Glass material as well as preparation method and application thereof

Abstract

The invention discloses a glass material as well as a preparation method and application thereof. The glass material provided by the invention comprises the following components by mole percent: 5-25% of lanthanum oxide; 40%-70% of bismuth oxide; 15%-40% of boron oxide; 0 to 10% of zirconium dioxide; 0 to 10% of tin dioxide; and 0 to 10% of neodymium oxide. The preparation method of the glass material comprises the following steps: 1) mixing all the raw materials, and grinding to prepare a mixture; and 2) melting the mixture, cooling to form a glass block, and carrying out ball milling to obtain a powdery glass material, or melting the mixture, injecting into a mold for molding, annealing, cutting and polishing to obtain a molded glass material. The glass material disclosed by the invention is relatively large in relative dielectric constant, low in dielectric loss, free of toxic elements, relatively low in melting temperature, relatively low in production cost, convenient to prepare a thin film and suitable for electronic packaging and glass thin film chip capacitors.

Description

Technical Field

[0001] The present invention relates to the technical field of dielectric materials, and in particular to glass materials and preparation methods and applications thereof. Background Art

[0002] Dielectric capacitors are a common type of capacitor. Dielectric materials directly affect the performance of dielectric capacitors. At present, dielectric materials can generally be divided into the following three types: 1) Ceramic dielectric materials: high relative dielectric constant (ε r >100), but the dielectric loss is high and the breakdown strength is low (<500kV / cm); 2) Polymer dielectric material: The dielectric breakdown strength is very high (1MV / cm~10MV / cm), but the relative dielectric constant is small (ε r <10), and the operating temperature range is small (<200°C); 3) Glass dielectric material: the dielectric breakdown strength is very high (1MV / cm~20MV / cm), the dielectric loss is low (<10 -3 ), good temperature stability, but low dielectric constant. In summary, existing dielectric materials have obvious disadvantages, and the dielectric capacitors made of them are still difficult to fully meet the growing practical application requirements.

[0003] In recent years, with the rapid development of microwave communication industry, electronic devices tend to be miniaturized. Single-layer capacitors are more in line with the requirements of high-frequency electronic circuits than multilayer capacitors due to their advantages such as low dielectric loss and no crosstalk effect. The high dielectric breakdown and low dielectric loss characteristics of glass are very consistent with the performance requirements of single-layer capacitors.

[0004] Therefore, it is of great significance to develop a glass dielectric material that has low dielectric loss and maintains a high dielectric constant. Summary of the invention

[0005] The object of the present invention is to provide a glass material and a preparation method and application thereof.

[0006] The technical solution adopted by the present invention is:

[0007] The present invention provides a glass material comprising the following components in molar percentage:

[0008] Lanthanum oxide: 5% to 25%;

[0009] Bismuth oxide: 40% to 70%;

[0010] Boron oxide: 15% to 40%;

[0011] Zirconium dioxide: 0-10%;

[0012] Tin dioxide: 0-10%;

[0013] Neodymium trioxide: 0-10%, of which:

[0014] The molar ratio of lanthanum oxide to boron oxide is 0.13 to 1.60:1;

[0015] The molar ratio of bismuth oxide to boron oxide is 1 to 4.6:1;

[0016] The ratio of the total molar amount of bismuth oxide and boron oxide to the total molar amount of zirconium dioxide, tin dioxide and neodymium trioxide is 2.5 to 11:1;

[0017] The method for preparing the glass material comprises the following steps:

[0018] 1) mixing lanthanum oxide, bismuth oxide, boron oxide, zirconium dioxide, tin dioxide and neodymium trioxide and grinding them to obtain a mixed material;

[0019] 2) Melting the mixture at 1000°C to 1200°C, cooling it to form a glass block, and then ball milling it to obtain a powdered glass material;

[0020] Alternatively, the mixture is melted at 1000°C to 1200°C, quickly poured into a preheated graphite mold for molding, annealed at 300°C to 500°C for 60 minutes, and then cut and polished to obtain a molded glass material with a thickness of 3 mm.

[0021] Preferably, the molar ratio of lanthanum oxide to boron oxide is 0.2 to 1:1.

[0022] More preferably, the molar ratio of lanthanum oxide to boron oxide is 0.3-0.7:1.

[0023] Preferably, the molar ratio of bismuth oxide to boron oxide is 2 to 4:1.

[0024] More preferably, the molar ratio of bismuth oxide to boron oxide is 2.2 to 3:1.

[0025] Preferably, the ratio of the total molar amount of bismuth oxide and boron oxide to the total molar amount of zirconium dioxide, tin dioxide and neodymium trioxide is 4.5 to 10:1.

[0026] More preferably, the ratio of the total molar amount of bismuth oxide and boron oxide to the total molar amount of zirconium dioxide, tin dioxide and neodymium trioxide is 5 to 9.5:1.

[0027] The present invention also provides a packaging glass powder, comprising the above-mentioned glass material.

[0028] The present invention also provides a solar cell comprising the above-mentioned glass material.

[0029] The present invention also provides a capacitor comprising the above-mentioned glass material.

[0030] The beneficial effects of the present invention are: the relative dielectric constant of the glass material of the present invention is greater than 20 (1MHz), the dielectric loss is less than 3.5×10 -3 (1MHz), does not contain toxic elements, has a low melting temperature, low production cost, and is easy to prepare thin films. It is suitable for electronic packaging and glass film chip capacitors. BRIEF DESCRIPTION OF THE DRAWINGS

[0031] In order to more clearly illustrate the embodiments of the present invention or the technical solutions in the prior art, the drawings required for use in the embodiments will be briefly introduced below. Obviously, the drawings described below are only some embodiments of the present invention. For ordinary technicians in this field, other drawings can be obtained based on these drawings without paying creative labor.

[0032] Figure 1 : are XRD patterns of the glass materials of Examples 1 to 4. DETAILED DESCRIPTION

[0033] The following will be combined with the drawings in the embodiments of the present invention to clearly and completely describe the technical solutions in the embodiments of the present invention. Obviously, the described embodiments are only part of the embodiments of the present invention, not all of the embodiments. Based on the embodiments of the present invention, all other embodiments obtained by ordinary technicians in this field without creative work are within the scope of protection of the present invention.

[0034] The purpose of the present invention is to provide a glass material and a preparation method and application thereof, so as to solve the problems existing in the prior art.

[0035] In order to make the above-mentioned objects, features and advantages of the present invention more obvious and easy to understand, the present invention is further described in detail below with reference to the accompanying drawings and specific embodiments.

[0036] Embodiment 1:

[0037] A glass material, the composition of which is shown in the following table:

[0038] Table 1 Composition of a glass material

[0039] Components Mole percentage (%) <![CDATA[Lanthanum Oxide (La2O3)]]> 16.6 <![CDATA[Bismuth oxide (Bi2O3)]]> 66.4 <![CDATA[Boron Oxide (B2O3)]]> 17

[0040] The method for preparing the glass material comprises the following steps:

[0041] 1) mixing lanthanum oxide, bismuth oxide and boron oxide and grinding them to obtain a mixed material;

[0042] 2) The mixture is melted at 1000° C. to 1200° C., and then quickly poured into a graphite mold preheated to 370° C. for molding, and then annealed at 420° C. to 470° C. for 60 min, and then cut and polished to obtain a molded glass material (thickness of 3 mm).

[0043] Embodiment 2:

[0044] A glass material, the composition of which is shown in the following table:

[0045] Table 2 Composition of a glass material

[0046] Components Mole percentage (%) <![CDATA[Lanthanum Oxide (La2O3)]]> 15.1 <![CDATA[Bismuth Oxide (Bi2P3)]]> 40.4 <![CDATA[Boron Oxide (B2O3)]]> 35.5 <![CDATA[Zirconium dioxide (ZrO2)]]> 9

[0047] The method for preparing the glass material comprises the following steps:

[0048] 1) mixing lanthanum oxide, bismuth oxide, boron oxide and zirconium dioxide and grinding them to obtain a mixed material;

[0049] 2) The mixed material is melted at 1000° C. to 1200° C., and then quickly poured into a graphite mold preheated to 400° C. for molding, and then annealed at 450° C. to 500° C. for 60 min, and then cut and polished to obtain a molded glass material (thickness of 3 mm).

[0050] Embodiment 3:

[0051] A glass material, the composition of which is shown in the following table:

[0052] Table 3 Composition of a glass material

[0053] Components Mole percentage (%) <![CDATA[Lanthanum Oxide (La2O3)]]> 7.3 <![CDATA[Bismuth oxide (Bi2O3 ) > 60.4 <![CDATA[Boron Oxide (B2O3 ) > 23.3 <![CDATA[Tin dioxide (SnO2)]]> 9

[0054] The method for preparing the glass material comprises the following steps:

[0055] 1) mixing lanthanum oxide, bismuth oxide, boron oxide and tin dioxide and grinding them to obtain a mixed material;

[0056] 2) The mixed material is melted at 1000° C. to 1200° C., and then quickly poured into a graphite mold preheated to 350° C. for molding, and then annealed at 400° C. to 450° C. for 60 min, and then cut and polished to obtain a molded glass material (thickness of 3 mm).

[0057] Embodiment 4:

[0058] A glass material, the composition of which is shown in the following table:

[0059] Table 4 Composition of a glass material

[0060] Components Mole percentage (%) <![CDATA[Lanthanum Oxide (La2O3)]]> 22.7 <![CDATA[Bismuth oxide (Bi2O3)]]> 40.4 <![CDATA[Boron Oxide (B2O3)]]> 27.9 <![CDATA[Neodymium(III) oxide (Nd2O3)]]> 9

[0061] The method for preparing the glass material comprises the following steps:

[0062] 1) mixing lanthanum oxide, bismuth oxide, boron oxide and neodymium trioxide and grinding them to obtain a mixed material;

[0063] 2) The mixed material is melted at 1000° C. to 1200° C., and then quickly poured into a graphite mold preheated to 400° C. for molding, and then annealed at 450° C. to 500° C. for 60 min, and then cut and polished to obtain a molded glass material (thickness of 3 mm).

[0064] Performance Test:

[0065] 1) The X-ray diffraction (XRD) patterns of the glass materials of Examples 1 to 4 are as follows: Figure 1 shown.

[0066] Depend on Figure 1 It can be seen that the glass materials of Examples 1 to 4 have no obvious crystallization phase.

[0067] 2) The performance test results of the glass materials of Examples 1 to 4 are shown in the following table:

[0068] Table 5 Performance test results of glass materials of Examples 1 to 4

[0069] Test items Example 1 Example 2 Example 3 Example 4 Glass transition temperature(℃) 577 576 581 567 Relative dielectric constant / 1MHz 23 26 28 34 <![CDATA[Dielectric loss / 1MHz (×10 -3 )]]> 2.2 3.3 1.8 3.4 <![CDATA[Resistivity (×10 11 ·cm)]]> 10.6 6.0 10.1 5.7 Hardness(GPa) 5.3 6.3 5.8 5.9 <![CDATA[Density (g / cm 3 )]]> 5.15 5.21 5.46 5.93

[0070] Note:

[0071] Glass transition temperature: refer to IOS11357-2, GB / T19466.2-2004 and other standards, use the equal distance method to find the midpoint of the straight line parallel to the baseline before and after the first endothermic peak on the DSC curve, and use the abscissa temperature corresponding to the midpoint as the T of the glass material sample. g ;

[0072] Relative dielectric constant and dielectric loss: The capacitance and dielectric loss of the glass material samples were tested using the E4990A impedance analyzer from Keysight, USA. The test frequency range was 1000Hz~1MHz and the test temperature was room temperature. Since the crystallization temperature of the Bi-based glass sample was lower than the sintering temperature of the silver paste, it was impossible to plate the electrode by screen printing. Therefore, the glass material sample was first polished to a thickness of about 2mm, ultrasonically cleaned and placed in a drying oven at 120°C for drying. Then, a high vacuum resistance evaporation coating machine was used to plate silver electrodes on both sides of the glass. The electrode size was 5mm×5mm. Finally, the relative dielectric constant k of the glass material sample was calculated using the formula;

[0073] Resistivity: The IV curve of the glass material sample was tested using a Keithley 2450 source meter with a voltage range of 0 to 200 V. The resistance under 100 V voltage was selected, and the volume resistivity ρ of the glass material sample was finally calculated using the formula;

[0074] Hardness: The glass material samples were finely polished to a mirror surface, and then the Vickers hardness of the glass material samples was tested using the Wilson-Wolpert Tukon2100B microhardness tester from Instron. The selected load was 1 kg, and the holding time was 10 seconds. The Vickers hardness of the glass material samples was calculated using the formula by measuring the length of the two diagonals of the indentation. Five positions were randomly selected for testing on each sample, and the average value was taken as the hardness value of the glass material sample.

[0075] Density: The Archimedes drainage method is used to test the volume density of glass material samples.

[0076] It can be seen from Table 5 that the glass materials of Examples 1 to 4 have excellent dielectric properties, with relative dielectric constants of 23 to 34 and dielectric losses of 1.8×10 -3 ~3.4×10 -3 , indicating that it has great application potential in electronic packaging and thin film chip capacitors.

[0077] The above embodiments are preferred implementation modes of the present invention, but the implementation modes of the present invention are not limited to the above embodiments. Any other changes, modifications, substitutions, combinations, and simplifications that do not deviate from the spirit and principles of the present invention should be equivalent replacement methods and are included in the protection scope of the present invention.

Claims

1. A glass material, characterized in that: The following components are included in mole percentage: Lanthanum oxide: 5% to 25%; Bismuth oxide: 40% to 70%; Boron oxide: 15% to 40%; Zirconium dioxide: 0-10%; Tin dioxide: 0-10%; Neodymium trioxide: 0-10%, of which: The molar ratio of lanthanum oxide to boron oxide is 0.13 to 1.60:1; The molar ratio of bismuth oxide to boron oxide is 1 to 4.6:1; The ratio of the total molar amount of bismuth oxide and boron oxide to the total molar amount of zirconium dioxide, tin dioxide and neodymium trioxide is 2.5 to 11:1; The method for preparing the glass material comprises the following steps: 1) mixing lanthanum oxide, bismuth oxide, boron oxide, zirconium dioxide, tin dioxide and neodymium trioxide and grinding them to obtain a mixed material; 2) Melting the mixture at 1000°C to 1200°C, cooling it to form a glass block, and then ball milling it to obtain a powdered glass material; Alternatively, the mixture is melted at 1000°C to 1200°C, quickly poured into a preheated graphite mold for molding, annealed at 300°C to 500°C for 60 minutes, and then cut and polished to obtain a molded glass material with a thickness of 3 mm.

2. The glass material according to claim 1, characterized in that: The molar ratio of the lanthanum oxide to the boron oxide is 0.2 to 1:

1.

3. The glass material according to claim 2, characterized in that: The molar ratio of the lanthanum oxide to the boron oxide is 0.3-0.7:

1.

4. The glass material according to claim 1, characterized in that: The molar ratio of bismuth oxide to boron oxide is 2 to 4:

1.

5. The glass material according to claim 4, characterized in that: The molar ratio of the bismuth oxide to the boron oxide is 2.2 to 3:

1.

6. The glass material according to claim 1, characterized in that: The ratio of the total molar amount of bismuth oxide and boron oxide to the total molar amount of zirconium dioxide, tin dioxide and neodymium trioxide is 4.5 to 10:

1.

7. The glass material according to claim 6, characterized in that: The ratio of the total molar amount of bismuth oxide and boron oxide to the total molar amount of zirconium dioxide, tin dioxide and neodymium trioxide is 5 to 9.5:

1.

8. A packaging glass powder, characterized in that: A glass material comprising the glass material according to any one of claims 1 to 7.

9. A solar cell, characterized in that: A glass material comprising the glass material according to any one of claims 1 to 7.

10. A capacitor, characterized in that: A glass material comprising the glass material according to any one of claims 1 to 7.

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