A Metallization Method for Ceramic Components

Abstract

The present invention relates to the technical field of ceramic metallization, specifically a method for metallizing ceramic components. Specifically, after the surface of the ceramic components is pretreated, a titanium carbonitride layer, a titanium nitride layer, and a metal layer are sequentially deposited, and then cleaned and dried. The method provided by the present invention has good bonding performance between the metal layer and the ceramic matrix, and also has excellent thermal shock resistance.

Description

Technical Field

[0001] The present invention relates to the technical field of ceramic metallization, and specifically to a method for metallizing ceramic components. Background Art

[0002] In the use of high-power electronic devices to achieve the interconnection between chips and electronic components, as a packaging substrate material, ceramics need to be metallized on their surfaces. However, since ceramic materials are strong covalent bond compounds, their electron coordination is very stable, they are not easy to react with other materials, and it is difficult to wet with common metals. Moreover, the performance after the surface metallization of ceramic substrates is closely related to the stability of power electronic devices during operation. Therefore, this is the reason restricting the wide application of ceramic packaging substrates. Thus, exploring the significance of ceramic surface metallization is very important. Currently, common methods for ceramic metallization mainly include electroless metallization and direct copper plating metallization. However, there are generally problems such as low bonding strength of the metallized layer, poor thermal shock resistance, and easy detachment of the metallized layer from the ceramic, which easily lead to sealing failure. Summary of the Invention

[0003] Object of the Invention: Aiming at the above technical problems, the present invention proposes a method for metallizing ceramic components.

[0004] The technical solution adopted is as follows:

[0005] A method for metallizing ceramic components:

[0006] After pre-treating the surface of the ceramic component, deposit a titanium carbonitride layer, a titanium nitride layer, and a metal layer in sequence, and then clean and dry it.

[0007] Further, the material of the ceramic component is alumina.

[0008] Further, the titanium nitride layer is also subjected to metal ion implantation treatment.

[0009] Further, the metal ion is a rare earth metal ion.

[0010] Further, the rare earth metal ion is Nd 3+ .

[0011] Further, after drying, immerse it in liquid nitrogen for 10 - 50 s.

[0012] Further, the pre-treatment includes solvent washing and acid leaching.

[0013] Further, the titanium carbonitride layer and the titanium nitride layer are prepared by chemical vapor deposition.

[0014] Further, the precursors for preparing the titanium carbonitride layer are titanium tetrachloride, ammonia gas, and methane, and the precursors for preparing the titanium nitride layer are titanium tetrachloride and ammonia gas.

[0015] Further, the metal layer is prepared by any one of physical sputtering, chemical vapor deposition, electroplating, electroless plating, and thermal evaporation.

[0016] Advantages of the present invention:

[0017] The present invention provides a method for metallizing ceramic components. The titanium carbonitride layer and the titanium nitride layer can form a thermal expansion gradient between the ceramic components and the metal layer, playing a certain buffering role when subjected to external stress and thermal shock during service, reducing the stress difference between the ceramic matrix and the metal layer, and improving the problem of mismatch in toughness and elastic modulus between the ceramic matrix and the metal layer. Moreover, after metal ion implantation, the titanium nitride layer has a good wetting effect with the metal layer, and the metal ions can also activate the titanium nitride layer and serve as a catalytic center for subsequent metal deposition, which is beneficial to improving the bonding strength of the deposited metal layer. In addition, due to the difference in thermal expansion coefficients of different materials, during liquid nitrogen impregnation, the shrinkage of the metal layer is greater than that of the titanium nitride layer, and the compressive stress at the bonding interface between the metal layer and the titanium nitride layer constitutes the bonding force between the metal layer and the titanium nitride layer, thereby improving the bonding strength between the titanium nitride layer and the metal layer. The bonding performance between the metal layer prepared by the method provided by the present invention and the ceramic matrix is good, and it also has excellent thermal shock resistance. Description of the Drawings

[0018] Figure 1 It is the SEM image of the copper plating layer on the surface of the specimen prepared in Example 1. It can be seen that the structure of the copper plating layer is dense and the grains are fine. Detailed Embodiments

[0019] For those not specified in the embodiments, they are carried out according to conventional conditions or the conditions recommended by the manufacturer. For reagents or instruments not specified by the manufacturer, they are all conventional products that can be obtained through commercial purchase. The technologies not mentioned in the present invention refer to the prior art. Unless otherwise specified, the following examples and comparative examples are parallel experiments and adopt the same treatment steps and parameters.

[0020] Example 1:

[0021] A method for metallizing ceramic components:

[0022] The alumina substrate was washed successively with deionized water and acetone, then dried with hot nitrogen gas, and then added to a hydrochloric acid solution with a concentration of 1 mol / L and soaked at 50 °C for 5 h, after which it was taken out, washed thoroughly with deionized water and dried. Then, a titanium carbonitride layer and a titanium nitride layer were successively deposited on the surface of the alumina substrate by chemical vapor deposition. When depositing the titanium carbonitride layer, the temperature was 800 °C, the protective gas was nitrogen, and titanium tetrachloride, ammonia, and methane were used as precursors. The flow rates of titanium tetrachloride, ammonia, methane, and nitrogen were 150 ml / min, 80 ml / min, 50 ml / min, and 670 ml / min respectively. The deposition time of the titanium carbonitride layer was controlled to be 360 s. After depositing the titanium carbonitride layer, the temperature of the reactor was reduced to 580 °C, methane was stopped being introduced, and the gas in the reactor was replaced with nitrogen. Then, using titanium tetrachloride and ammonia as precursors and nitrogen as the protective gas, a titanium nitride layer was prepared. The flow rates of titanium tetrachloride, ammonia, and nitrogen were 150 ml / min, 80 ml / min, and 670 ml / min respectively. The deposition time of the titanium nitride layer was controlled to be 240 s. After the deposition was completed, the specimen was taken out and fixed on the target disk of the ion implanter. The titanium nitride layer on the surface of the specimen was perpendicular to the ion incident direction. Then, the target chamber was evacuated to about 1×10 -4 Pa, the valve between the implanter and the target chamber was opened. The ion implantation material was neodymium metal with a purity of 99.99%, and the ion implantation parameters were: pulse frequency 20 Hz, acceleration voltage 40 keV, implantation dose 5×10 l6 ion / cm 2 , and after ion implantation, electroless copper plating was directly carried out. The formula and process conditions were as follows: CuSO4·5H2O 12.5 g / L, formaldehyde 10 ml / L, sodium potassium tartrate 56 g / L, sodium hydroxide 20 g / L, potassium ferrocyanide 5 mg / L, pH 12.5 - 13.0, temperature 40 °C, time 30 min. After the plating was completed, it was taken out, first washed thoroughly with deionized water, dried in an oven at 120 °C for 24 h, and then soaked in liquid nitrogen for 30 s.

[0023] Example 2:

[0024] It was basically the same as Example 1, except that nickel ion implantation was used. The specific method was as follows:

[0025] The alumina substrate was washed successively with deionized water and acetone, dried with hot nitrogen, then added to a hydrochloric acid solution with a concentration of 1 mol / L and soaked at 50 °C for 5 h, taken out, washed thoroughly with deionized water and dried. Then, a titanium carbonitride layer and a titanium nitride layer were successively deposited on the surface of the alumina substrate by chemical vapor deposition. When depositing the titanium carbonitride layer, the temperature was 800 °C, the protective gas was nitrogen, and titanium tetrachloride, ammonia, and methane were used as precursors. The flow rates of titanium tetrachloride, ammonia, methane, and nitrogen were 150 ml / min, 80 ml / min, 50 ml / min, and 670 ml / min respectively. The deposition time of the titanium carbonitride layer was controlled to be 360 s. After depositing the titanium carbonitride layer, the temperature of the reactor was lowered to 580 °C, methane injection was stopped, and the gas in the reactor was replaced with nitrogen. Then, using titanium tetrachloride and ammonia as precursors and nitrogen as the protective gas, a titanium nitride layer was prepared. The flow rates of titanium tetrachloride, ammonia, and nitrogen were 150 ml / min, 80 ml / min, and 670 ml / min respectively. The deposition time of the titanium nitride layer was controlled to be 240 s. After the deposition was completed, the specimen was taken out and fixed on the target disk of the ion implanter. The titanium nitride layer on the surface of the specimen was perpendicular to the ion incident direction. Then, the target chamber was evacuated to about 1 × 10 -4 Pa, the valve between the implanter and the target chamber was opened. The ion implantation material was metallic nickel with a purity of 99.99%, and the ion implantation parameters were: pulse frequency 20 Hz, acceleration voltage 40 keV, implantation dose 5 × 10 l6 ion / cm 2 , and after ion implantation, electroless copper plating was directly carried out. The formula and process conditions were as follows: CuSO4·5H2O 12.5 g / L, formaldehyde 10 ml / L, sodium potassium tartrate 56 g / L, sodium hydroxide 20 g / L, potassium ferrocyanide 5 mg / L, pH 12.5 - 13.0, temperature 40 °C, time 30 min. After the plating was completed, it was taken out, first washed thoroughly with deionized water, dried in an oven at 120 °C for 24 h, and then soaked in liquid nitrogen for 30 s.

[0026] Example 3:

[0027] It was basically the same as Example 1, except that copper ion implantation was used. The specific method was as follows:

[0028] The alumina substrate was washed successively with deionized water and acetone, dried with hot nitrogen, then added to a hydrochloric acid solution with a concentration of 1 mol / L and soaked at 50 °C for 5 h, taken out, washed thoroughly with deionized water and dried. Then, a titanium carbonitride layer and a titanium nitride layer were successively deposited on the surface of the alumina substrate by chemical vapor deposition. When depositing the titanium carbonitride layer, the temperature was 800 °C, the protective gas was nitrogen, and titanium tetrachloride, ammonia and methane were used as precursors. The flow rates of titanium tetrachloride, ammonia, methane and nitrogen were 150 ml / min, 80 ml / min, 50 ml / min and 670 ml / min respectively. The deposition time of the titanium carbonitride layer was controlled to be 360 s. After depositing the titanium carbonitride layer, the temperature of the reactor was reduced to 580 °C, methane injection was stopped, and the gas in the reactor was replaced with nitrogen. Then, using titanium tetrachloride and ammonia as precursors and nitrogen as the protective gas, a titanium nitride layer was prepared. The flow rates of titanium tetrachloride, ammonia and nitrogen were 150 ml / min, 80 ml / min and 670 ml / min respectively. The deposition time of the titanium nitride layer was controlled to be 240 s. After the deposition was completed, the specimen was taken out and fixed on the target disk of the ion implanter. The titanium nitride layer on the surface of the specimen was perpendicular to the ion incident direction. Then, the target chamber was evacuated to about 1×10 -4 Pa, the valve between the implanter and the target chamber was opened. The ion implantation material was metallic copper with a purity of 99.99%, and the ion implantation parameters were: pulse frequency 20 Hz, acceleration voltage 40 keV, implantation dose 5×10 l6 ion / cm 2 . After ion implantation, electroless copper plating was directly carried out. The formula and process conditions were as follows: CuSO4·5H2O 12.5 g / L, formaldehyde 10 ml / L, sodium potassium tartrate 56 g / L, sodium hydroxide 20 g / L, potassium ferrocyanide 5 mg / L, pH 12.5 - 13.0, temperature 40 °C, time 30 min. After the plating was completed, it was taken out, washed thoroughly with deionized water, dried in an oven at 120 °C for 24 h, and then soaked in liquid nitrogen for 30 s.

[0029] Example 4:

[0030] Basically the same as Example 1, the difference is that ion implantation was not carried out. The specific method is as follows:

[0031] The alumina substrate was washed successively with deionized water and acetone, dried with hot nitrogen, then added to a hydrochloric acid solution with a concentration of 1 mol / L and soaked at 50 °C for 5 h, taken out, washed thoroughly with deionized water and dried. Then, a titanium carbonitride layer and a titanium nitride layer were successively deposited on the surface of the alumina substrate by chemical vapor deposition. When depositing the titanium carbonitride layer, the temperature was 800 °C, the protective gas was nitrogen, and titanium tetrachloride, ammonia, and methane were used as precursors. The flow rates of titanium tetrachloride, ammonia, methane, and nitrogen were 150 ml / min, 80 ml / min, 50 ml / min, and 670 ml / min respectively. The deposition time of the titanium carbonitride layer was controlled to be 360 s. After depositing the titanium carbonitride layer, the temperature of the reactor was lowered to 580 °C, methane was stopped from being introduced, and the gas in the reactor was replaced with nitrogen. Then, a titanium nitride layer was prepared using titanium tetrachloride and ammonia as precursors and nitrogen as the protective gas. The flow rates of titanium tetrachloride, ammonia, and nitrogen were 150 ml / min, 80 ml / min, and 670 ml / min respectively. The deposition time of the titanium nitride layer was controlled to be 240 s. After the deposition was completed, the specimen was taken out and directly subjected to electroless copper plating. The formula and process conditions were as follows: CuSO4·5H2O 12.5 g / L, formaldehyde 10 ml / L, sodium potassium tartrate 56 g / L, sodium hydroxide 20 g / L, potassium ferrocyanide 5 mg / L, pH 12.5 - 13.0, temperature 40 °C, time 30 min. After the plating was completed, it was taken out, washed thoroughly with deionized water, dried in an oven at 120 °C for 24 h, and then soaked in liquid nitrogen for 30 s.

[0032] Example 5:

[0033] Basically the same as Example 1, the difference is that it does not go through liquid nitrogen cleaning. The specific method is as follows:

[0034] The alumina substrate was washed successively with deionized water and acetone, then dried with hot nitrogen gas. It was then added to a hydrochloric acid solution with a concentration of 1 mol / L and soaked at 50 °C for 5 h, after which it was taken out, washed thoroughly with deionized water and dried. Then, using chemical vapor deposition technology, a titanium carbonitride layer and a titanium nitride layer were successively deposited on the surface of the alumina substrate. When depositing the titanium carbonitride layer, the temperature was 800 °C, the protective gas was nitrogen, and titanium tetrachloride, ammonia, and methane were used as precursors. The flow rates of titanium tetrachloride, ammonia, methane, and nitrogen were 150 ml / min, 80 ml / min, 50 ml / min, and 670 ml / min respectively. The deposition time of the titanium carbonitride layer was controlled to be 360 s. After depositing the titanium carbonitride layer, the temperature of the reactor was lowered to 580 °C, methane injection was stopped, and the gas in the reactor was replaced with nitrogen. Then, using titanium tetrachloride and ammonia as precursors and nitrogen as the protective gas, a titanium nitride layer was prepared. The flow rates of titanium tetrachloride, ammonia, and nitrogen were 150 ml / min, 80 ml / min, and 670 ml / min respectively. The deposition time of the titanium nitride layer was controlled to be 240 s. After the deposition was completed, the specimen was taken out and fixed on the target disk of the ion implanter. The titanium nitride layer on the surface of the specimen was perpendicular to the ion incident direction. Then, the target chamber was evacuated to about 1 × 10 -4 Pa. The valve between the implanter and the target chamber was opened. The ion implantation material was neodymium metal with a purity of 99.99%. The ion implantation parameters were: pulse frequency 20 Hz, acceleration voltage 40 keV, implantation dose 5 × 10 l6 ions / cm 2 . After ion implantation, electroless copper plating was carried out directly. The formula and process conditions were as follows: CuSO4·5H2O 12.5 g / L, formaldehyde 10 ml / L, sodium potassium tartrate 56 g / L, sodium hydroxide 20 g / L, potassium ferrocyanide 5 mg / L, pH 12.5 - 13.0, temperature 40 °C, time 30 min. After the plating was completed, it was taken out, washed thoroughly with deionized water first, and then dried in an oven at 120 °C for 24 h.

[0035] Comparative Example 1:

[0036] It was basically the same as Example 1, except that it did not contain a titanium carbonitride layer. The specific method was as follows:

[0037] The alumina substrate was washed successively with deionized water and acetone, dried with hot nitrogen, then added to a hydrochloric acid solution with a concentration of 1 mol / L and soaked at 50 °C for 5 h, taken out, washed thoroughly with deionized water and dried. Then, a titanium nitride layer was deposited on the surface of the alumina substrate successively by chemical vapor deposition technology. The temperature during the deposition of the titanium nitride layer was 580 °C. Using titanium tetrachloride and ammonia as precursors and nitrogen as the protective gas, the flow rates of titanium tetrachloride, ammonia and nitrogen were 150 ml / min, 80 ml / min and 670 ml / min respectively. The deposition time of the titanium nitride layer was controlled to be 240 s. After the deposition was completed, the specimen was taken out and fixed on the target disk of the ion implanter. The titanium nitride layer on the surface of the specimen was perpendicular to the ion incident direction. Then, the target chamber was evacuated to about 1×10 -4 Pa. The valve between the implanter and the target chamber was opened. The ion implantation material was neodymium metal with a purity of 99.99%. The ion implantation parameters were: pulse frequency of 20 Hz, acceleration voltage of 40 keV, and implantation dose of 5×10 l6 ion / cm 2 . After ion implantation, electroless copper plating was carried out directly. The formula and process conditions were as follows: CuSO4·5H2O 12.5 g / L, formaldehyde 10 ml / L, sodium potassium tartrate 56 g / L, sodium hydroxide 20 g / L, potassium ferrocyanide 5 mg / L, pH 12.5 - 13.0, temperature 40 °C, time 30 min. After the plating was completed, the specimen was taken out, washed thoroughly with deionized water first, dried in an oven at 120 °C for 24 h, and then soaked in liquid nitrogen for 30 s.

[0038] Comparative Example 2:

[0039] It was basically the same as Example 1, except that the titanium nitride layer was not included. The specific method was as follows:

[0040] The alumina substrate was washed successively with deionized water and acetone, dried with hot nitrogen, then added to a hydrochloric acid solution with a concentration of 1 mol / L and soaked at 50 °C for 5 h, taken out, washed thoroughly with deionized water and dried. Then, a titanium carbonitride layer was deposited on the surface of the alumina substrate successively by chemical vapor deposition technology. The temperature during the deposition of the titanium carbonitride layer was 800 °C. The protective gas was nitrogen. Using titanium tetrachloride, ammonia and methane as precursors, the flow rates of titanium tetrachloride, ammonia, methane and nitrogen were 150 ml / min, 80 ml / min, 50 ml / min and 670 ml / min respectively. The deposition time of the titanium carbonitride layer was controlled to be 360 s. After the deposition was completed, the specimen was taken out and fixed on the target disk of the ion implanter. The titanium carbonitride layer on the surface of the specimen was perpendicular to the ion incident direction. Then, the target chamber was evacuated to about 1×10 -4 Pa. The valve between the implanter and the target chamber was opened. The ion implantation material was neodymium metal with a purity of 99.99%. The ion implantation parameters were: pulse frequency of 20 Hz, acceleration voltage of 40 keV, and implantation dose of 5×10l6 ions / cm 2 , After ion implantation, electroless copper plating is directly carried out. The formula and process conditions are as follows: CuSO4·5H2O 12.5 g / L, formaldehyde 10 ml / L, sodium potassium tartrate 56 g / L, sodium hydroxide 20 g / L, potassium ferrocyanide 5 mg / L, pH 12.5 - 13.0, temperature 40 °C, time 30 min. After the plating is completed, take it out, first wash it thoroughly with deionized water, then dry it in an oven at 120 °C for 24 h, and then soak it in liquid nitrogen for 30 s.

[0041] Performance test:

[0042] Perform performance tests on the specimens prepared in Examples 1 - 5 and Comparative Examples 1 - 2 of the present invention respectively;

[0043] Use an electrothermal blast drying oven to conduct a thermal shock experiment to test the bonding performance of the copper coating. The temperature is set at (250 ± 10) °C, keep it warm for 30 min, then quickly put the specimen into an ice - water mixture at 0 °C for rapid cooling, and repeat it 35 times.

[0044] Use a Rockwell hardness tester to conduct an indentation test on the bonding force of the copper coating: a 120° conical diamond indenter, apply a pressure of 60 kg, keep it for 30 s, and obvious indentations appear. Use a NovaNanoSEM50 type field emission scanning electron microscope (FE - SEM) to observe the microscopic morphology and cracks of the indentations.

[0045] Use the adhesive peeling method to detect the bonding strength of the copper coating, record the peak value F (N) of the tensile force required for the copper coating to peel off on a tensile force tester, and then calculate the bonding strength P (N / mm 2 ), S is the contact area (mm 2 ).

[0046] The test results are shown in Table 1 below:

[0047] Table 1:

[0048]

[0049] As can be seen from Table 1 above, the bonding performance between the metal layer and the ceramic matrix prepared by the method provided by the present invention is good, and it also has excellent thermal shock resistance.

[0050] The above embodiments are only used to illustrate the technical solutions of the present invention, rather than to limit it; although the present invention has been described in detail with reference to the foregoing embodiments, those of ordinary skill in the art should understand that: they can still modify the technical solutions recorded in the foregoing embodiments, or perform equivalent replacements on some of the technical features; and these modifications or replacements do not make the essence of the corresponding technical solutions deviate from the spirit and scope of the technical solutions of the embodiments of the present invention.

Claims

1. A method for metallization of a ceramic component, characterized in that, After the surface of the ceramic component is pretreated, a titanium carbonitride layer, a titanium nitride layer and a metal layer are sequentially deposited, followed by cleaning and drying; The pretreatment includes solvent washing and acid pickling; The material of the ceramic component is alumina; The titanium nitride layer is also treated by metal ion implantation; The metal ion is a rare earth metal ion, and the rare earth metal ion is Nd 3+ ; After drying, it is immersed in liquid nitrogen for 10 - 50 s; The titanium carbonitride layer and the titanium nitride layer are prepared by chemical vapor deposition; The precursors for preparing the titanium carbonitride layer are titanium tetrachloride, ammonia and methane, and the precursors for preparing the titanium nitride layer are titanium tetrachloride and ammonia.

2. The method for metallizing a ceramic component according to claim 1, wherein, The metal layer is prepared by any one of physical sputtering, chemical vapor deposition, electroplating, electroless plating, and thermal evaporation.

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