Glass actuator element and method for manufacturing the same

Abstract

To improve electrical-mechanical energy conversion performance of a glass actuator element.SOLUTION: A method for manufacturing a glass actuator element is provided that includes a glass layer having an opposing surface and an electrode layer provided on each of the opposing surfaces of the glass layer. The glass layer is a phosphate-based glass containing at least one metal selected from Ag, Cu, and K, and / or a clad layer is provided that is made of a dielectric material having a thickness of less than 10 μm between the glass layer and the electrode layer. It is possible to perform electric-displacement conversion.SELECTED DRAWING: Figure 1

Description

[Technical Field]

[0001] The present disclosure relates to glass actuator elements and methods for manufacturing the same. [Background technology]

[0002] In recent years, advances in the robotics industry and MEMS (Micro Electro Mechanical Systems) have led to the development of a variety of actuators for a variety of applications as electromechanical energy conversion elements. Polymer actuators work by causing ions to migrate and segregate within the polymer when a voltage is applied, resulting in a volume change that causes the polymer layer to bend (Patent Documents 1 and 2). However, polymer actuators have drawbacks in terms of their use at high temperatures, rigidity, and transparency. Furthermore, piezoelectric ceramic actuators have drawbacks such as a low electromechanical energy conversion rate and lack of transparency.

[0003] In order to solve these problems, the present inventors have proposed a glass actuator element having a glass laminate structure of an ion-conductive core glass layer and a clad glass layer covering it, in which stress is induced by ion conduction and space charge polarization induced in the core glass layer when a voltage is applied, thereby causing deformation and displacement of the glass laminate structure in response to an electric signal (voltage) (Patent Document 3). However, this glass actuator element is composed of a core glass layer and a clad glass layer having a predetermined thickness in order to ensure the heat resistance and strength of the element, and further improvement in terms of electromechanical energy conversion performance is desired. [Prior art documents] [Patent documents]

[0004] [Patent Document 1] Japanese Patent Application Laid-Open No. 2011-045221 [Patent Document 2] Japanese Patent Application Laid-Open No. 2006-204099 [Patent Document 3] Patent No. 6937597 Summary of the Invention [Problem to be solved by the invention]

[0005] It is an object of the present disclosure for the present inventors to improve the electro-mechanical energy conversion performance of glass actuator elements and to provide a method for manufacturing such glass actuator elements. [Means for solving the problem]

[0006] To achieve the above objectives, the present disclosure provides the following: (Aspect 1) The glass substrate includes glass layers having opposing surfaces, and electrode layers provided on each of the opposing surfaces of the glass layers, The glass layer is a phosphate-based glass containing at least one metal selected from Ag, Cu, and K, and / or a clad layer made of a dielectric material and having a thickness of less than 10 μm is provided between the glass layer and the electrode layer, Capable of electro-mechanical energy conversion, A glass actuator element characterized by: (Aspect 2) 2. The glass actuator element according to embodiment 1, wherein the phosphate-based glass contains 30 mol % or more of P2O5. (Aspect 3) The glass actuator element according to aspect 1, wherein the phosphate-based glass contains Ag2O in an amount of 5 mol % or more, preferably 10 mol % or more, and more preferably 20 mol % or more. (Aspect 4) The glass actuator element according to aspect 1, wherein the phosphate-based glass contains at least one oxide selected from the group consisting of MoO3, WO3, TeO2, and B2O3, in addition to one or more of Ag2O, CuxO, and K2O and P2O5. (Aspect 5) A glass actuator element according to any one of aspects 1 to 4, wherein the glass layer has a Young's modulus of 65 GPa or less and / or a Poisson's ratio of 0.27 or more. (Aspect 6) 2. The glass actuator element of embodiment 1, wherein the glass layer is transparent. (Embodiment 7) The glass actuator element according to embodiment 1, wherein the dielectric of the cladding layer is made of a crystalline or amorphous inorganic material. (Aspect 8) 2. The glass actuator element according to aspect 1, wherein the dielectric of the cladding layer is selected from TiO2, BaTiO3, SrTiO2, Al2O3, MgO, ZrO2, MgAl2O4, RNbO3 (R=Li, Na or K or a combination thereof). (Aspect 9) The glass actuator element according to any one of embodiments 1 to 4 and 6 to 8, wherein the cladding layer has a higher dielectric constant than the glass layer. (Aspect 10) The glass actuator element according to any one of embodiments 1 to 4 and 6 to 8, wherein the cladding layer has a thickness of less than 1 μm. (Aspect 11) The glass actuator element according to any one of embodiments 1 to 4 and 6 to 8, wherein the cladding layer is an electrical insulator. (Aspect 12) providing glass layers having opposing surfaces; forming an electrode layer on each of opposing surfaces of the glass layer; The glass layer is formed from a phosphate-based glass containing at least one metal selected from Ag, Cu, and K, and / or a clad layer made of a dielectric material is formed between the glass layer and the electrode layer by a vapor deposition method; Producing a glass actuator element capable of electromechanical energy conversion; A method for manufacturing a glass actuator element, comprising: (Aspect 13) 13. The method of claim 12, wherein the cladding layer has a thickness of less than 10 μm, preferably less than 1 μm. (Aspect 14) 14. The method of claim 12 or 13, wherein the cladding layer is an electrical insulator. [Effects of the Invention]

[0007] According to the glass actuator element of the present disclosure, the electromechanical energy conversion performance of the glass actuator element can be improved by using a phosphate-based glass containing at least one metal selected from Ag, Cu, and K as the glass layer and / or by using a cladding layer made of a dielectric material with a thickness of less than 10 μm. Furthermore, by forming the cladding layer by a thin film deposition method, the thickness of the cladding layer can be reduced and the adhesion between the cladding layer and the glass layer can be improved. According to a preferred embodiment of the present disclosure, a transparent glass layer can be provided. [Brief explanation of the drawings]

[0008] [Figure 1] FIG. 1 is a schematic longitudinal cross-sectional view showing an example of the structure of an actuator element according to the present disclosure. [Figure 2] FIG. 2 shows an example of the glass manufacturing process. [Figure 3] FIG. 3 is a diagram illustrating a method for processing a glass layer in Example 4. In FIG. [Figure 4] Figure 4 is a photograph showing the appearance of the fiber glass before processing in Example 4 (top image), the appearance of the rectangular glass rod obtained by processing the fiber glass (middle image), and the cross section of the glass rod (bottom image). [Figure 5] Figures 5(a)-(d) show how the ultrasonic pulse method is used to measure the propagating waves in order to measure Young's modulus and Poisson's ratio. [Figure 6] Figures 6(a)-(c) show how the density of a sample is measured using an ultrapycnometer. [Figure 7] FIG. 7 is a graph showing the relative dielectric constants of the samples measured in Example 5. [Figure 8]Figure 8(a) is a photograph showing glasses with compositions of 40Ag2O-10WO3-10MoO3-(40-x)TeO2-xP2O5 (mol%) where x = 0, 4, 8, 16, and 40. Figure 8(b) is a photograph showing glasses with compositions of 40Ag2O-yMoO3-(10-y)WO3-40P2O5 (mol%) where y = 0, 3.3, 6.7, 10, 13.3, 16.7, and 20. [Figure 9] FIG. 9 is a graph showing the light transmittance of the sample measured in Example 7. [Figure 10] FIG. 10 shows an example of a facing target sputtering apparatus. [Figure 11] FIG. 11 shows the deposition conditions of the cladding layer in Example 8 and the thickness of the obtained cladding layer. [Figure 12] FIG. 12 shows a chart of the XPS spectrum of Ti2p obtained by analyzing the cladding layer in Example 8. [Figure 13] FIG. 13 shows a chart of a thin film XRD spectrum obtained by analyzing the cladding layer in Example 8. [Figure 14] FIG. 14 is a diagram illustrating the sample for which the Young's modulus was measured in Example 5. [Figure 15] 15(a) and (b) are diagrams illustrating the measurement of Young's modulus of glass in Example 5. [Figure 16] Figures 16(a) and (b) show how vibration of the actuator element in response to an AC electric field is measured in Example 10. Figure 16(c) is a chart showing the frequency dependence of the measured amplitude. [Figure 17] 17(a) and (b) are diagrams showing the frequency dependence of vibration measured in Example 10. [Figure 18] FIG. 18 is a diagram showing the frequency dependence of the amplitude measured in Example 10. [Figure 19] 19(a) and 19(b) are diagrams showing vibration shapes measured in Example 10. [Figure 20] FIG. 20 is a diagram showing the voltage dependence of the amplitude measured in Example 10. [Figure 21-1] FIG. 21-1(a) shows a plan view of the cantilever indicating the measurement position for Experiment 1 of Example 10, and FIG. 21-1(b) shows the displacement velocity versus the frequency of the applied AC electric field. [Figure 21-2] FIG. 21-2(c) shows the displacement velocity (Velocity) versus the observed frequency, and FIG. 21-2(d) plots the relationship between the applied AC electric field frequency and the observed frequency when the displacement velocity (Velocity) peaks. [Figure 21-3] FIG. 21-3(e) shows a plot of the amplitude at the measurement position for various applied AC field frequencies. [Figure 22] Figures 22(a)-(d) relate to Experiment 2 of Example 10. Figure 22(a) is a schematic plan view showing the measurement position of the cantilever. Figure 22(b) shows the measured displacement velocity. Figure 22(c) is a schematic plan view showing the measurement position of the cantilever. Figure 22(d) shows the amplitude of the cantilever due to the electric field and impact. [Figure 23] Figure 23(a) shows the amplitude of the cantilever tip plotted against the observed frequency obtained in Experiment 3 of Example 10. Figure 23(b) shows the displacement velocity against the observed frequency at low AC electric field frequencies obtained in Experiment 3 of Example 10. DETAILED DESCRIPTION OF THE INVENTION

[0009] The present disclosure will now be described in detail and with reference to figures, but the present disclosure is not limited to these descriptions and figures.

[0010] [First aspect: actuator element] In a first aspect, the present disclosure provides a method for manufacturing a semiconductor device comprising: (A) a glass layer having opposing surfaces and an electrode layer provided on each of the opposing surfaces of the glass layer; (B) the glass layer is a phosphate-based glass containing at least one metal selected from Ag, Cu, and K, and / or (C) a clad layer made of a dielectric material having a thickness of less than 10 μm is provided between the glass layer and the electrode layer, (D) Capable of electromechanical energy conversion; The present invention provides a glass actuator element characterized by the above-mentioned.

[0011] The glass actuator element according to a first aspect of the present disclosure comprises a glass layer, an electrode layer, and an optional cladding layer (Requirement A), and is capable of electro-mechanical energy conversion (Requirement D). Patent Document 3 discloses a glass actuator element in which a silicate-based glass or a Na-containing phosphate-based glass is used as the core glass (the examples use silicate-based glass), and a laminated glass structure is disclosed in which the core glass is laminated with a cladding glass having a thickness of 10 μm or more (the examples use a core glass thickness of 439 μm, and a cladding glass thickness of 361 μm or 477 μm). In contrast, the glass actuator element according to the present disclosure can improve its electro-mechanical energy conversion efficiency by using a phosphate-based glass containing at least one metal selected from Ag, Cu, and K as the glass of the element body (Requirement B), and / or by having a cladding layer made of a dielectric material having a thickness of less than 10 μm (Requirement C).

[0012] <Electromechanical energy conversion; Requirement D> The glass actuator element according to the first aspect of the present disclosure is an element that performs electro-mechanical energy conversion using glass. Electro-mechanical energy conversion using glass in the present disclosure refers to converting electrical energy into mechanical energy by applying an electric field to the glass to deform or displace the glass, and converting mechanical energy into electrical energy by deforming or displacing the glass to change the electric field, and is also referred to as the electrostrictive effect. Hereinafter, for simplicity, electro-mechanical energy conversion will also be referred to as the electrostrictive effect.

[0013] The electromechanical energy conversion in the glass actuator element according to the first aspect of the present disclosure, i.e., the electrostrictive effect, is an effect in which application of an electric field to glass causes macroscopic or microscopic charge polarization in the glass, which in turn causes deformation or displacement in the glass, or vice versa.

[0014] In one embodiment, an ion-conductive glass is used as the glass layer. When a DC electric field is applied, cations such as silver ions migrate to the negative electrode side of the glass layer and accumulate near the boundary with the clad layer (ion segregation). On the other hand, the silver ions decrease on the positive electrode side, causing vacancies to accumulate. As a result, the volume of the side where the silver ions have accumulated expands, and the volume of the side where the vacancies have accumulated contracts. This stress causes the glass layer to typically distort and displace (deform). Furthermore, when the glass layer is deformed or displaced, cations in particular migrate in response to the deformation or displacement, causing changes in the space charge polarization formed by the applied electric field, resulting in a change in the electric field. This change in the electric field can also be sensed. This electrostrictive effect can be referred to as a DC electrostrictive effect.

[0015] In another embodiment, when an AC electric field is applied to a glass, preferably an ion-conductive glass, displacement and movement occur between the atoms constituting the glass according to their electronegativity and electropositivity, generating local charge polarization. However, the direction of the local charge polarization also reverses in response to AC changes in the direction of the electric field, causing atoms (ions) to approach or recede in response to the AC electric field, causing the glass to repeatedly expand and contract. As a result, the glass experiences macroscopic mechanical strain (expansion and contraction), deforming and displacing. This electrostrictive effect can be called an AC electrostrictive effect.

[0016] The electromechanical energy conversion (electrostrictive effect) in the glass actuator element of the present disclosure includes both the electrostrictive effect caused by direct current and the electrostrictive effect caused by alternating current. Patent Document 3 discloses the electrostrictive effect caused by direct current using ion conductive glass, but according to the present disclosure, it has been discovered that the glass actuator element provided by the present disclosure is capable of not only the electrostrictive effect caused by direct current but also the electrostrictive effect caused by alternating current when using ion conductive glass. Furthermore, glass that can be used in the glass actuator element utilizing the electrostrictive effect caused by alternating current of the present disclosure is not limited to ion conductive glass, but may be any glass capable of generating local charge polarization by an electric field. Glass is widely and generally capable of generating local charge polarization by an electric field.

[0017] An example of a glass actuator element according to the first aspect of the present disclosure is shown in a longitudinal cross-sectional view in a schematic manner. In Fig. 1, the glass actuator element has a glass layer made of ion-conductive glass, clad layers laminated on both sides of the glass layer (the clad layers are not essential), and electrode layers provided on the outside of the clad layers. The glass actuator element according to the first aspect of the present disclosure preferably includes a clad layer, and at least a glass actuator element utilizing ion conductivity and space charge polarization includes a clad layer.

[0018] 1, when a DC electric field is applied to the glass layer, the glass layer is made of ion-conductive glass, so that in response to the electric field, metal ions in particular migrate to the cathode side, atomic vacancies are formed on the anode side, and spatial charge polarization occurs throughout the glass layer. As a result, the glass layer expands on the cathode side where metal ions have accumulated, and contracts on the cathode side, causing deformation (displacement) of the glass layer so that it curves. This utilizes the electrostrictive effect of DC.

[0019] The glass actuator element according to the first aspect of the present disclosure, which utilizes an AC current, may have a structure similar to that shown in FIG. 1 . The glass layer may be, but need not be, an ion-conductive glass. FIG. 1 illustrates the application of a DC voltage and does not illustrate the application of an AC voltage. However, when an AC electric field is applied to the glass layer of a glass actuator element having the shape shown in FIG. 1 , microscopically, metals (metal ions) in particular are displaced toward the cathode, while oxygen and phosphorus (anions) are displaced toward the anode, resulting in localized charge polarization (localized charge polarization). The magnitude of the unit localized charge polarization is not limited to glass without ion conductivity, but is generally considered to be within a range that maintains the glass network structure. However, according to the present disclosure, the electrostrictive effect has also been confirmed in glass with ion conductivity. In this case, ions can easily move beyond the boundaries of the glass network structure, and therefore the magnitude of the localized charge polarization is considered to be larger than that in glass without ion conductivity. Therefore, the electrostrictive effect of ion-conductive glass can be enhanced compared to that of non-ion-conductive glass, making ion-conductive glass suitable for use as a glass actuator element. The effect depends on the glass composition, applied voltage, applied frequency, temperature, and other factors, making it difficult to generalize. Metal ions, in particular, may be displaced and moved beyond atomic size. The glass expands and contracts locally in response to local charge polarization. When an AC electric field is applied, the direction of the local charge polarization and the direction of expansion and contraction change repeatedly. Furthermore, the local charge polarization occurs throughout the glass. As a result, the glass expands and contracts and vibrates as a whole. The local expansions and contractions and vibrations of the glass due to the local charge polarizations overlap. Furthermore, these local and overlapping expansions and contractions and vibrations resonate with the natural vibration of the glass layer, ultimately producing vibrations with waveforms as shown in Figures 15(b) and 20(b), as observed in the examples. The amplitudes shown in Figure 20(b) are absolute values, and the amplitude (displacement) at the end of the cantilever that is farther from the base is actually the amplitude (displacement) in the negative direction of the graph, which corresponds to the secondary vibration mode shown in Figure 15(b).15(b) and 20(b) show only the first and second vibrations, but third and higher vibrations can also occur. This utilizes the electrostrictive effect in alternating current. The principles of the electrostrictive effect in alternating current have been speculated and explained above, but the present disclosure should be interpreted based on the structure (and effect) of the disclosed glass actuator element and is not limited to the principles of this explanation.

[0020] <Glass layer; Requirement A> In the first embodiment (requirement B), the glass layer used as the element body in the glass actuator element according to the first aspect of the present disclosure (hereinafter also simply referred to as the glass layer) is made of phosphate-based glass containing at least one metal selected from Ag, Cu, and K, but in the second embodiment (requirement C), it is not limited to phosphate-based glass containing at least one metal selected from Ag, Cu, and K. The following description of the glass layer will broadly refer to the glass layer used in the second embodiment (requirement C), but it should be understood that the following general description of the glass layer also applies to the first embodiment (requirement B), and, except for the limitation to a specific glass composition, the requirements, characteristics, and technical matters common to the glass layers of both embodiments.

[0021] The glass layer of the glass actuator element according to the first aspect of the present disclosure is one in which ions contained in the glass move macroscopically or microscopically upon application of an electric field, causing polarization, thereby generating mechanical deformation (displacement) in the glass layer, or one in which a change in the electric field occurs in the glass layer when the glass layer is deformed (displaced) by an external force. In other words, the glass layer is capable of converting electrical energy into mechanical energy and / or mechanical energy into electrical energy, or is capable of converting either or both of these.

[0022] In this disclosure, glass refers to amorphous materials that exhibit a glass transition. Glass may be mineral glass or organic glass. By using glass for the body of the actuator element in this disclosure, compared to the use of polymers as in Patent Documents 1 and 2, the mechanical strength and heat resistance are greater, making it possible to use it in high-strength and / or high-temperature applications that are not possible with polymers. Furthermore, compared to ceramics, glass has the advantage of being able to increase the efficiency of electrical-mechanical energy conversion and can be manufactured at lower temperatures than ceramics. Furthermore, the use of glass has the advantage of being able to make the material transparent, although this depends on the composition.

[0023] When glass has electronegativity or electropositivity, or contains elements that are easily ionized, applying an electric field to the glass causes ions, especially cations, to move macroscopically within the glass in response to the electric field (ionic conductivity, space charge polarization), and elements with electronegativity or electropositivity, or cations and anions, to move, fluctuate, or displace microscopically, resulting in spatial or local charge polarization (local charge polarization).

[0024] Here, space charge polarization refers to charge polarization at the external dimension (i.e., spatial) level of ionically conductive glass. When a DC electric field is applied to ionically conductive glass, ion segregation and space charge polarization occur within the glass, and the glass deforms (displaces) based on the ion segregation. On the other hand, local charge polarization refers to charge polarization primarily at the interatomic level that occurs within the network structure when atoms that make up the glass network structure move from an electrically neutral state with no charge polarization within the network structure that makes up the glass to an oppositely charged atom with an electric field, moving toward or away from neighboring atoms. Local charge polarization is relatively local (micro or nano) in comparison to space charge polarization, which is macroscopic.

[0025] In this disclosure, the inventors have confirmed (discovered) that ion conductive glass also exhibits an electrostrictive effect when an AC electric field is applied. According to this disclosure, ion conductive glass can undergo deformation (displacement) based on space charge polarization when a DC electric field is applied, and can also undergo deformation (displacement) based on the electrostrictive effect when an AC electric field is applied.

[0026] In the present disclosure, the ion-conductive glass that can be suitably used may be any glass having ion conductivity, but typically, glass containing a metal element, particularly a metal element that is likely to generate cations with high ion mobility, particularly at least one of Ag, Na, K, and Cu, preferably Ag, Cu and / or K, particularly Ag, can be used. Although silicate glass can also be used as the ion-conductive glass layer, glass having high ion conductivity, a high Poisson's ratio or a low Young's modulus, and a low melting point is preferred, and phosphate-based glass or borate-based glass is preferably selected.

[0027] Specific compositions of the ion-conductive glass, for example, when containing Na, are preferably 50P2O5-50Na2O, 50P2O5-45Na2O-5B2O3, 50P2O5-10TeO2-40Na2O, 50P2O5-5TeO2-40Na2O-5NaCl, 45P2O5-10TeO2-40Na2O-5NaCl, 37.5P2O5-37.5B2O3-25Na2O, 27.5P2O5-27.5B2O3-45Na2O, 30P2O5-30B2O3-40Na2O, 35P2O5-35B2O3-30Na2O, etc. When K is contained, Na in the above Na-containing glass may be replaced with K. When Ag or Cu is contained, it will be described separately.

[0028] The glass used for the glass layer of the glass actuator element of the present disclosure is not limited to ion-conductive glass. Glass that does not have ion conductivity or has only low ion conductivity can also be used as the glass layer of a glass actuator element that utilizes an AC electric field, as long as it is a glass that can be locally charged polarized. One example of such glass can be found in glass having a composition similar to that of ion-conductive glass. For example, one option is glass that has a composition similar to that of ion-conductive glass but does not contain an element that serves as an ion source, or that contains a small amount of an element that serves as an ion source.

[0029] (phosphate glass) The glass used for the glass layer of the glass actuator element of the present disclosure, in the case of the second aspect (requirement C) described above, i.e., when the element has a cladding layer made of a dielectric, may be any glass capable of producing an electrostrictive effect, and may be selected from a wide range of common glasses, including silicate-based glasses, borate-based glasses, and phosphate-based glasses. However, one preferred glass is a phosphate-based glass. Phosphate-based glasses are glasses containing at least P2O5, and may be glasses consisting only of P2O5, but may also optionally contain other oxides, particularly metal oxides. Examples of metals that may be contained include Na, K, Ag, and Cu.

[0030] Phosphate-based glass will be described in detail below in connection with the first aspect (requirement B) when describing phosphate-based glass containing at least one metal selected from Ag, Cu, and K. Therefore, reference is made to the following description for the definition, properties, and the like of phosphate-based glass. In short, the phosphate-based glass differs only in that, in the following description of phosphate-based glass containing at least one metal selected from Ag, Cu, and K, the at least one metal selected from Ag, Cu, and K may or may not be included, and may contain other metals, such as Na or Fe, instead of or in addition to the at least one metal selected from Ag, Cu, and K. In particular, it should be noted that the phosphate-based glass may be glass consisting only of P2O5 without any metal oxides, or may be phosphate-based glass containing Na.

[0031] ( Phosphate-based glass containing at least one metal selected from Ag, Cu, and K; Requirement C ) In one embodiment of the first aspect of the present disclosure, the glass layer is made of a phosphate-based glass containing at least one metal selected from Ag, Cu, and K (requirement C). The phosphate-based glass containing at least one metal selected from Ag, Cu, and K is a glass containing P2O5 and Ag2O, K2O, Cu2O, or CuO (Cu x O) as the main component, and P2O5 and Ag2O, K2O, Cu2O or CuO (Cu x O), and may consist of only two components, P2O5 and Ag2O, K2O, Cu2O or CuO (Cu x O), and may further contain other metal oxides such as MoO3, WO3, TeO2, B2O3, GeO2, Nb2O5, Bi2O3, and the like.

[0032] Phosphate-based glasses have a looser network structure than silicate-based glasses. In silicate-based glasses, the three-dimensional network structure based on metal-oxygen (MO) bonds is rigid, resulting in low mobility of the network and metal ions. In contrast, the network structure of phosphate-based glasses is relatively linear compared to silicate-based glasses. Therefore, phosphate-based glasses have a soft structure in which the glass network and metal ions can easily move, fluctuate, and displace at least microscopically, and, depending on the composition, ions can also move macroscopically (spatially). Therefore, phosphate-based glasses have a structure that facilitates local charge polarization, which at least exerts an electrostrictive effect, and they also have ionic conductivity and can increase ionic conductivity.

[0033] Phosphate-based glasses are also characterized by their ability to contain large amounts of Ag (Ag ions, AgO), Cu (Cu ions, CuO or CuO), and K (K ions, KO), making them suitable for the glass body of glass actuator elements. While silicate-based glasses can contain only up to about 50 mol% of NaO or KO, about 20 mol% of CuxO, and a few mol% or less of AgO, phosphate-based glasses can contain AgO, KO, and CuxO, for example, up to about 70 mol%, or at least 60 mol%. The ability to contain large amounts of Ag, Cu, and K and the ability to retain glass properties even when containing large amounts of Ag, Cu, and K is advantageous for both DC and AC electrostrictive effects and also allows for excellent ionic conductivity.

[0034] On the other hand, Ag, Cu, and K are preferred as metal ion sources for phosphate-based glasses because they have the property of being easily polarized in response to an electric field. The HSAB principle (hard and soft acids and bases law) is a guideline for qualitatively expressing this property, and according to this, glasses are classified as shown in Table 1 below. [Table 1] Ag + ,Cu +is a soft acid, that is, an ion whose electron cloud is easily deformed in an electric field. This responsiveness is preferable because it works effectively on ionic conductivity and electrostriction effect. + is classified as a hard acid, but Na + Since it has a relatively large atomic number compared to the above, it can be positioned on the softer side and is similarly preferable.

[0035] In comparison with Na and Ag, according to the literature (Hall et al., J. Phys. Condens. Matter., 19 (2007) 415115), Ag is shown in Fig. 1. x Na 1-x The electrical conductivity (DC) of PO3 glass is shown, and Ag + The ion is Na + The conductivity is about three orders of magnitude greater than that of ions. This is also interpreted as being due to the properties of the soft acid mentioned above. Incidentally, the ionic radius is Na + : 0.99-1.18nm, Ag + : 1.00-1.28nm (coordination number 4-8). Such a large difference in electrical conductivity is advantageous in that mobility can be maintained even at low temperatures. This value is + Regarding Cu + ,K + About Na + is superior to the above for similar reasons.

[0036] Thus, the ionic conductivity of Ag- and Cu-containing phosphate glass, especially at room temperature, is + and Cu +Because Ag is a soft acid, i.e., an ion whose electron cloud easily deforms in an electric field, it always exhibits higher ionic conductivity than sodium-containing phosphate-based glasses with the same AgO, CuO, and NaO content (Reference: J. Mitroy, MS Safronova, CW Clark, “Theory and applications of atomic and ionic polarizabilities,” J. Phys. B: At. Mol. Opt. Phys., 43(2010)202001). Furthermore, when Ag is replaced with K, the ionic conductivity is not significantly higher than that of sodium, but the ionic polarizability is at least 5 to 10 times higher than that of sodium, thereby increasing the dielectric constant. Thus, Ag-, Cu-, and K-containing phosphate-based glasses are superior to sodium-containing phosphate-based glasses in terms of the electrical properties required for glass used in glass actuator elements.

[0037] Furthermore, using the Makishima-Mackenzie equation, the Young's modulus of glass can be approximated as the sum of the products of the volume fractions of the constituent components of the glass and their dissociation energies, and because Ag2O, Cu2O, and K2O have dissociation energies that are equal to or smaller than those of Na2O, they are excellent for reducing the Young's modulus of phosphate-based glasses. Therefore, even in terms of the mechanical properties required of glass used in glass actuator elements, when considering the rigidity of the glass (small displacement), phosphate-based glasses are superior to silicate-based glasses, but even within the same phosphate-based glasses, phosphate-based glasses containing Ag, Cu, and K are superior to Na-containing phosphate-based glasses and are therefore highly useful.

[0038] In phosphate-based glasses containing Ag, Cu, and K, the P2O5 content is preferably 30 mol% or more, more preferably 35 mol% or more, and particularly preferably 36 mol% or more, 37 mol% or more, 38 mol% or more, 39 mol% or more, or 40 mol% or more. The upper limit of the P2O5 content may be the remainder of the second component, Ag, Cu, K, or their oxides, such as Ag2O. When a metal oxide other than these oxides (third component), such as Ag2O, is included, the upper limit may be the remainder. The upper limit of the P2O5 content may be, for example, 99 mol%, 90 mol%, 80 mol%, 70 mol%, 50 mol%, or 40 mol%. Metal oxides as third components can be added to modify various physical properties and characteristics of phosphate-based glasses containing Ag, Cu, and K. For example, they can be added to adjust mechanical strength (Young's modulus, Poisson's ratio, stiffness, etc.), optical properties (transparency, hue, etc.), heat resistance, etc. The selection of such a third component and the adjustment of its content are known to those skilled in the art, or can be carried out appropriately.

[0039] In phosphate-based glasses containing Ag, Cu, and K, the contents of Ag, Cu, and K, calculated as Ag2O, Cu2O, and K2O, are preferably 1 mol% or more, more preferably 3 mol% or more, and particularly preferably 5 mol% or more, 10 mol% or more, 15 mol% or more, 20 mol% or more, 30 mol% or more, or 40 mol% or more. The upper limit of the contents of Ag2O, Cu2O, and K2O may be the remainder of P2O5, or, if a metal oxide (third component) other than Ag2O, Cu2O, and K2O is contained, it may be the remainder of both. The upper limit of the contents of Ag2O, Cu2O, and K2O may be, for example, 70 mol%, 60 mol%, 50 mol%, 45 mol%, 40 mol%, or 35 mol%.

[0040] Phosphate-based glass containing Ag, Cu, and K, for example, is aAg2O-bMO x-cP2O5 (where M is one or more metal elements, x is a value obtained by dividing the value of the metal M by 2, and 1≦a≦(100−c), 0≦b≦69, 30≦c≦(100−a), and a+b+c=100). For phosphate-based glasses containing Ag, Cu, and K, Ag may be substituted with at least one of Ag, Cu, and K in the above-mentioned example of phosphate-based glasses containing Ag. Preferred examples of the numerical ranges of a and c are described above. b is (100−a−c), and the preferred range can be calculated from the preferred ranges of a and c. When M is a plurality of metal elements, the numerical range may be determined depending on the type of each metal element. For example, in the case of MoO3, WO3, or TeO2, b may be, for example, 0 to 20, preferably 5 to 15, and more preferably 8 to 12.

[0041] Similarly, phosphate-based glasses containing Ag (phosphate-based glasses containing Ag, Cu, and K may have Ag substituted with at least one of Ag, Cu, and K) may be, for example, glasses having a composition of Ag2O-MoO3-WO3-TeO2-P2O5 (however, one of the TeO2 and P2O5 systems may be omitted). Glasses having this composition have high ionic conductivity, and glasses not containing either TeO2 or P2O5 (i.e., glasses in which part of the TeO2 in Ag2O-MoO3-WO3-P2O5 is substituted with P2O5) are particularly preferred because they have high ionic conductivity, high light transmittance, and particularly transparency. For example, glasses having a composition of 40Ag2O-10MoO3-10WO3-(40-x)TeO2-xP2O5 (where 0≦x≦40) are preferred. In this glass composition, the composition (content ratio) of Ag2O, MoO3, WO3, and P2O5 before substituting a portion of TeO2 with P2O5 is not limited to 40Ag2O-10MoO3-10WO3-40P2O5, but may be, for example, (30-50)Ag2O-(5-15)MoO3-(5-15)WO3-(30-50)P2O5 (where the total content ratio of Ag2O, MoO3, WO3, and P2O5 is 100). Experiments by the present inventors have shown that glass having this composition has an optical absorption edge wavelength that is reduced to around 400 nm, and transparency is improved, compared to glass before substituting a portion of TeO2 with P2O5.

[0042] In one preferred embodiment of the present disclosure, the glass may be an Ag2O-MoO3-WO3-P2O5-based glass (Ag may be substituted with at least one of Ag, Cu, and K). Glass of this composition is preferred because it has excellent ionic conductivity, as well as higher light transmittance, and is particularly transparent. For example, glass having a composition of 40Ag2O-yMoO3-(20-y)WO3-40P2O5 (where 0≦y≦40) is preferred. In this glass composition, the composition (content ratio) of Ag2O, WO3, and P2O5 before substituting a portion of WO3 with MoO3 is not limited to 40Ag2O-20WO3-40P2O5, but may be, for example, (30-50)Ag2O-(5-15)WO3-(30-50)P2O5 (where the total content ratio of Ag2O, WO3, and P2O5 is 100). Experiments by the present inventors have shown that glass having a composition of 40Ag2O-20WO3-40P2O5 has high transparency, and that transparency gradually decreases when a portion of WO3 is substituted with MoO3.

[0043] (General characteristics, shape, etc. of the glass layer) Various preferred properties of the glass layer used in the glass actuator element of the first aspect of the present disclosure are described below, and while such preferred properties are easily achieved in phosphate-based glass containing at least one metal selected from Ag, Cu, and K, the glass layer used in the glass actuator element of the first aspect of the present disclosure is not limited to glass layers exhibiting such preferred values ​​for its properties. In particular, in the case of a glass actuator element satisfying requirement C, the glass layer is not limited to phosphate-based glass containing at least one metal selected from Ag, Cu, and K, and therefore the glass layer may exhibit a wide range of properties rather than such preferred values.

[0044] (electrical conductivity) The glass actuator element according to the first aspect of the present disclosure may be any element that exhibits an electrostrictive effect (local charge polarization) due to alternating current, and therefore the glass layer used does not need to be electrically conductive, but one that has ion conductivity is preferred. In one preferred embodiment of the present disclosure, when ion-conductive glass is used as the glass layer, the higher the ion conductivity of the glass, the better. While not limited to this, for example, at temperatures of 0°C to 400°C, particularly at room temperature (25°C), the ion conductivity of the glass is preferably 10 -9 S / cm or more, preferably 10 -7 ~10 -2 S / cm, 10 -5 ~10 -2 S / cm, and even 10 -2 In a preferred embodiment of the first aspect of the present disclosure, as shown in the examples, the glass can exhibit such ionic conductivity at low temperatures, including room temperature (25°C) (for example, 300°C or less, 200°C or less, or even 100°C or less, with the lower limit being 0°C), which is extremely advantageous in terms of actuator applications, compared to the ionic conductivity exhibited only at high temperatures, such as 350°C, by the glass of Patent Document 3. Phosphate-based glasses containing Ag, Cu, and K are preferred because they can easily achieve such suitable ionic conductivity. Electrical conductivity and ionic conductivity can be measured by the two-terminal method using an impedance analyzer. Measurements are performed at room temperature (25°C).

[0045] (Young's modulus) The Young's modulus of the glass layer used in the present disclosure is not particularly limited and may be 70 GPa or greater, but is preferably less than 70 GPa, more preferably 65 GPa or less, 60 GPa or less, 50 GPa or less, 40 GPa or less, 35 GPa or less, or 30 GPa or less. Generally, a larger reciprocal of Young's modulus, i.e., a smaller Young's modulus, is preferable because it results in a superior electromechanical energy conversion coefficient and electrostriction coefficient of the actuator element. The lower limit of the Young's modulus of the glass layer may be, for example, 30 GPa, 20 GPa, 10 GPa, or 5 GPa from the viewpoint of the strength required for functioning as an actuator element. Incidentally, the Young's modulus of silicate-based glass is, for example, 70 GPa or greater, while the Young's modulus of polymers, such as polyurethane, is 1 GPa or less. Phosphate-based glass containing Ag, Cu, and K is preferred because it can easily achieve the above-described desirable Young's modulus. Young's modulus and Poisson's ratio can be measured using an ultrasonic pulse method. The ultrasonic pulse method involves transmitting an ultrasonic pulse through a sample and calculating the Young's modulus and Poisson's ratio from the propagation velocity of the longitudinal and shear waves that propagate within the sample. For example, a V110, 5MHz transducer for longitudinal waves and a V156, 5MHz transducer for shear waves can be used. The vibration of the sample is measured with an oscilloscope, and the Young's modulus and Poisson's ratio of the sample can be calculated from the resulting waveform. Young's modulus and Poisson's ratio are measured at room temperature (25°C).

[0046] (Poisson's ratio) The preferred mechanical deformation ratio of the glass layer can also be expressed in terms of Poisson's ratio rather than Young's modulus. The Poisson's ratio may be 0.20 or greater, greater than 0.25, 0.26 or greater, 0.27 or greater, 0.30 or greater, 0.32 or greater, 0.34 or greater, or 0.35 or greater. Generally, a higher Poisson's ratio is preferable because it increases the electrical-mechanical energy conversion coefficient. Incidentally, the Poisson's ratio of silicate-based glasses is, for example, 0.25 or less, and the Poisson's ratio of polymers, such as polyurethane, is 0.4 or greater. Phosphate-based glasses containing Ag, Cu, and K are preferred because they can easily achieve such a suitable Poisson's ratio. The upper limit of the Poisson's ratio is not limited, but may be, for example, 0.50 or less, less than 0.40, or 0.35 or less.

[0047] (Dielectric constant / relative permittivity) It is generally known that the electrostrictive coefficient of a material (the larger the electrostrictive coefficient, the greater the electrostrictive effect) is, as the dielectric constant of the material increases. Therefore, the higher the dielectric constant of the glass layer, the better. However, the relative dielectric constant may be, for example, 1 or greater, 2 or greater. Preferably, particularly when condition B is satisfied (but this is not a limitation), the relative dielectric constant may be 5 or greater, 7 or greater, and may be 10 or greater, greater than 10, 12 or greater, 15 or greater, or 20 or greater. Furthermore, particularly for ion-conductive glass, the relative dielectric constant may be, for example, approximately 100 to 200, or even approximately 300, and depending on the applied electric field frequency, approximately 300 to 400 or even greater. The relative dielectric constant can be measured by measuring ionic conductivity using a two-terminal method with an impedance analyzer and analyzing the ionic conductivity measurement. Measurements are performed at room temperature (25°C).

[0048] (transparency) In the glass actuator element according to the first aspect of the present disclosure, it may be preferable for the glass layer to have transparency depending on the application. Transparency can be evaluated by light transmittance, and for example, at a predetermined thickness, it is preferably 30% or more, more preferably 40% or more, and even more preferably 50% or more. The predetermined thickness may be, for example, 10 to 100 μm. An important critical value for this purpose is that an object, character, etc. on the opposite side of the glass layer can be recognized through the glass layer by a viewer. When an object on the opposite side of the glass layer can be recognized, it can be said to be transparent in the narrow sense.

[0049] (shape) In the glass actuator element according to the first aspect of the present disclosure, the shape of the glass layer is preferably a plate-like shape (the dimension in the direction of the opposing surface is greater than the thickness) that has excellent deformability for generating displacement, and further, the opposing surface is preferably a flat plate-like shape, particularly a plate-like shape having parallel flat surfaces, but may also be a curved shape, a shape with irregularities, etc. When the glass layer is a plate-like shape, the shape of the opposing surface is not limited to an elongated shape and may be various shapes, such as a button shape, a circle, an oval, a square, a rectangle, a dogleg shape, an S-shape, etc.

[0050] (size) The dimensions of the glass layer in the glass actuator element according to the first aspect of the present disclosure depend on the performance and application required of the glass actuator, and may vary from large to small, and are not limited to a single dimension. Therefore, without being limited thereto, the ratio of length to thickness may be, for example, 1 to 10,000 times, or even 5 to 5,000 times, or even 10 to 1,000 times. A preferred thickness may be 5 nm to 1,000 μm, 1 to 100 μm, or even 10 μm to 50 μm. A preferred length may be 1 mm to 50 cm, or even 2 mm to 100 mm, for example, 3 mm to 20 mm, and may be 2 mm to 10 mm when the thickness is 30 μm.

[0051] <Cladding layer> In the glass actuator element of the first aspect of the present disclosure, a cladding layer is not required. In the glass actuator element of the first aspect of the present disclosure, a cladding layer is not required, particularly in glass actuator elements utilizing an electrostrictive effect under alternating current. However, a cladding layer may be present in both glass actuator elements utilizing an electrostrictive effect under alternating current and an electrostrictive effect under direct current. The cladding layer is composed of a material capable of blocking charges (ions, electrons), particularly ions in ion-conductive glass. However, the cladding layer may be provided for the purpose of preventing or suppressing reactions between the glass layer and the electrode layer. In particular, when an electric field is applied, it is undesirable for ions of a metal such as Ag contained in the glass layer to react with electrons supplied from the electrode layer to precipitate the metal such as Ag. Therefore, it may be preferable to insert an electrical insulator as a cladding layer between the glass layer and the electrode layer. In one preferred embodiment (requirement C) of the first aspect of the present disclosure, the glass actuator element has a cladding layer, which is composed of a dielectric material having a thickness of less than 10 μm.

[0052] In the glass actuator element according to the first aspect of the present disclosure, the cladding layer is formed on the surface of the glass layer between the glass layer and the electrode, and serves the function of blocking charges, particularly ions, that move within the glass layer. The cladding layer is made of a material with low electrical conductivity, preferably a dielectric, particularly an electrical insulator.

[0053] (dielectric) The cladding layer has low ionic or electrical conductivity to block ions or electrons, and is most preferably a dielectric, particularly an insulator. A dielectric is a material in which dielectric properties predominate over electrical conductivity, has a wide band gap, and is usually an electrical insulator that does not conduct electricity with DC voltage, but can at least be an electrical insulator. Although a dielectric passes electricity in an AC electric field, this is because it functions as a capacitor. Even when an AC electric field is applied to a dielectric, ions and electrons do not penetrate the dielectric, move within the dielectric, and pass through the dielectric, so the ion-blocking ability of the dielectric is not lost even in the case of an AC electric field.

[0054] In Patent Document 3, the cladding layer is made of glass, which limits the choice of cladding layer material, but in the present disclosure, the cladding layer is made of a wide range of dielectrics, which broadens the range of choices for cladding layer materials and manufacturing methods, thereby improving the performance, characteristics, manufacturing flexibility, etc. of the glass actuator element. In the present disclosure, the dielectric may be made of a dielectric other than glass, but may also be glass.

[0055] (thickness of cladding layer) In the glass actuator element of the present disclosure, the thickness of the cladding layer may be, for example, 1 mm or less, 100 μm or less, 50 μm or less, 30 μm or less, 20 μm or less, or 10 μm or less, particularly in an embodiment that satisfies requirement B, but in a glass actuator element of a preferred embodiment of the present disclosure (when requirement C is satisfied), the cladding layer is made of a dielectric material with a thickness of less than 10 μm. A thinner cladding layer increases the flexibility (flexibility) of the cladding layer, improving adhesion to the glass layer and also increasing the relative electric field applied to the glass layer, thereby improving the performance of the glass actuator element. The thickness of the cladding layer is preferably less than 10 μm, and particularly by forming it by a thin film method, it can be made less than 10 μm, 8 μm or less, 5 μm or less, 3 μm or less, 2 μm or less, 1 μm or less, and particularly less than 1 μm, and can also be 800 nm or less, 500 nm or less, 200 nm or less, 100 nm or less, 50 nm or less, 30 nm or less, 20 nm or less, 10 nm or less, or 5 nm or less. The lower limit of the cladding layer thickness is not limited as long as it can be manufactured or has the structural strength required for the element, but may be, for example, 2 nm or more, 3 nm or more, 5 nm or more, or 10 nm or more, or 20 nm or more.

[0056] ( Cladding layer made of dielectric material less than 10 μm thick; Requirement C ) In one embodiment of the glass actuator element according to the first aspect of the present disclosure, the cladding layer is made of a dielectric material having a thickness of less than 10 μm (requirement C). The glass actuator element of Patent Document 3 uses a glass cladding of a predetermined thickness (although in practice there are thought to be limitations on the glass composition), but if the cladding layer is made of a dielectric material having a thickness of less than 10 μm, the range of materials that can be selected for the cladding layer is wider than that of the glass cladding of Patent Document 3, and properties such as blocking performance (electrical insulation) and dielectric constant can be excellent, and the small thickness also means that flexibility (flexibility) and adhesion to the glass layer can be excellent.

[0057] In the glass actuator element of Patent Document 3, the cladding layer is composed of thick glass, which limits the choice of material. Furthermore, in Patent Document 3, the cladding layer is limited to glass, and the cladding glass of a predetermined thickness must be pre-fabricated and laminated. Therefore, the composition of the cladding glass layer must be determined based on compatibility with the core glass layer, which limits the materials that can be used for the cladding layer. This limits the electrical and mechanical properties of the cladding layer, such as its dielectric constant and electrical insulation. In contrast, in the glass actuator element of the present disclosure, the cladding layer can be made of a wide range of dielectrics, which broadens the range of materials that can be used for the cladding layer and enables the cladding layer's electrical and mechanical properties to be further optimized. In particular, the cladding layer's dielectric constant can be increased or it can be made an electrical insulator, thereby improving the performance and electro-mechanical energy conversion efficiency of the glass actuator element. Details of the types and properties of dielectrics that can be used for the cladding layer of the glass actuator element of the present disclosure are described elsewhere.

[0058] In the glass actuator element of Patent Document 3, the cladding layer is composed of thick glass, which results in low flexibility (flexibility) of the cladding layer. Furthermore, due to the manufacturing process in which cladding glass of a predetermined thickness is manufactured and laminated in advance, there are problems such as low adhesion of the cladding layer to the core glass layer. Furthermore, in Patent Document 3, the cladding layer is limited to glass, and due to the constraint of manufacturing and laminating cladding glass of a predetermined thickness in advance, the composition of the cladding glass layer must take into consideration compatibility with the core glass layer, which places restrictions on the material of the cladding layer. In contrast, in the actuator element of a preferred embodiment of the present disclosure, by setting the thickness to less than 10 μm, the small thickness gives the cladding layer flexibility (flexibility) and excellent adhesion to the glass layer during use. Furthermore, since a thin-film method (vapor-phase deposition method) can be used for dielectrics with a thickness of less than 10 μm, excellent adhesion to the glass layer during manufacturing can also be achieved.

[0059] When the cladding layer is made of a dielectric material with a thickness of less than 10 μm, the cladding layer can be formed by, but is not limited to, a thin-film method (vapor-phase deposition method) rather than a melting method as in the case of the glass cladding layer of Patent Document 3. Using a thin-film method (vapor-phase deposition method) allows the cladding layer to be formed by depositing microparticles, molecules, or atoms on the glass layer, and the thickness of the cladding layer can be reduced. Furthermore, since a thin dielectric can also be flexible, the cladding layer can have excellent adhesion to the glass layer (main glass layer), especially compared to a glass cladding layer. Excellent adhesion between the cladding layer and the glass layer allows the glass actuator element to have excellent durability against repeated deformation.

[0060] When the cladding layer is composed of a dielectric material with a thickness of less than 10 μm, the small thickness of the cladding layer increases the flexibility (flexibility) of the cladding layer, allowing for excellent adhesion to the glass layer even when the glass layer deforms (displaces) or changes in volume during use of the glass actuator element. Furthermore, since more of the electric field applied to the glass actuator element can be distributed to the glass layer, the electricity-deformation / displacement conversion efficiency of the glass actuator element is improved, resulting in improved performance of the glass actuator element. Furthermore, since the cladding layer is composed of a dielectric material, the material is not limited to glass, allowing for a wider range of material options and making it possible to further optimize the electrical and mechanical properties of the cladding layer.

[0061] The thickness of the cladding layer can be less than 10 μm, 8 μm or less, 5 μm or less, 3 μm or less, 2 μm or less, 1 μm or less, particularly less than 1 μm, particularly when forming it by a thin film method, particularly when requirement C is satisfied, but is not limited to this, and can also be 800 nm or less, 500 nm or less, 200 nm or less, 100 nm or less, 50 nm or less, 30 nm or less, 20 nm or less, 10 nm or less, or 5 nm or less.

[0062] (Dielectric constant and relative permittivity of cladding layer) In the glass actuator element of the present disclosure, it is generally known that the electrostriction coefficient of a material (the larger the electrostriction coefficient, the greater the electrostriction effect) is, as the dielectric constant of the material increases. Therefore, the higher the dielectric constant and relative permittivity of the cladding layer, the better, whether the embodiment satisfies requirement B or requirement C. In the embodiment satisfying requirement B, the relative permittivity of the cladding layer may be, for example, 1 or more, 2 or more, or 4 or more. Preferably, particularly when requirement C is satisfied, the relative permittivity may be 5 or more, 7 or more, or 10 or more, and may even be 20 or more, 50 or more, 100 or more, or 200 or more. There is no particular upper limit, but it may be 1,000 or less, 500 or less, 300 or less, 200 or less, etc. In the glass actuator element of a preferred embodiment of the present disclosure (when requirement C is satisfied), the cladding layer is composed of a dielectric material having a thickness of less than 10 μm. This eliminates the material restrictions of Patent Document 3, and allows for a higher dielectric constant than that of Patent Document 3. If the cladding layer has a high dielectric constant, or if its thickness is small as described below, it is possible to distribute more of the electric field applied to the actuator element to the glass layer, thereby improving the electricity-deformation / displacement conversion efficiency of the glass actuator element and improving the performance of the glass actuator element. The dielectric constant of the cladding layer is not limited, but it is preferable that it is as high as possible. The method for measuring the dielectric constant and relative permittivity can be the same as for glass.

[0063] (electrical conductivity) In the actuator element according to a preferred embodiment of the present disclosure, the cladding layer preferably has a lower electrical conductivity (electrical conductivity), particularly an ionic conductivity, than the glass layer, and is preferably an insulator. Dielectrics are generally insulators against direct current and satisfy the desirable properties of an insulator. The electrical conductivity or ionic conductivity of the cladding layer is preferably lower than the electrical conductivity or ionic conductivity of the glass layer (for example, 10 -8 ~10 -2The dielectric constant must be at least one to two orders of magnitude lower, and even at least three orders of magnitude lower, than the electrical conductivity (S / cm), and it is particularly preferable that the cladding layer is an electrical insulator (electronic conductivity and ionic conductivity are 0), but the dielectric may also be an electrical insulator. The method for measuring electrical conductivity may be the same as for glass.

[0064] (dielectric materials) The dielectrics used in the cladding layers of preferred embodiments of the present disclosure can be inorganic and organic dielectrics, such as crystalline or amorphous inorganic materials, ceramics, glasses, polymers, etc. Suitable dielectrics include crystalline and amorphous inorganic and organic materials having dielectric properties (particularly piezoelectric and ferroelectric properties), among others, Pb(Zr,Ti)O3 (PZT), PbTiO3, PbNb2O6, BaTiO3, Bi4Ti3O 12 Piezoelectric ceramics such as (Bi,Na)TiO3, (K,Na)NbO3 (KNN); crystalline inorganic materials such as PZT, ZnO, AIN / ScAIN, KNN, TiO x Examples of suitable materials include amorphous inorganic materials such as SrTiO3, silicon, and organic materials such as PVDF (polyvinylidene fluoride) and PLA (polylactic acid). In a preferred embodiment of the present disclosure, the cladding layer is a dielectric. However, if the material is amorphous, glasses that exhibit a glass transition are excluded; instead, the material is an amorphous material that does not exhibit a glass transition (amorphous material in the narrow sense). In one preferred embodiment, the dielectric material of the cladding layer may be selected from TiO2, BaTiO3, SrTiO2, Al2O3, MgO, ZrO2, MgAl2O4, and RNbO3 (R = Li, Na, or K, or a combination thereof). The cladding layer in the present disclosure is not limited to glass as in Patent Document 3, but can be other than glass. For example, the above-mentioned crystalline and amorphous inorganic and organic materials can also be preferably other than glass. Many of the above-mentioned dielectrics are other than glass. In the glass actuator element (requirement B) using a phosphate-based glass containing at least one metal selected from Ag, Cu, and K, a glass is provided that can operate at low temperatures, including room temperature, so that materials with low heat resistance, such as organic polymers, can be advantageously used.

[0065] (Manufacturing method) The cladding layer can be formed by a vapor phase deposition method (thin film method), and is preferably formed by a vapor phase deposition method (preferred manufacturing methods will be described later), but it may also be formed by methods other than the thin film method, such as a thick film method.

[0066] <Electrode layer; Requirement A> In the glass actuator element of the present disclosure, when a clad layer is provided on the opposing surface of the glass layer, an electrode layer is provided on the outside of the clad layer. The electrode layer is preferably present as widely as possible along the surface of the glass layer. However, it is not essential that the electrode layer be formed on the entire surface of the glass layer, and the shape or pattern of the electrode layer may be, for example, provided on the entire surface of the clad layer or in a mesh, stripe, or lattice pattern.

[0067] The electrode layers connected to opposing surfaces of the glass layer must be electrically isolated from each other. Typically, electrode layers are formed only on the two opposing surfaces of the plate-shaped glass layer (or clad layer), and no electrode layers are formed on the side surfaces of the plate-shaped glass layer (clad layer). The electrode layer formed on the surface of the clad layer is further electrically connected to a power source, but the connection method is arbitrary and may be any known method.

[0068] The electrode layer can be made of a conductive material, particularly a metal material, a conductive ceramic, a conductive polymer, etc. Suitable examples include metals such as Ag, Al, and Pt, and conductive oxide films such as ITO (tin-doped indium oxide).

[0069] The thickness of the electrode layer may be sufficient to maintain its own mechanical strength and to allow a sufficient electric field to be applied to the glass layer, but it is preferable that the thickness is thin enough not to impede deformation or displacement of the glass layer. For example, the thickness of the electrode layer may be 1 nm to 10 μm, and in one preferred example, it may be 1 nm to 0.1 μm or 1 nm to 50 nm.

[0070] (glass actuator element) An example of the structure of the glass actuator element according to the first aspect of the present disclosure is shown schematically in FIG.

[0071] Also, electromechanical energy conversion in the glass actuator element according to the first aspect of the present disclosure has been described above.

[0072] The glass actuator element according to the first aspect of the present disclosure has a glass layer as its main body, and is therefore characterized by excellent mechanical strength, heat resistance, chemical stability, durability, and the like.

[0073] The glass actuator element according to the first aspect of the present disclosure has an operating temperature of 0 to 400°C, and is advantageous in that it can be used even at high temperatures. However, in particular, according to a preferred embodiment of the glass layer of the present disclosure, the glass actuator element can operate at low temperatures, particularly at room temperature, which is a novel and particularly advantageous effect.

[0074] The glass actuator element according to the first aspect of the present disclosure generates displacement by applying an electric field, and is therefore useful in the following applications.

[0075] 1) Displacement element Path switching using MEMS optical switches: Glass actuator elements are displaced periodically or aperiodically in response to electrical signals, changing the transmission direction, refraction angle, or reflection angle of light propagating through the optical circuit, thereby enabling path switching.

[0076] 2) Vibration element Vibration element for moving and transporting objects and generating sound: By periodically applying an electric signal and modulating it by the shape and position of the electrodes, the density of the element is induced, generating vibrations and transverse waves. These waves can move and transport materials, and depending on the frequency, can function as a source of elastic waves and sound waves.

[0077] 3) The sensor A sensor with piezoelectric properties that converts force into an electrical signal: A sensor that detects the force (pressure) applied to an element in a state where a bias electric field is applied and space charge polarization or local charge polarization is created as an electrical signal generated between the two electrodes. In addition to pressure, this sensor can also detect temperature, light, sound (microphone, etc.), wind speed, etc.

[0078] [Second aspect: manufacturing method of glass actuator element] In a second aspect, the present disclosure provides a method for manufacturing a semiconductor device comprising: (A1) providing glass layers having opposing surfaces; (A2) forming an electrode layer on each of the opposing surfaces of the glass layer; (B1) forming the glass layer from a phosphate-based glass containing at least one metal selected from Ag, Cu, and K, and / or (E) forming a clad layer made of a dielectric between the glass layer and the electrode layer by a vapor deposition method; (D1) Producing a glass actuator element capable of electromechanical energy conversion; The present invention provides a method for manufacturing a glass actuator element characterized by the above-mentioned.

[0079] The configuration of the glass actuator element manufactured in the second aspect of the present disclosure (glass layer, electrode layer, and optionally cladding layer) can be the same as the configuration of the glass actuator element described in the first aspect (Requirements A1 and A2), and therefore a detailed description thereof will be omitted. In particular, the description of the first aspect is referred to for the configuration and effects of forming the glass layer from a phosphate-based glass containing at least one metal selected from Ag, Cu, and K (Requirement B1), and forming a cladding layer made of a dielectric between the glass layer and the electrode layer (Requirement E), as well as the significance of forming the cladding layer by a vapor-phase deposition method (Requirement E).

[0080] The glass layer is typically formed by a melting process, but it can also be formed by thick-film methods such as coating or other methods. In the melting process, a core glass layer, optionally composed of ion-conductive glass, is typically produced through the following steps: batch mixing → melting → pouring → slow cooling → cutting and polishing, as shown in Figure 2. The right side of Figure 2 shows an example of producing an AgO-WO-P2O5-based glass. For example, after batch mixing the oxide powder raw materials AgO, P2O5, AgNO3, and WO3, the mixture may be melted at 800-1000°C for 0.5-1 hour, poured onto a brass plate, quenched, maintained at 260°C for 30 minutes, and then cooled at a rate of 1°C / min to produce the glass layer (in this example, ion-conductive glass). The produced glass layer can be cut to a predetermined size and polished to produce the glass layer.

[0081] When forming a cladding layer, the cladding layer is formed on both sides of the glass layer. The method for forming the cladding layer is not limited, and may be a vapor-phase deposition method (thin-film method) or other method such as a thick-film method. However, in the second aspect of the present disclosure, the cladding layer is preferably formed by a vapor-phase deposition method (thin-film method), particularly when the cladding layer is made of a dielectric (Requirement E). Examples of vapor-phase deposition methods include evaporation, sputtering, atomic layer deposition (ALD), and chemical vapor deposition (CVD). These deposition methods may be either physical deposition or chemical deposition. Vapor-phase deposition (thin-film method) allows the cladding layer (hereinafter simply referred to as the dielectric) to be deposited as a thin film, making it possible to reduce the thickness of the cladding layer. This ability to reduce the thickness of the dielectric layer is advantageous for forming a cladding layer that utilizes the properties of a dielectric. Furthermore, using vapor deposition, the substances deposited on the glass layer consist of minute substances such as atoms, molecules, ions, atomic groups, atomic group ions, and microparticles, so the cladding layer is deposited in a manner that adapts to the unevenness of the surface of the glass layer, and based on the principles of deposition, the deposited cladding layer can have excellent adhesion to the glass layer. Furthermore, dielectrics are more likely to be flexible and pliable than glass, and vapor deposition (thin film) allows the cladding layer to be made thinner, further increasing its flexibility and pliability, and further improving the adhesion of the cladding layer to the glass layer. Excellent adhesion between the cladding layer and the glass layer provides the glass actuator element with excellent strength and durability, extending its lifespan against repeated displacement (deformation).

[0082] According to the manufacturing method of the second aspect of the present disclosure, the thickness of the cladding layer can be 10 μm or more or less than 10 μm. The thickness of the cladding layer, particularly in embodiments that satisfy requirement B1, may also be, for example, 1 mm or less, 100 μm or less, 50 μm or less, 30 μm or less, 20 μm or less, or 10 μm or less, even when requirement E is also satisfied. However, the thickness of the cladding layer, particularly in embodiments that satisfy requirement E, can be preferably less than 10 μm, 5 μm or less, 3 μm or less, 2 μm or less, or 1 μm or less, particularly less than 1 μm, and can also be 100 nm or less, 30 nm or less, 20 nm or less, 10 nm or less, or 5 nm or less. The lower limit of the cladding layer thickness is not limited as long as it is manufacturable or has sufficient structural strength as an element, but may be, for example, 2 nm or more, 3 nm or more, 5 nm or more, 10 nm or more, or 20 nm or more. The thickness of the cladding layer and its significance are described in the first aspect, and reference is made to that description.

[0083] The conditions for forming the cladding layer by vapor deposition are appropriately selected depending on the type of cladding layer (dielectric or the like) used, the type of glass layer, the dimensions of the cladding layer, etc., but are basically known to or can be easily implemented by those skilled in the art. Examples will be described later.

[0084] The electrode layer may be formed by any method for depositing a conductive material. For example, the electrode layer may be formed by a vapor phase deposition method (thin film method) or other methods such as a thick film method. The electrode layer may also be connected to a power source by a known method. [Example]

[0085] The present disclosure will be further described below based on examples, but it is clear that the present disclosure is not limited to the examples.

[0086] Example 1 (Glass Preparation) Glass with a composition of 40Ag2O-20WO3-40P2O5 (mol%) was prepared through the following steps: batch mixing → melting → pouring → slow cooling. Samples for evaluating physical properties were prepared by cutting and polishing the prepared glass.

[0087] Specifically, referring to FIG. 2, Ag2O-P2O5, AgNO3, and WO3 oxide powder raw materials were batch mixed, and then the mixture was melted at 800-1000°C for 0.5-1 hour, poured onto a brass plate, rapidly cooled, and then maintained at 260°C for 30 minutes, after which the temperature was lowered at a rate of 1°C / min to produce glass (ionically conductive glass).

[0088] Example 2 (Glass Preparation) Glass (ionically conductive glass) having the composition 40Ag2O-10WO3-10MoO3-(40-x)TeO2-xP2O5 (mol %), where x = 0, 4, 8, 16, or 40, was prepared in the same manner as in Example 1, except that the powder raw materials were changed to Ag2O-P2O5, AgNO3, WO3, MoO3, and TeO2.

[0089] Example 3 (Glass Preparation) In the same manner as in Example 1, except that the powder raw materials were changed to Ag2O-P2O5, AgNO3, MoO3, and WO3, glasses (ionically conductive glasses) were prepared with the compositions 40Ag2O-yMoO3-(20-y)WO3-40P2O5 (mol%), where y = 0, 3.3, 6.7, 10, 13.3, 16.7, and 20.

[0090] Example 4 (Glass Processing) The glasses prepared in Examples 1 to 3 were melted and extruded to prepare glass fibers with a diameter of approximately 150 μm. The obtained glass fibers were processed into glass rods using a uniaxial hot press, and then cut and polished to prepare beam-shaped glass samples.

[0091] The glass layer processing method will be explained with reference to Figure 3. The left side of Figure 3 is a photograph showing the entire uniaxial hot pressing apparatus, and the right side is a schematic diagram showing the processing of a beam-shaped glass layer from fiberglass. In the right side, two fiberglass strands are placed side by side on the lower mold of an upper and lower mold member with parallel surfaces that make up the sample stage. As can be seen in the left side, the sample stage with the fiberglass strands placed side by side between the mold members in the uniaxial hot pressing apparatus was placed in a tubular furnace, and the mold member was uniaxially hot pressed from above and below via bearings using the rod shown in the right side at a temperature of 335°C to process the beam-shaped glass layer. Two beam-shaped glass layers were produced.

[0092] Figure 4 shows photographs of the appearance of the fiberglass before processing using the above method (top), the appearance of the rectangular glass rod obtained by processing the fiberglass (middle), and the cross-section of the glass rod (bottom). Example dimensions are written on each photograph in Figure 4. In the example photograph, the rectangular glass rod was cut into 5 mm pieces, and its thickness was approximately 30 μm, as shown in the cross-section photograph in the lower right, and its width was approximately 100 μm.

[0093] Example 5 (mechanical properties of glass) (Measurement of Young's modulus and Poisson's ratio) The Young's modulus and Poisson's ratio of the glasses prepared in Examples 1 to 3 were measured using the ultrasonic pulse method. The ultrasonic pulse method involves transmitting an ultrasonic pulse through a sample and calculating the Young's modulus and Poisson's ratio from the propagation velocities of longitudinal and shear waves propagating within the sample. Referring to Figures 5(a)-(d), the left side of the photograph in Figure 5(a) shows a pulser receiver (5072 PR, Olympus NDT), and the right side shows an oscilloscope (WJ312A, LECROY). Figure 5(b) shows a longitudinal wave transducer (V110, 5 MHz). The shear wave transducer was V156, 5 MHz. Figure 5(c) shows an example of the waveform data obtained. As shown in Figure 5(d), a glass sample that has been processed to a specified shape and size and mirror-polished is fixed to a laboratory bench with adhesive to increase adhesion, and a specified ultrasonic wave is applied to the sample from a pulse generator. The vibration of the sample is measured with an oscilloscope, and the Young's modulus and Poisson's ratio of the sample can be calculated from the obtained waveform. This Young's modulus and Poisson's ratio were measured at room temperature (25°C).

[0094] The density of the sample was measured by gas phase substitution using an ultrapycnometer. As shown in Figure 6(a), the measurement sample was placed in the sample chamber on the left, and N2 gas was supplied from the expansion chamber on the right to perform gas phase substitution. Figure 6(b) shows the sample to be measured, in this case the sample with composition No. 5: 40Ag2O-20WO3-40P2O5 used in the actuator fabrication. The ultrapycnometer device used, ULTRAPYCNOMETER 1000 (Quantachrome), is shown in Figure 6(c). The measurement conditions were 1 min. / measurement, 3 measurements were performed 3 times, and the average value was calculated.

[0095] Young's modulus and Poisson's ratio are expressed by the following formulas.

number

[0096] The measured samples and the measurement results are shown in Table 2. The samples were No. 1: 40Ag2O-20MoO3-40P2O5, No. 2: 40Ag2O-16.7MoO3-3.3WO3-40P2O5, No. 3: 40Ag2O-10MoO3-10WO3-40P2O5, No. 4: 40Ag2O-3.3MoO3-16.7WO3-40P2O5, and No. 5: 40Ag2O-20WO3-40P2O5. [Table 2] In the glass compositions in Table 2, Ag, Mo, W, and P represent Ag2O, MoO3, WO3, and P2O5, respectively, and the numbers represent the molar ratios.

[0097] Young's modulus was measured for sample No. 5: glass having a composition of 40Ag2O-20WO3-40P2O5 (glass of Example 1) at a density of 4700 kg / m 3 The Young's modulus was calculated to be 35 GPa. However, since the density of samples No. 1 to No. 4 was not measured, the Young's modulus was not calculated.

[0098] Since typical alkali silicate glass has a Poisson's ratio of approximately 0.22 and a Young's modulus of approximately 75 GPa, it can be seen that the phosphate-based glass of Example 3 has a larger Poisson's ratio and a significantly lower Young's modulus than silicate glass. Therefore, when the same level of charge polarization is induced in an actuator element, a glass actuator element using a glass layer according to an example of the present disclosure can achieve a larger displacement (deformation) by the amount corresponding to the difference in Poisson's ratio and Young's modulus compared to silicate glass when using a phosphate-based glass. In other words, the phosphate-based glass according to the present disclosure retains its strength as glass, allowing it to withstand high loads that cannot be achieved by polymer actuator elements, and also enabling it to achieve large displacements that cannot be achieved by alkali silicate glass, thereby improving its practicality as a glass actuator element.

[0099] Example 6 (Electrical properties of glass) The ionic conductivity and dielectric constant of Sample No. 5 (glass having a composition of 40Ag2O-20WO3-40P2O5) prepared in Example 1 were measured. The ionic conductivity was measured by the two-terminal method using an impedance analyzer. The dielectric constant can be derived from the analysis of the ionic conductivity measurement. All measurements in Example 6 were carried out at room temperature (25°C).

[0100] As a result, the ionic conductivity was 5.00 × 10 at room temperature (25°C). ―7 S / cm, and the relative dielectric constant was 100 to 200 at 100 Hz, as shown in Figure 7. In phosphate glasses other than Sample No. 5, 40Ag2O-20MO x Since these glasses have a composition of -40P2O5 (M is one or more metal elements, and x is the molar ratio for electrical neutrality in MOx), the ionic conductivity of these glasses can be considered to be equivalent to that of sample No. 5.

[0101] Typical alkali silicate glasses do not exhibit significant electrical conductivity (ionic conductivity) unless heated to around 300°C, so the fact that the phosphate-based glasses of the Examples exhibit significant electrical conductivity (ionic conductivity) at room temperature means that glass actuator elements using the glasses of the Examples of the present invention can be used at room temperature, clearly demonstrating their superiority over the glass actuator element of Patent Document 3. It is also clear that the phosphate-based glasses of the Examples of the present invention exhibit higher electrical conductivity (ionic conductivity) than alkali silicate glasses when heated, and so glass actuator elements using the phosphate-based glasses of the Examples of the present invention are superior to the glass actuator element of Patent Document 3 even when used at high temperatures.

[0102] In addition, the ionic conductivity of the Ag-containing phosphate glass of this example, particularly at room temperature, is as described above. +AgO is a soft acid, i.e., an ion whose electron cloud easily deforms in an electric field. Compared to the ionic conductivity of sodium-containing phosphate-based glasses with the same AgO and NaO content, it always exhibits a higher value (reference: J. Mitroy, MS Safronova, C.W. Clark, “Theory and Applications of Atomic and Ionic Polarizabilities,” J.Phys.B:At.Mol.Opt.Phys., 43(2010)202001), making it a superior glass for glass actuator elements. Furthermore, even when the Ag in the Ag-containing phosphate-based glass of this example is substituted with Cu, it is still superior to the sodium-containing phosphate-based glass for the same reasons as above. Furthermore, when Ag is substituted with potassium, the ionic conductivity does not increase, but the ionic polarizability is 5.4 times greater than that of sodium, increasing the dielectric constant, making it a superior glass for glass actuator elements.

[0103] Furthermore, the Young's modulus of glass can be approximated by the Makishima-Mackenzie formula as the sum of the products of the volume fractions of the constituent components of the glass and the dissociation energies, and Ag2O, Cu2O, and K2O have dissociation energies that are equal to or smaller than Na2O, making them superior as glasses for glass actuator elements in terms of reducing the Young's modulus of phosphate-based glasses.The Poisson's ratio and Young's modulus of Ag-containing phosphate-based glasses were confirmed and evaluated in Example 5.

[0104] Example 7 (Optical properties of glass) Figure 8(a) is a photograph showing the glass compositions prepared in Example 2, 40Ag2O-10WO3-10MoO3-(40-x)TeO2-xP2O5 (mol %), where x = 0, 4, 8, 16, and 40. The glass had a thickness of 1.2 mm. The leftmost glass, with x = 0, is the glass described in Patent Document 1 and is opaque. The photograph to the right shows a glass with a composition in which part of the TeO2 has been replaced with P2O5. It can be seen in Figure 8(a) that the transmittance of the glass improves as the value of x increases.

[0105] Figure 8(b) is a photograph showing glass compositions of 40Ag2O-yMoO3-(20-y)WO3-40P2O5 (mol%), prepared by varying the MoO3 and WO3 contents while setting the TeO2 content to 0, based on the results of Figure 3(a), where the transparency is high when the value of x is large in Figure 8(a). The glass was 1.2 mm thick. The glass on the far left with a composition of y = 0 (40Ag2O-20WO3-40P2O5) was the most transparent. As the value of y increased, the glass's transmittance decreased, but transparency was still evident even at y = 20.

[0106] The results of measuring the optical absorptance of some of the phosphate-based glasses produced in Examples 2 and 3 are shown in Figure 9. As shown in Figure 9, the phosphate-based glasses produced in Examples 2 and 3 have low optical absorption at wavelengths of approximately 500 μm or more, and are therefore highly transparent. In fact, these samples had transparency that allowed the image on the back side of the sample to be clearly visible (see Figures 8(a) and (b)). This type of transparency was not achieved by the glass actuator element of Patent Document 3.

[0107] Example 8 (Preparation of Clad Layer) Using the facing-target sputtering system shown in Figure 10, a TiO2 film was fabricated on a substrate by reactive sputtering of metallic titanium. The facing-target sputtering system shown in Figure 10 holds the substrate in the space on the right side of the vacuum chamber. Oxygen gas can be supplied to this space, which is separated from the space on the left side where the sputtering target is installed by an openable shutter. In the space where the sputtering target is installed on the left side, targets are installed at the top and bottom of the figure, and magnets are placed above and below to create a vertical magnetic field. Ar gas is supplied as an inert gas to the space where the sputtering target is installed on the left side. When a voltage is applied between the substrate as the anode and the target as the cathode, electrons are confined between the targets by the magnetic flux in the space where the sputtering target is installed on the left side, enabling film deposition at low temperatures. Furthermore, the long distance between the target and substrate in this system is expected to result in low-damage film deposition.

[0108] Metallic Ti was used as the target, and oxygen and argon were used as reactive gases. Amorphous TiO2 (hereinafter referred to as cladding layer) was deposited on the substrate by adjusting the flow rate of oxygen gas, target current, and deposition time in particular.

[0109] The deposited cladding layer was analyzed for the XPS spectrum of Ti2p using thin-film XRD, and the film thickness was measured using a film thickness meter (Dekak). Furthermore, the thin-film XRD analysis confirmed that the deposited film was amorphous TiO2.

[0110] FIG. 11 shows the deposition conditions and the thickness of the obtained cladding layer, and FIG. 12 shows a chart of the XPS spectrum of Ti2p obtained by analyzing the cladding layer.

[0111] Figure 11 shows that the cladding layer thickness is 300 nm or less, and further 100 nm or less, and 30 nm or less. Figure 12 also shows that in multiple cladding layers, there is a low binding energy peak at 464.2 eV and a high binding energy peak at 458.6 eV, indicating that the material is in the TiO2 state. Amorphous TiO2 does not exhibit a glass transition and is not glass.

[0112] 13 shows an example of a thin film XRD of amorphous TiO2, and it is known that the relative dielectric constant of amorphous TiO2 is 10 to 100, while the relative dielectric constant of rutile (polycrystalline) TiO2 is 120. Since insulating or low-conductivity glasses used as cladding layers generally have a relative dielectric constant less than 10 (usually less than 5), the relative dielectric constant of the amorphous TiO2 produced in Example 8 is significantly greater than the relative dielectric constant of such glasses (at least the cladding glass of Patent Document 3).

[0113] The cladding layer produced in Example 8 was confirmed to be an electrical insulator and a dielectric by measuring its electrical resistance.

[0114] According to Example 8, a thin cladding layer that is both an insulator and a dielectric and has a high dielectric constant can be deposited using vapor deposition, and the adhesion to the glass layer is also excellent. The significance of being able to form a thin cladding layer that is both an insulator and a dielectric with a high dielectric constant in a glass actuator element is clear. If the cladding layer is an insulator, there is no power loss, and because it has a high dielectric constant and is thin, the effective voltage acting on the glass layer out of the applied voltage can be increased, thereby improving the power efficiency and performance of the glass actuator element.

[0115] Example 9 (glass actuator element) Referring to Figure 14, as can be seen in the upper left diagram, the beam (cantilever) of the actuator element is composed of a 30 μm glass layer, a 60 nm thick cladding layer, and an aluminum electrode layer. One end of this beam is fixed to a base, the surface of which is pre-coated with an Ag paste electrode, onto which one end of the beam is fixed. The length of the part of the beam not fixed to the base is 20 mm, and the width is 0.5 mm.

[0116] where: Actuator length: a = 20 (mm) Glass layer thickness: h=30×10 -6 (m) Cladding layer thickness: t = 60 × 10 -9 (m) Dielectric constant of glass layer: ε Core =1400ε0 Dielectric constant of the cladding layer: ε Clad =10ε0 Voltage between electrodes: V=2(V) Thickness of the unevenly distributed layer: δ = 1 / 10 h (assumed) Ag ion radius: r = 1.26 × 10 -19 (m) Elementary charge: e = 1.6 × 10 -19 (C) Then,

[0117] The radius of curvature of the cantilever [m] is

number

number

[0118] Example 10 (Vibration measurement of glass actuator element) The glass produced in Example 1 was used and processed as in Example 4. A clad layer was deposited on the resulting glass beam as in Example 8, and an electrode layer was then formed to produce a glass actuator element, and vibration measurements were performed using a laser Doppler vibrometer.

[0119] Referring to Figure 15(a), the glass actuator element is a cantilever made of a laminate consisting of a glass layer of 40Ag2O-20WO3-40P2O5 (mol%) glass, a clad layer of amorphous TiO2, and an electrode layer of aluminum. The glass layer is 30 μm thick, the clad layers are each 60 nm thick, the cantilever is 0.5 mm wide, one end of the cantilever is fixed to a base, and the length of the freely movable part of the cantilever is 4 mm.

[0120] The glass actuator element has an Ag film coated on the joint of the base and is connected to the lower electrode layer of the cantilever laminate, and wiring is provided to the upper electrode of the cantilever laminate, so that a voltage can be applied between the electrode layers, and when a voltage is applied, the beam part of the glass actuator element can be displaced. In this example, when an AC voltage of 0.1 to 1.5 V with an AC field frequency of 1 to 2500 Hz is applied to the glass actuator element, the beam part of the glass actuator element vibrates.

[0121] Referring to Figure 15(a), a laser Doppler vibrometer uses a sensor head (Polytec GmnH CLV700) positioned above the cantilever of a glass actuator element as a laser light source. The laser Doppler vibrometer controller (CFV2500) controls the laser light to illuminate a specific position on the cantilever, which is vibrating due to the application of an AC voltage. The frequency of the reflected light from the cantilever is observed with the same sensor head, and the Doppler-shifted reflected light is measured and analyzed with an FFT analyzer (OROS OR34), which outputs the velocity and displacement of the cantilever (target object). Figure 15(b) shows a schematic diagram of the common vibration modes (primary and secondary vibrations) of a cantilever. The waveforms are for the primary and secondary natural frequencies.

[0122] Figures 16(a) and 16(b) show photographs illustrating the measurement process. In Figure 16(a), four samples (No. 1–No. 4) of the same actuator element are fixed in a row to the left edge of the black base (shown on the right). A freely vibrating beam (cantilever) protrudes from the left side of the base. The actuator element's underside is connected to a thin-film electrode formed on the surface of the base, and its top surface is connected to wiring extending from the four electrode terminals on the left side of the figure. Sound-absorbing material is laid between the base and the electrode terminals. Figure 16(b) shows how the Doppler effect is measured by shining a laser beam from above the cantilever of the sample shown in Figure 16(a) (shown in the lower right) and observing the reflected light. Figure 16(c) shows an example graph showing the change in amplitude versus measurement frequency. Significant noise is observed at low frequencies, which is likely due to the effect of DC voltage on AC voltage, and is therefore ignored in the analysis of AC vibration.

[0123] In this way, the frequency dependence, vibration shape, and voltage dependence were measured using a laser Doppler vibrometer.

[0124] As a result, the natural frequencies of the glass actuator were found to be 757 Hz for the primary vibration (measured by impact excitation method) and 5306 Hz for the secondary vibration (calculated from the measurement results).

[0125] Figures 17(a) and (b) show the measurement results of the dependence of the vibration frequency on the applied voltage frequency. Figure 17(a) is a graph showing the vibration velocity of the cantilever observed when the applied AC frequency was 10 Hz, with the observed frequency on the horizontal axis; the cantilever vibration frequency was 20 Hz. Figure 17(b) is a similar graph showing the vibration frequency observed when the applied AC frequency was changed; it can be seen that the observed vibration frequency is twice the applied AC frequency.

[0126] Figure 18 shows the measurement results of the frequency dependence of amplitude. Figure 18 is a graph showing the amplitude of cantilever vibration on the vertical axis versus the observed frequency on the horizontal axis, with an enlarged graph of amplitude also shown for the observation frequency range of 15,000 Hz to 5,500 Hz. This amplitude (displacement) was calculated based on D = V / 2πf (D is displacement, V is voltage, and f is frequency). The horizontal axis is the observed frequency at which vibration was observed, which is twice the frequency of the applied AC electric field.

[0127] According to Figure 18, there is a large peak at 758 Hz, which coincides with the primary natural frequency of 757 Hz measured by striking the cantilever, and there is also a small peak at 5000 Hz, which coincides with the secondary natural frequency of 5306 Hz measured by striking the cantilever. It can be seen that the amplitude increases due to resonance at the primary and secondary natural frequencies.

[0128] Figures 19(a) and 19(b) show the measurement results of the vibration shape. Figures 19(a) and 19(b) are graphs showing the observed amplitude on the vertical axis against the distance from the base of the cantilever on the horizontal axis. Figure 19(a) shows the amplitude when the applied AC field frequency is 10 Hz, and Figure 19(b) shows the amplitude when the applied AC field frequency is 2500 Hz. Figures 19(a) and 19(b) show primary vibration at the low frequency of 10 Hz, and secondary vibration at the high frequency of 2500 Hz.

[0129] Figure 20 shows the measurement results for the voltage dependence of amplitude. Figure 20 shows the measurement results when the applied voltage frequency is 380 Hz, and the horizontal axis is the square of the applied voltage V (V 2 ), and the vertical axis represents the amplitude (nm). According to FIG. 20, the amplitude of the cantilever is the square of the applied voltage V (V 2 ) The amplitude of this cantilever is proportional to the square of the applied voltage V (V 2 It has been confirmed that the proportional relationship between the applied voltage frequency and the applied voltage is also the same when the applied voltage frequency is other than 380 Hz.

[0130] From the measurement results of Example 10, particularly Figure 20, it is believed that the driving principle of the cantilever (glass actuator element) of Example 10 is the so-called "electrostrictive effect." This is a phenomenon in which, when an electric field is applied to a dielectric, a strain proportional to the square of the electric field occurs, and this phenomenon occurs in all dielectrics, including crystals with centrosymmetrical properties and isotropic solids. Furthermore, based on previous research on the electrostrictive effect of glass (ionic polarization) by V. Sundar, R. Yimnirun, B. G. Itken, and RE Newnham, Materials Research Bulletin. 1998, Vol. 33, No. 9, pp. 1307-1314, it is believed to be the electrostrictive effect.

[0131] At this time, the polarization of the glass actuator element is + The strain s of the cantilever due to the electrostrictive effect is

number

[0132] (Details of Doppler effect measurement) The details of the Doppler effect measurement described above are described below. As shown in Figure 16, an AC electric field was applied to four actuator elements (cantilever samples No. 1-No. 4), and the vibration of the actuator elements was measured using the Doppler effect. Samples No. 1-No. 4 are the same cantilevers as described in Example 10, except for their cantilever lengths. Displacement was calculated using the velocity value of the displacement output based on the Doppler effect measurement. If the displacement is expressed as a sinusoidal wave with a single frequency, it can be calculated using D = V / 2πf (D is displacement, V is voltage, and f is frequency). Figure 16(c) shows the cantilever amplitude (vertical axis) versus the frequency of the vibration observed in the cantilever when sample No. 4 was driven under conditions of an applied voltage of 1.5 V and an applied AC electric field frequency of 10 Hz. Significant noise was observed at low observation frequencies below 10 Hz. This is thought to be due to the effect of DC on the AC behavior of the applied voltage at low frequencies, and is therefore ignored as noise in this analysis, which analyzes the effect of AC applied voltage.

[0133] (Experiment 1) For cantilever sample No. 4, the driving conditions of the element were AC 1.5V, and the applied AC electric field frequencies were 5Hz, 10Hz, 20Hz, 30Hz, 40Hz, and 60Hz. Laser light was irradiated onto each of positions P1 to P20 (each of the 19 equal positions of the 6 mm length) of the cantilever (vibration length 6 mm) shown in the plan view of Figure 21-1(a), and the reflected light was analyzed to determine the displacement velocity at each of positions P1 to P20.

[0134] Figure 21-1(b) shows the displacement velocity at positions P5, P11, and P17 versus the observed frequency when an AC field frequency of 5 Hz is applied. For reference, the bottom chart, V=0, shows the measurement results when the applied voltage is 0. However, as can be seen in the V=0 chart, noise (peaks) exist near 50 Hz even when the applied voltage is 0. This is thought to be due to the surrounding current, so the peak near 50 Hz in the measurement chart when voltage is applied is ignored as noise. In Figure 21-1(b), 10 Hz vibrations (peaks in displacement velocity) were observed at positions P5, P11, and P17. While Figure 21-1(b) shows the results for only positions P5, P11, and P17, sample No. 4 exhibited 10 Hz vibrations at all positions P1 through P20, indicating that the cantilever vibrated as a single unit.

[0135] Figure 21-2(c) shows the displacement velocity versus frequency (hereinafter simply referred to as the observed frequency) when the applied AC electric field frequency is 5 Hz, 10 Hz, 20 Hz, 30 Hz, 40 Hz, and 60 Hz, and the observed displacement velocity is Fourier transformed from the observed time change (i.e., vibration). Figure 21-2(d) plots the relationship between the applied AC electric field frequency at which the displacement velocity peak appears and the observed frequency, based on the peaks observed in Figure 21-2(c). Figures 21-2(c) and 21-2(d) show that in all cases, the observed frequency peaks are twice the applied AC electric field frequency.

[0136] Figure 21-3(e) plots the cantilever amplitude at measurement positions P1 to P20 for cantilever sample No. 4 when the applied AC field frequency is 5 Hz, 10 Hz, 20 Hz, 30 Hz, 40 Hz, and 60 Hz. At all applied AC field frequencies, the observed amplitude increases as the distance from the fixed end of the cantilever to measurement positions P1 to P20 increases, i.e., from P1 to P20.

[0137] (Experiment 2) As in Experiment 1, except for Sample No. 3, the driving conditions of the element were AC 1.5 V and the applied AC electric field frequency was 10 Hz. Laser light was irradiated onto the free end of the cantilever (vibration length 4 mm) shown in the plan view of Figure 22(a), and the reflected light was analyzed to determine the displacement velocity.

[0138] The results are shown in Figure 22(b), which is a chart showing the displacement velocity versus the observed frequency, similar to Figure 21-2(b), and shows that the displacement velocity peaks at 20 Hz when the applied AC field frequency is 10 Hz.

[0139] Next, as shown in Figure 22(c), the fixed end of the cantilever of sample No. 3 was designated P1 and the free end was designated P10. Laser light was irradiated at each of the nine positions P1 to P10 along the length, as in Experiment 1, and the amplitude at positions P1 to P10 was calculated from the analysis of the reflected light.

[0140] The results are shown in Figure 22(d), where the amplitude at each measurement position P1 to P10 is plotted. As shown in Figure 22(d), as the distance from the fixed end of the cantilever to measurement positions P1 to P10 increases, the observed amplitude increases from P1 to P10, just as in Figure 21-3(e).

[0141] Based on the results of Experiments 1 and 2, the cantilever lengths (longer sides, i.e., the length of the vibrating portion) and the amplitude of the cantilever tip in Samples No. 3 and No. 4 are compared and shown in Table 3 below. (Table 3) Sample No. No.3 No.4 Cantilever length: Approx. 4 mm Approx. 6 mm Tip amplitude 71.3mm 218mm

[0142] Comparing sample No. 3 and sample No. 4, it can be seen that the longer the cantilever, the larger the amplitude at the tip. However, the measured amplitude is affected by the measurement environment, particularly the instability of the cantilever fixation, so the reliability of the difference in the absolute value of the amplitude is low.

[0143] (Experiment 3) As in Experiment 2, for cantilever sample No. 3, the driving conditions of the element were AC 1.5 V and the applied AC electric field frequency was 10 Hz to 520 Hz. Laser light was irradiated onto the free end of the cantilever (vibration length 4 mm). The reflected light was analyzed to determine the displacement velocity, and the amplitude of the cantilever tip was calculated from the measured value.

[0144] Figure 23(a) shows the amplitude of the cantilever tip obtained, plotted against the observed frequency. Also shown in Figure 23(a) is the result of measuring the amplitude of the cantilever tip when the cantilever of the same sample No. 3 was struck and vibrated, with the observed frequency plotted on the horizontal axis.

[0145] In the diagram of FIG. 23(a), noise is large at low frequencies in all charts, but as can be seen in FIG. 16(c), low frequency noise is common in vibration measurements in this example and can be ignored.

[0146] According to Figure 23(a), the vibrations induced by the electric field in the cantilever of sample No. 3 and the vibrations induced by impact are almost perfectly consistent, and it can be seen that the amplitude peak at the observed frequency of 844 Hz (applied electric field frequency of 422 Hz) is the natural frequency of the cantilever.

Claims

1. The glass substrate includes glass layers having opposing surfaces, and electrode layers provided on each of the opposing surfaces of the glass layers, the glass layer is a phosphate-based glass containing at least one metal selected from Ag, Cu, and K, and / or a clad layer made of a dielectric material and having a thickness of less than 10 μm is provided between the glass layer and the electrode layer; Capable of electro-mechanical energy conversion, A glass actuator element characterized by:

2. The phosphate glass is P ２ O ５ 2. The glass actuator element according to claim 1, comprising 30 mol % or more of

3. The phosphate glass is Ag ２ 2. The glass actuator element according to claim 1, containing O at 5 mol % or more, preferably 10 mol % or more, and more preferably 20 mol % or more.

4. The phosphate glass is Ag ２ O and P ２ O ５ In addition, MoO ３ , W.O. ３ , TeO ２ , B ２ O ３ 2. The glass actuator element according to claim 1, comprising at least one oxide selected from the group consisting of:

5. 5. A glass actuator element according to claim 1, wherein the glass layer has a Young's modulus of 65 GPa or less and / or a Poisson's ratio of 0.27 or more.

6. 10. The glass actuator element of claim 1, wherein the glass layer is transparent.

7. 2. The glass actuator element according to claim 1, wherein the dielectric of the cladding layer is made of a crystalline or amorphous inorganic material.

8. The dielectric of the cladding layer is TiO ２ , BaTiO ３ , SrTiO ２ , Al ２ O ３ , MgO, ZrO ２ , MgAl ２ O ４ , RNbO ３ 2. The glass actuator element according to claim 1, wherein R is selected from the group consisting of Li, Na, and K, and a combination thereof.

9. 9. A glass actuator element according to claim 1, wherein the cladding layer has a higher dielectric constant than the glass layer.

10. A glass actuator element according to any one of claims 1 to 4 and 6 to 8, wherein the cladding layer has a thickness of less than 1 µm.

11. The glass actuator element according to any one of claims 1 to 4 and 6 to 8, wherein the cladding layer is an electrical insulator.

12. providing glass layers having opposing surfaces; forming an electrode layer on each of opposing surfaces of the glass layer; the glass layer is formed from a phosphate-based glass containing at least one metal selected from Ag, Cu, and K, and / or a clad layer made of a dielectric material and having a thickness of less than 10 μm is formed between the glass layer and the electrode layer by a vapor deposition method; Producing a glass actuator element capable of electromechanical energy conversion; A method for manufacturing a glass actuator element, comprising:

13. 13. The method of claim 12, wherein the thickness of the cladding layer is less than 10 μm, preferably less than 1 μm.

14. 14. The method of claim 12 or 13, wherein the cladding layer is an electrical insulator.

Images