A modified titanium dioxide ceramic material with high dielectric constant and preparation method thereof

Abstract

The invention discloses a modified titanium dioxide ceramic material with a high dielectric constant and a preparation method thereof, and relates to the technical field of ceramic materials. The general formula of the ceramic material is (A 0.4 B 0.6 ) x (C 0.5 D 0.5 ) y (Ti 1‑z E z ) 1‑x‑y O2, wherein A is Re, B is at least one of Ba, Ni, and Cu; C is at least one of In, Ho, and Er; D is at least one of Ta, Nb, and V; E is at least one of Zr, Hf, Si, and Ge; x=0.001-0.02, y=0.005-0.15, and z=0.005-0.15. The ceramic material has a high dielectric constant, low dielectric loss, and a high electric field strength resistance.

Description

Technical Field

[0001] The invention relates to the technical field of ceramic materials, and in particular to a modified titanium dioxide ceramic material with a high dielectric constant and a preparation method thereof. Background Art

[0002] With the continuous progress and innovation of semiconductor technology, the microelectronics industry based on the semiconductor industry has made great progress and has become an important pillar of the national economy of various countries. The miniaturization, integration and high density of devices have become important factors in promoting the development of the microelectronics industry, and high dielectric constant materials have also played an increasingly important role in microelectronic devices.

[0003] Titanium dioxide-based ceramic materials with high dielectric constants have been a hot topic in recent years. However, the relative dielectric constant ε of pure titanium dioxide ceramic materials is r It is relatively small, about 90. In order to achieve a high dielectric constant, it is usually necessary to ion-dope the titanium dioxide ceramic material. The existing ion-doped ceramic material apparently exhibits a larger relative dielectric constant ε r value, but the dielectric loss tanδ is also large, and the electric field strength E b The value is low, and thus loses its application value.

[0004] In order to solve the above problems, the Chinese invention patent with authorization announcement number CN104478431B discloses an ion-modified titanium dioxide ceramic material with high dielectric constant and low dielectric loss and its preparation method, which belongs to the field of environmentally friendly dielectric ceramics. The ceramic material described in the invention is represented by the general formula (A 0.5 Nb 0.5 ) x Ti 1-x O2, wherein A is Bi, Al, Ga, Y, Sc, Yb, Dy, Sm, Gd and Pr, 0.005≤x≤0.150 molar content; the ceramic material is prepared by a conventional solid phase sintering process, and different trivalent A elements and the same pentavalent Nb element are added to the general formula ingredients; the dielectric constant of the obtained ceramic material is as high as 10 6 , the dielectric loss is as low as 6%. The ceramics prepared by this invention have great practical value in today's era of miniaturization and lightweight of electronic components. In particular, the devices prepared by this ceramic have practical application value in various electronic devices such as capacitors and dynamic memories. However, its dielectric loss still needs to be further reduced, and the electric field strength needs to be further improved.

[0005] It can be seen that the art still needs a modified titanium dioxide ceramic material with a high dielectric constant, low dielectric loss, and high electric field strength resistance, and a preparation method thereof. Summary of the invention

[0006] The purpose of the present invention is to overcome the shortcomings of the prior art and provide a modified titanium dioxide ceramic material with high dielectric constant, low dielectric loss and high electric field strength resistance and a preparation method thereof.

[0007] To achieve the above object, the technical solution adopted by the present invention is: a modified titanium dioxide ceramic material with a high dielectric constant, the general formula of the ceramic material is (A 0.4 B 0.6 ) x (C 0.5 D 0.5 ) y (Ti 1-z E z ) 1-x-y O2, wherein A is Re, B is at least one of Ba, Ni, and Cu; C is at least one of In, Ho, and Er; D is at least one of Ta, Nb, and V; E is at least one of Zr, Hf, Si, and Ge; x=0.001-0.02, y=0.005-0.15, and z=0.005-0.15.

[0008] Another object of the present invention is to provide a method for preparing the modified titanium dioxide ceramic material with a high dielectric constant, comprising the following steps:

[0009] Step S1, using analytically pure oxide as raw material; mixing the ingredients according to the general metering ratio, and preparing the modified titanium dioxide ceramic dry powder through mixed ball milling, drying, pre-sintering, and secondary ball milling steps;

[0010] Step S2, granulating and molding the modified titanium dioxide ceramic dry powder processed in step S1, debinding the molded body, and then sintering it to obtain a modified titanium dioxide ceramic material with a high dielectric constant.

[0011] Preferably, the ball milling in step S1 is rolling ball milling using anhydrous ethanol as a medium, and the ball milling time is 18-22 hours.

[0012] Preferably, the drying time in step S1 is 15-24 hours and the temperature is 85-95°C.

[0013] Preferably, the pre-calcination temperature in step S1 is 1040-1120° C. and the pre-calcination time is 3-5 hours.

[0014] Preferably, an organic binder is added during the granulation process in step S2.

[0015] Preferably, the mass ratio of the modified titanium dioxide ceramic dry powder to the organic binder is 100:(5-8).

[0016] Preferably, the organic adhesive comprises the following components in parts by weight: 1-3 parts of tea polyphenols, 2-5 parts of diisocyanate polyethylene glycol, 1-3 parts of stevioside, 3-5 parts of water-soluble hyperbranched polyamidoamine, and 100 parts of water.

[0017] Preferably, the number average molecular weight of the diisocyanate polyethylene glycol is 400, and it is provided by Guangdong Wengjiang Chemical Reagent Co., Ltd.

[0018] Preferably, there is no special requirement for the source of the water-soluble hyperbranched polyamidoamine. In one embodiment of the present invention, the water-soluble hyperbranched polyamidoamine is prepared according to the method of Example 1 of the Chinese invention patent with authorization announcement number CN105348542B.

[0019] Preferably, the molding process in step S2 is to press into small discs using a mold; the pressing pressure is 10-20 MPa.

[0020] Preferably, the debinding in step S2 is performed in a vacuum environment, the debinding temperature is 550-650° C., and the debinding time is 2-4 hours.

[0021] Preferably, the sintering temperature in step S2 is 1300-1520° C. and the sintering time is 8-12 hours.

[0022] Due to the application of the above technical solution, the present invention has the following beneficial effects:

[0023] (1) The method for preparing the modified titanium dioxide ceramic material with a high dielectric constant disclosed in the present invention has a simple preparation process, is easy to implement, has good repeatability, a high yield rate, strong practicability, is easy to produce, and has a high value for promotion and application.

[0024] (2) The modified titanium dioxide ceramic material with a high dielectric constant disclosed in the present invention has the general formula (A 0.4 B 0.6 ) x (C 0.5 D 0.5 ) y (Ti 1-z E z ) 1-x-y O2, wherein A is Re, B is at least one of Ba, Ni, and Cu; C is at least one of In, Ho, and Er; D is at least one of Ta, Nb, and V; E is at least one of Zr, Hf, Si, and Ge; x = 0.001 to 0.02, y = 0.005 to 0.15, and z = 0.005 to 0.15. Through the mutual coordination and joint action of the various components, the ceramic material has a high dielectric constant, low dielectric loss, and a high electric field strength resistance.

[0025] (3) The modified titanium dioxide ceramic material with a high dielectric constant disclosed in the present invention, the organic binder comprises the following components by weight: 1-3 parts of tea polyphenols, 2-5 parts of diisocyanate polyethylene glycol, 1-3 parts of stevioside, 3-5 parts of water-soluble hyperbranched polyamide amine, and 100 parts of water. By rationally selecting the types and dosage ratios of each component, the internal density of the ceramic material can be improved, thereby improving the processing performance. In combination with other preparation raw materials, the dielectric constant and electric field strength can be further improved, and the dielectric loss can be reduced.

[0026] (4) The modified titanium dioxide ceramic material with a high dielectric constant disclosed in the present invention has a higher dielectric constant, lower dielectric loss and greater electric field strength resistance through the reasonable selection of various process parameters during the preparation process and the doping of other components in the general formula. DETAILED DESCRIPTION

[0027] The following description is used to disclose the present invention so that those skilled in the art can implement the present invention. The preferred embodiments described below are only examples, and those skilled in the art may think of other obvious variations.

[0028] Example 1, a modified titanium dioxide ceramic material with a high dielectric constant, the general formula of the ceramic material is (A 0.4 B 0.6 ) x (C 0.5 D 0.5 ) y (Ti 1-z E z ) 1-x-y O2, where A is Re, B is Ba, C is In, D is Ta, E is Zr, x=0.001, y=0.005, z=0.1.

[0029] A method for preparing the modified titanium dioxide ceramic material with a high dielectric constant comprises the following steps:

[0030] Step S1, using analytically pure oxide as raw material; mixing the ingredients according to the general metering ratio, and preparing the modified titanium dioxide ceramic dry powder through mixed ball milling, drying, pre-sintering, and secondary ball milling steps;

[0031] Step S2, granulating and molding the modified titanium dioxide ceramic dry powder processed in step S1, debinding the molded body, and then sintering it to obtain a modified titanium dioxide ceramic material with a high dielectric constant.

[0032] The ball milling in step S1 is a rolling ball mill using anhydrous ethanol as the medium, and the ball milling time is 18 hours; the drying time in step S1 is 15 hours, and the temperature is 85°C; the pre-calcining temperature in step S1 is 1040°C, and the time is 3 hours; an organic binder is added during the granulation process in step S2; the mass ratio of the modified titanium dioxide ceramic dry powder and the organic binder is 100:5.

[0033] The organic adhesive comprises the following components in parts by weight: 1 part of tea polyphenols, 2 parts of diisocyanate polyethylene glycol, 1 part of stevioside, 3 parts of water-soluble hyperbranched polyamide amine, and 100 parts of water; the number average molecular weight of the diisocyanate polyethylene glycol is 400, and it is provided by Guangdong Wengjiang Chemical Reagent Co., Ltd.; the water-soluble hyperbranched polyamide amine is prepared according to the method of Example 1 of the Chinese invention patent with authorization announcement number CN105348542B.

[0034] The molding process described in step S2 is to use a mold to press into small discs; the pressing pressure is 10MPa; the debinding described in step S2 is carried out in a vacuum environment, the debinding temperature is 550°C, and the debinding time is 2h; the sintering temperature described in step S2 is 1300°C, and the time is 8 hours; the sintering conditions are powder buried sintering in air.

[0035] Example 2, a modified titanium dioxide ceramic material with a high dielectric constant, the general formula of the ceramic material is (A 0.4 B 0.6 ) x (C 0.5 D 0.5 ) y (Ti 1-z E z ) 1-x-y O2, where A is Re, B is Ni, C is Ho, D is Nb, E is Hf, x=0.004, y=0.05, z=0.01.

[0036] A method for preparing the modified titanium dioxide ceramic material with a high dielectric constant comprises the following steps:

[0037] Step S1, using analytically pure oxide as raw material; mixing the ingredients according to the general metering ratio, and preparing the modified titanium dioxide ceramic dry powder through mixed ball milling, drying, pre-sintering, and secondary ball milling steps;

[0038] Step S2, granulating and molding the modified titanium dioxide ceramic dry powder processed in step S1, debinding the molded body, and then sintering it to obtain a modified titanium dioxide ceramic material with a high dielectric constant.

[0039] The ball milling in step S1 is a rolling ball mill using anhydrous ethanol as the medium, and the ball milling time is 19 hours; the drying time in step S1 is 17 hours, and the temperature is 87°C; the pre-calcining temperature in step S1 is 1070°C, and the time is 3.5 hours; an organic binder is added during the granulation process in step S2; the mass ratio of the modified titanium dioxide ceramic dry powder and the organic binder is 100:6.

[0040] The organic adhesive comprises the following components in parts by weight: 1.5 parts of tea polyphenols, 3 parts of diisocyanate polyethylene glycol, 1.5 parts of stevioside, 3.5 parts of water-soluble hyperbranched polyamide amine, and 100 parts of water; the number average molecular weight of the diisocyanate polyethylene glycol is 400, which is provided by Guangdong Wengjiang Chemical Reagent Co., Ltd.; the water-soluble hyperbranched polyamide amine is prepared according to the method of Example 1 of the Chinese invention patent with authorization announcement number CN105348542B.

[0041] The molding process described in step S2 is to use a mold to press into small discs; the pressing pressure is 13MPa; the debinding described in step S2 is carried out in a vacuum environment, the debinding temperature is 570°C, and the debinding time is 2.5h; the sintering temperature described in step S2 is 1360°C, and the time is 9 hours; the sintering conditions are powder buried sintering in air.

[0042] Example 3, a modified titanium dioxide ceramic material with a high dielectric constant, the general formula of the ceramic material is (A 0.4 B 0.6 ) x (C 0.5 D 0.5 ) y (Ti 1-z E z ) 1-x-y O2, where A is Re, B is Cu, C is Er, D is V, E is Si, x=0.01, y=0.1, z=0.005.

[0043] A method for preparing the modified titanium dioxide ceramic material with a high dielectric constant comprises the following steps:

[0044] Step S1, using analytically pure oxide as raw material; mixing the ingredients according to the general metering ratio, and preparing the modified titanium dioxide ceramic dry powder through mixed ball milling, drying, pre-sintering, and secondary ball milling steps;

[0045] Step S2, granulating and molding the modified titanium dioxide ceramic dry powder processed in step S1, debinding the molded body, and then sintering it to obtain a modified titanium dioxide ceramic material with a high dielectric constant.

[0046] The ball milling in step S1 is a rolling ball mill using anhydrous ethanol as the medium, and the ball milling time is 20 hours; the drying time in step S1 is 20 hours, and the temperature is 90°C; the pre-calcining temperature in step S1 is 1090°C, and the time is 4 hours; an organic binder is added during the granulation process in step S2; the mass ratio of the modified titanium dioxide ceramic dry powder and the organic binder is 100:6.5.

[0047] The organic adhesive comprises the following components in parts by weight: 2 parts of tea polyphenols, 3.5 parts of diisocyanate polyethylene glycol, 2 parts of stevioside, 4 parts of water-soluble hyperbranched polyamide amine, and 100 parts of water; the number average molecular weight of the diisocyanate polyethylene glycol is 400, which is provided by Guangdong Wengjiang Chemical Reagent Co., Ltd.; the water-soluble hyperbranched polyamide amine is prepared according to the method of Example 1 of the Chinese invention patent with authorization announcement number CN105348542B.

[0048] The molding process described in step S2 is to use a mold to press into small discs; the pressing pressure is 15MPa; the debinding described in step S2 is carried out in a vacuum environment, the debinding temperature is 600°C, and the debinding time is 3h; the sintering temperature described in step S2 is 1450°C, and the time is 10 hours; the sintering conditions are powder buried sintering in air.

[0049] Example 4, a modified titanium dioxide ceramic material with a high dielectric constant, the general formula of the ceramic material is (A 0.4 B 0.6 ) x (C 0.5 D 0.5 ) y (Ti 1-z E z ) 1-x-y O2, wherein A is Re, B is a mixture of Ba, Ni and Cu in a molar ratio of 1:1:2; C is a mixture of In, Ho and Er in a molar ratio of 1:3:2; D is a mixture of Ta, Nb and V in a molar ratio of 1:1:1; E is a mixture of Zr, Hf, Si and Ge in a molar ratio of 1:3:1:1; x=0.016, y=0.15, z=0.1.

[0050] A method for preparing the modified titanium dioxide ceramic material with a high dielectric constant comprises the following steps:

[0051] Step S1, using analytically pure oxide as raw material; mixing the ingredients according to the general metering ratio, and preparing the modified titanium dioxide ceramic dry powder through mixed ball milling, drying, pre-sintering, and secondary ball milling steps;

[0052] Step S2, granulating and molding the modified titanium dioxide ceramic dry powder processed in step S1, debinding the molded body, and then sintering it to obtain a modified titanium dioxide ceramic material with a high dielectric constant.

[0053] The ball milling in step S1 is a rolling ball mill using anhydrous ethanol as the medium, and the ball milling time is 21 hours; the drying time in step S1 is 22 hours, and the temperature is 93°C; the pre-calcining temperature in step S1 is 1110°C, and the time is 4.5 hours; an organic binder is added during the granulation process in step S2; the mass ratio of the modified titanium dioxide ceramic dry powder and the organic binder is 100:7.5.

[0054] The organic adhesive comprises the following components in parts by weight: 2.5 parts of tea polyphenols, 4.5 parts of diisocyanate polyethylene glycol, 2.5 parts of stevioside, 4.5 parts of water-soluble hyperbranched polyamide amine, and 100 parts of water; the number average molecular weight of the diisocyanate polyethylene glycol is 400, which is provided by Guangdong Wengjiang Chemical Reagent Co., Ltd.; the water-soluble hyperbranched polyamide amine is prepared according to the method of Example 1 of the Chinese invention patent with authorization announcement number CN105348542B.

[0055] The molding process described in step S2 is to use a mold to press into small discs; the pressing pressure is 19MPa; the debinding described in step S2 is carried out in a vacuum environment, the debinding temperature is 630°C, and the debinding time is 3.5h; the sintering temperature described in step S2 is 1500°C, and the time is 11 hours; the sintering conditions are powder buried sintering in air.

[0056] Example 5, a modified titanium dioxide ceramic material with a high dielectric constant, the general formula of the ceramic material is (A 0.4 B 0.6 ) x (C 0.5 D 0.5 ) y (Ti 1-z E z ) 1-x-y O2, wherein A is Re, B is Cu; C is a mixture of Ho and Er in a molar ratio of 3:5; D is a mixture of Ta and Nb in a molar ratio of 1:2; E is a mixture of Zr, Hf and Ge in a molar ratio of 1:2:3; x=0.02, y=0.15, z=0.15.

[0057] A method for preparing the modified titanium dioxide ceramic material with a high dielectric constant comprises the following steps:

[0058] Step S1, using analytically pure oxide as raw material; mixing the ingredients according to the general metering ratio, and preparing the modified titanium dioxide ceramic dry powder through mixed ball milling, drying, pre-sintering, and secondary ball milling steps;

[0059] Step S2, granulating and molding the modified titanium dioxide ceramic dry powder processed in step S1, debinding the molded body, and then sintering it to obtain a modified titanium dioxide ceramic material with a high dielectric constant.

[0060] The ball milling in step S1 is a rolling ball mill using anhydrous ethanol as the medium, and the ball milling time is 22 hours; the drying time in step S1 is 24 hours, and the temperature is 95°C; the pre-calcining temperature in step S1 is 1120°C, and the time is 5 hours; an organic binder is added during the granulation process in step S2; the mass ratio of the modified titanium dioxide ceramic dry powder and the organic binder is 100:8.

[0061] The organic adhesive comprises the following components in parts by weight: 3 parts of tea polyphenols, 5 parts of diisocyanate polyethylene glycol, 3 parts of stevioside, 5 parts of water-soluble hyperbranched polyamide amine, and 100 parts of water; the number average molecular weight of the diisocyanate polyethylene glycol is 400, which is provided by Guangdong Wengjiang Chemical Reagent Co., Ltd.; the water-soluble hyperbranched polyamide amine is prepared according to the method of Example 1 of the Chinese invention patent with authorization announcement number CN105348542B.

[0062] The molding process described in step S2 is to press into small discs using a mold; the pressing pressure is 20MPa; the debinding described in step S2 is carried out in a vacuum environment, the debinding temperature is 650°C, and the debinding time is 4h; the sintering temperature described in step S2 is 1520°C, and the time is 12 hours; the sintering conditions are powder buried sintering in air.

[0063] Comparative Example 1, a modified titanium dioxide ceramic material with a high dielectric constant and a preparation method thereof, is substantially the same as Example 1, except that the general formula of the ceramic material is (C 0.5 D 0.5 ) y (Ti 1-z E z ) 1-y O2, where C is In; D is Ta; E is Zr; y=0.005, z=0.1.

[0064] Comparative Example 2, a modified titanium dioxide ceramic material with a high dielectric constant and a preparation method thereof, is substantially the same as Example 1, except that the general formula of the ceramic material is (A 0.4 B 0.6 ) x (Ti 1-z E z ) 1-x O2, where A is Re, B is Ba; E is Zr; x=0.001, z=0.1.

[0065] In order to further illustrate the beneficial technical effects of the modified titanium dioxide ceramic material with a high dielectric constant involved in each embodiment of the present invention, the modified titanium dioxide ceramic material with a high dielectric constant involved in Examples 1-5 and Comparative Examples 1-2 was subjected to relevant performance tests. The test results are shown in Table 1. The test method is as follows: the surface of the ceramic material prepared in each example was ground and polished to a thickness of 0.5 mm, ultrasonically and wiped clean, and a silver paste with a thickness of 0.02 mm was coated on the upper and lower surfaces respectively, placed in a muffle furnace at 700°C for 30 minutes, and naturally cooled to room temperature. The dielectric properties of the ceramic material were tested using an Agilent 4294A precision impedance analyzer and an E4980A LCR tester. For the electric field strength Eb value, a high voltage DC voltage was applied to the ceramic sample in silicone oil at room temperature using a Keithley 2410 digital source meter for IV testing.

[0066] Table 1

[0067] project <![CDATA[Dielectric constant ε r at (1 kHz)]]> Dielectric loss value (1kHz) Withstand electric field strength (KV / cm) Example 1 230370 0.032 22.3 Example 2 234157 0.017 23.1 Example 3 235230 0.012 23.6 Example 4 236742 0.010 24.6 Example 5 237803 0.007 25.0 Comparative Example 1 211350 0.079 20.7 Comparative Example 2 200278 0.091 19.9

[0068] As can be seen from Table 1, the modified titanium dioxide ceramic material with a high dielectric constant involved in the embodiment of the present invention has a higher dielectric constant, lower dielectric loss, and greater electric field strength resistance than the comparative product; the combined modification of A, B, C, and D is beneficial to improving the above properties.

[0069] The above embodiments are only for illustrating the technical concept and features of the present invention, and their purpose is to enable people familiar with this technology to understand the contents of the present invention and implement them accordingly. They cannot be used to limit the protection scope of the present invention. All equivalent changes or modifications made according to the spirit of the present invention should be included in the protection scope of the present invention.

Claims

1. A modified titanium dioxide ceramic material with a high dielectric constant, characterized in that: The general formula of the ceramic material is (A 0.4 B 0.6 ) x (C 0.5 D 0.5 ) y (Ti 1-z E z ) 1-x-y O2, wherein A is Re, B is at least one of Ba, Ni, and Cu; C is at least one of In, Ho, and Er; D is at least one of Ta, Nb, and V; E is at least one of Zr, Hf, Si, and Ge; x=0.001 to 0.02, y=0.005 to 0.15, and z=0.005 to 0.15; The method for preparing the modified titanium dioxide ceramic material with a high dielectric constant comprises the following steps: Step S1, using analytically pure oxide as raw material; mixing the ingredients according to the general metering ratio, and preparing the modified titanium dioxide ceramic dry powder through mixed ball milling, drying, pre-sintering, and secondary ball milling steps; Step S2, granulating and molding the modified titanium dioxide ceramic dry powder processed in step S1, debinding the molded body, and then sintering it to obtain a modified titanium dioxide ceramic material with a high dielectric constant.

2. The modified titanium dioxide ceramic material with a high dielectric constant according to claim 1, characterized in that: The ball milling in step S1 is rolling ball milling with anhydrous ethanol as the medium, and the ball milling time is 18-22 hours.

3. The modified titanium dioxide ceramic material with a high dielectric constant according to claim 1, characterized in that: The drying time in step S1 is 15-24 hours and the temperature is 85-95°C.

4. The modified titanium dioxide ceramic material with a high dielectric constant according to claim 1, characterized in that: The pre-calcination temperature in step S1 is 1040-1120° C. and the pre-calcination time is 3-5 hours.

5. The modified titanium dioxide ceramic material with a high dielectric constant according to claim 1, characterized in that: An organic binder is added during the granulation process in step S2; the mass ratio of the modified titanium dioxide ceramic dry powder to the organic binder is 100:(5-8).

6. The modified titanium dioxide ceramic material with a high dielectric constant according to claim 5, characterized in that: The organic adhesive comprises the following components in parts by weight: 1-3 parts of tea polyphenols, 2-5 parts of diisocyanate polyethylene glycol, 1-3 parts of stevioside, 3-5 parts of water-soluble hyperbranched polyamide amine, and 100 parts of water.

7. The modified titanium dioxide ceramic material with a high dielectric constant according to claim 6, characterized in that: The number average molecular weight of the diisocyanate polyethylene glycol is 400.

8. The modified titanium dioxide ceramic material with a high dielectric constant according to claim 1, characterized in that: The molding process in step S2 is to use a mold to press into small discs; the pressing pressure is 10-20MPa.

9. The modified titanium dioxide ceramic material with a high dielectric constant according to claim 1, characterized in that: The debinding in step S2 is carried out in a vacuum environment, the debinding temperature is 550-650° C., and the debinding time is 2-4 hours; the sintering temperature in step S2 is 1300-1520° C., and the time is 8-12 hours.