The impedance curves as a function of frequency for both planar and vertical devices generated with the Keysight B1500A multifrequency module have allowed to estimate also the capacitance values as a function of frequency and to observe that, at a fixed frequency value, εr has very different values in planar and vertical duts (FIGS. 10A, 10B). In particular, in vertical devices, εr decreases from 44 at 1 kHz to 39 at about 400 kHz. In planar devices, εr decreases from 1200 at 1 kHZ to 1024 at 1 MHz.

Example 2

BNZT-BCNT—Preparation and Characterization

[0113] The salts of barium and calcium, barium acetate and calcium acetate monohydrate, are dissolved in 50 ml of butanol in a 1-liter glass flask connected to a rotary evaporator by setting an oil bath temperature of 85° C. for about 1 h. Then the oil bath temperature is raised to 125° C. to completely dehydrate the salts.

[0114] At the same time, in a nitrogen atmosphere the titanium butoxide, zirconium butoxide and niobium ethoxide with suitable stoichiometric concentrations are stabilized: in detail, the titanium butoxide is dissolved in 10 ml of acetic acid and stirred and after 15 minutes the zirconium butoxide is also added and after other 10 minutes the niobium ethoxide is also added. About 1 h is awaited for the complete stabilization.

[0115] Once the alkoxides have been stabilized, 50 ml of anhydrous butanol and 10 ml of glacial acetic acid are added. This solution is added to the dehydrated salts in the evaporator with 10 ml of anhydrous ethylene glycol, inside the flask to dissolve the dehydrated salts. The volume of any lost solvent is added to achieve the desired molarity. A precursor solution is thus obtained.

[0116] The precursor solution is suitably dried at 120° C. in order to obtain an amorphous gel which is calcined in a muffle at 600° C. for 5 min to remove the organic fraction. Subsequently, the powder thus obtained is homogenized in a mortar and pressed. The obtained tablet is sintered at 130° C. to obtain a dense BNZT-BCNT tablet. The comparison between the diffraction spectra of the BNZT-BCNT and BZT-BCT tablets obtained under the aforesaid conditions is reported in FIG. 12.

[0117] It may be noted that both samples have a pure perovskite crystalline phase without the presence of secondary phases. This indicates that the Nb.sup.5+ is incorporated in the crystalline phase replacing the Ti.sup.4+ given the similar ionic radius.

[0118] In order to measure the properties of the BNZT-BCNT (Nb doped BZT-BCT), a test structure 20 was prepared, shown in FIG. 13.

[0119] In detail, the test structure 20 has a vertical configuration and comprises a tablet 21 of BNZT-BCNT, that is disc-shaped, prepared as described above, and electrodes 22 of Ag, having circular shape (electrodes in Ag/AgCl solution, annealed at 600° C. for 30′).

[0120] The tablet 21 of BNZT-BCNT was tested by connecting it to a test equipment by two coaxial cables 23; similar measurements were carried out for a BZT-BCT tablet.

[0121] Their performances were evaluated by measuring the ferroelectric properties (TFA2000 Aixact), measuring the polarization curve as a function of the electric field, and by measuring the dielectric properties (B1500A Keysight), measuring the capacitance.

[0122] The results of the characterizations carried out have been reported in Tables 2 and 3.

TABLE-US-00003 TABLE 2 Freq. ΔEc ΔPr Tested device [kHz] [kV/cm] [uC/cm2] BZT-BCT tablet 1  510 0.0028 BNZT-BCNT tablet 1 1550 0.0340

[0123] The values of ΔPr and ΔEc reported in Table 2 were obtained from the measured experimental ferroelectric curves.

[0124] FIG. 14 shows the ferroelectric curves measured at the frequency of 1 kHz for the two discs described.

[0125] As apparent in the comparison between the curves, with the same device, the film containing Nb in the vertical configuration described has better ferroelectric characteristics. Furthermore, by measuring the dielectric constant of both tablets, it was observed that, as expected, the Nb doping also contributes to the improvement of the dielectric properties with the dielectric constant measured at 1 kHz which switches from a value of 507 for the sole BZT-BCT to 1958 for the BNZT-BCNT disc containing the Nb.

TABLE-US-00004 TABLE 3 Freq. Tested device [kHz] ε BZT-BCT disc 1  507 BNZT-BCNT disc 1 1958

[0126] Table 3 shows that, with the same configuration, the BNZT-BCNT tablet in the vertical configuration described has an increase in dielectric constant ε due to the denser structure of the Nb-doped tablet.

[0127] The addition of Nb as a dopant to the BZT-BCT lead-free material prepared with the described sol-gel method allows to obtain denser and better crystallized thin films, with better stability and better ferroelectric and dielectric performances.

[0128] This material may therefore be used in all industrial processes used for the manufacturing of piezoelectric actuation or detection MEMS devices.

[0129] A method for the preparation of a precursor solution for a ceramic of the BZT-αBXT type wherein X is selected from Ca, Sn, Mn and Nb and a is a molar fraction selected in the range between 0.10 and 0.90 may be summarized as including the steps of a) dissolving at least one barium precursor compound and at least one precursor compound selected from the group consisting of a calcium precursor compound, a tin precursor compound, a manganese precursor compound and a niobium precursor compound in a linear or branched anhydrous alkyl alcohol containing from 2 to 6 carbon atoms and, after dissolution, dehydrating by stripping, to obtain a first solution; b) dissolving at least one zirconium precursor compound and at least one titanium precursor compound in a linear or branched anhydrous alkyl alcohol containing from 2 to 6 carbon atoms in the presence of an anhydrous chelating agent to obtain a second solution; c) joining said first and said second solutions in an anhydrous environment and dehydrating by stripping to obtain said precursor solution.

[0130] Said step b) may be further carried out in the presence of at least one niobium or tungsten precursor compound.

[0131] Said precursor of calcium, barium, tin, manganese, niobium, zirconium, titanium and tungsten may be selected from the group consisting of metal alkoxides, their partial hydrolysates and metal carboxylates, metal-diol complexes, metal-thiol complexes, metal carboxylates, metal-3-diketonate complexes, metal-3-diketoester complexes, metal-3-iminoketo complexes, metal-amine complexes.

[0132] Said barium precursor compound may be barium acetate.

[0133] Said calcium precursor compound may be calcium acetate.

[0134] Said titanium precursor compound may be selected from the group consisting of titanium tetraethoxide, titanium tetraisopropoxide, titanium tetra-n-butoxide, titanium tetraisobutoxide, titanium tetra-t-butoxide, and titanium dimethoxy diisopropoxide.

[0135] Said zirconium precursor compound may be selected from the group consisting of zirconium n-propoxide, zirconium tetraethoxide, zirconium tetraisopropoxide, zirconium tetra-n-butoxide, zirconium tetraisobutoxide, zirconium tetra-t-butoxide, and zirconium dimethoxy diisopropoxide.

[0136] Said niobium precursor compound may be selected from the group consisting of niobium alkoxides.

[0137] Said tungsten precursor compound may be selected from the group consisting of tungsten alkoxides.

[0138] Said chelating agent may be selected from the group consisting of glacial acetic acid and anhydrous ethylene glycol.

[0139] Said steps a) and c) may be carried out in a rotary evaporator.

[0140] A precursor solution for a ceramic of the BZT-αBXT type wherein X may be selected from Ca, Sn, Mn and Nb and a may be a molar fraction selected in the range between 0.10 and 0.90 obtained with the method.

[0141] A method for the preparation of a film of piezoelectric material made of a ceramic of the BZT-αBXT type wherein X may be selected from Ca, Sn, Mn and Nb and a is a molar fraction selected in the range between 0.10 and 0.90 may include a step of depositing on a substrate a precursor solution, a calcining step and a sintering step.

[0142] A piezoelectric material made of a ceramic of the BZT-αBXT type wherein X may be selected from Ca, Sn, Mn and Nb and a may be a molar fraction selected in the range between 0.10 and 0.90 obtained from a precursor solution.

[0143] The piezoelectric material may be in the form of a film or powder.

[0144] An electronic device may include an active region configured to deform under the action of an external quantity or of a polarization electrical quantity, may include a layer of piezoelectric material.

[0145] The various embodiments described above can be combined to provide further embodiments. Aspects of the embodiments can be modified, if necessary to employ concepts of the various patents, applications and publications to provide yet further embodiments.

[0146] These and other changes can be made to the embodiments in light of the above-detailed description. In general, in the following claims, the terms used should not be construed to limit the claims to the specific embodiments disclosed in the specification and the claims, but should be construed to include all possible embodiments along with the full scope of equivalents to which such claims are entitled. Accordingly, the claims are not limited by the disclosure.