CN102515848A - Black pigment for electronic packaging ceramic and preparation method thereof - Google Patents

Abstract

The invention discloses a black pigment for electronic packaging ceramics, which is composed of the following raw material components according to a certain weight percentage: Fe ₂ O ₃ , Cr ₂ O ₃ , MnCO ₃ , CoO, SiO ₂ , TiO ₂ and MgO. The invention also discloses a preparation method of the black pigment. The specific steps are: cleaning each solid material separately, passing through a screen and drying, then weighing the required raw materials, mixing, ball milling, drying, high-temperature sintering, and crushing, Pass through a sieve, ball mill again, and dry to obtain it. The invention discloses a black pigment for electronic packaging ceramics, which can make the packaging ceramics appear black, make the packaging ceramics have light-shielding properties, and do not affect the heat, strength and insulation packaging requirements of the packaging ceramics. The preparation method of the invention has simple steps and is easy to realize.

Description

A kind of black pigment for electronic packaging ceramics and preparation method thereof

technical field

The invention belongs to the technical field of electronic ceramic packaging materials, and in particular relates to a black pigment for electronic packaging ceramics, and also relates to a preparation method of the black pigment for electronic packaging ceramics.

Background technique

Electronic packaging material is a material used to carry electronic components, ensure circuit connection and have good electrical insulation, thermal conductivity and other comprehensive properties. It is required that the packaging material and the packaged components have electrical, physical and chemical properties. Good fit. As a kind of packaging material, ceramic materials are more and more widely used because of their special properties. The main properties of ceramic materials include: good thermal conductivity, high insulation performance, similar linear expansion coefficient to components, excellent high-frequency characteristics, stable chemical properties and other comprehensive properties, widely used in integrated circuits, multi-chip modules packaging and multilayer laminated ceramic substrates. Commonly used ceramic packaging materials mainly include Al ₂ O ₃ , AlN, SiC, BN, and BeO.

With the rapid development of electronic technology, electronic components are developing toward chip type, miniaturization, and high integration, and the precision requirements for integrated circuits are getting higher and higher, so the requirements for packaging materials are also getting higher and higher. Material packaging can greatly reduce the size of components, and at the same time can improve the accuracy and sensitivity of the circuit. For example, a crystal oscillator packaged with ceramic materials can reduce the volume by 30 to 100 times, while the corresponding accuracy and stability are greatly reduced. improve. However, for semiconductor integrated circuits and some electronic products (such as quartz crystal oscillators, nixie tube lining boards, etc.), which have obvious photosensitivity, traditional packaging materials can no longer meet the requirements, so the packaging materials are required to have certain light-shielding properties. The color can be changed by adding an appropriate amount of colorant to the ceramic material, and the addition of black colorant can make the packaging ceramic appear black, making it have a certain light absorption, thereby ensuring the high accuracy and sensitivity of electronic components. Black pigment is an important part of packaging ceramics, which determines the final color rendering effect and other related properties of packaging materials. Traditional black pigments for ceramics mainly have two types of applications: glazes and blanks, such as daily-use ceramics, colored glazed tiles, decorative ceramics, etc., but there are few reports on electronic packaging ceramics. As a colorant for packaging ceramic materials, in addition to considering the coloring effect, it is also necessary to ensure other properties that the packaging material should have, such as high insulation, mechanical strength, thermal properties, etc.

Contents of the invention

The purpose of the present invention is to provide a black pigment for electronic packaging ceramics, which can make the packaging ceramics appear black, make the packaging ceramics have light-shielding properties, and do not affect the thermal, strength and insulating packaging requirements of the packaging ceramics.

Another object of the present invention is to provide a method for preparing the black pigment for electronic packaging ceramics, which has simple steps and is easy to implement.

The technical solution adopted in the present invention is a black pigment for electronic packaging ceramics, which is characterized in that it consists of the following raw material components in terms of weight percentage: Fe ₂ O ₃ 20% to 30%, Cr ₂ O ₃ 30% ~ 35%, MnCO ₃ 25% ~ 35%, CoO 0% ~ 5%, SiO ₂ 1% ~ 2%, TiO ₂ 1.5% ~ 2.5%, MgO 0.5% ~ 2.5%, the sum of the weight percentages of the above components is 100%.

Another technical solution adopted in the present invention is a method for preparing a black pigment for electronic packaging ceramics, characterized in that the specific steps are as follows:

Step 1. Put Fe ₂ O ₃ , Cr ₂ O ₃ , MnCO ₃ , CoO, SiO ₂ , TiO ₂ , and MgO solid materials into solvents and clean them in an ultrasonic cleaner, and pass the cleaned raw materials through sieves Afterwards, place in a drying oven to dry;

Step 2. Among the raw materials obtained in step 1, weigh them according to weight percentage: Fe ₂ O ₃ 20%-30%, Cr ₂ O ₃ 30%-35%, MnCO ₃ 25%-35%, CoO 0% ～5%, SiO ₂ 1%～2%, TiO ₂ 1.5%～2.5%, MgO 0.5%～2.5%, the sum of the weight percentages of the above components is 100%;

Step 3. After mixing the raw materials weighed in step 2, add an appropriate amount of solvent, and place in a ball mill for ball milling for 4h to 10h;

Step 4: put the material obtained in step 3 into a drying oven, and dry at a temperature of 100°C to 120°C for 1h to 3h;

Step 5: Put the material obtained in Step 4 into a crucible, heat it to 1200°C-1350°C in a high-temperature sintering furnace, and keep it warm for 1h-2h;

Step 6: after pulverizing the material obtained in step 5, pass through a 300-mesh sieve, add an appropriate amount of solvent, and place it in a ball mill for ball milling for 3 hours to 5 hours;

Step 7: put the material obtained in step 6 into a drying oven, and dry at a temperature of 100° C. to 120° C. for 1 h to 3 h to obtain the product.

In step 1, the frequency of ultrasonic cleaning is 1 to 2 times, and the cleaning time is 10 minutes to 30 minutes each time.

In step 1, step 3 and step 6, the solvent used is pure water, ethanol, acetone or toluene.

In step 3 and step 6, during ball milling, the ball mill used is a planetary ball mill, and the ball mill used is a corundum ceramic ball mill, zirconia ceramic ball mill, aluminum nitride ceramic ball mill, nylon ball mill or polyurethane ball mill, The grinding balls used are corundum ceramic grinding balls, zirconia ceramic grinding balls, aluminum nitride ceramic grinding balls or agate grinding balls.

The black pigment for electronic package ceramics of the present invention has the following advantages:

1. It is widely used and can be used in various packaging ceramics, such as alumina, zirconia, aluminum nitride, silicon nitride packaging ceramics, etc.

2. By adding an appropriate amount of the black pigment to the package ceramic material, after sintering, the package ceramic can appear black and absorb light, thereby ensuring the high accuracy and sensitivity of the electronic components.

3. After adding the colorant to the packaging ceramic material, it can be sintered under atmospheric conditions or in vacuum.

4. Good high-temperature stability, the packaged ceramics added with this colorant can be sintered in a wide temperature range and at a high temperature (900°C-1400°C), has good coloring effect and is not easy to volatilize.

5. The packaged ceramics added with black pigments, in terms of physical and chemical properties, such as insulation, mechanical strength, dielectric properties, thermal conductivity, etc., all meet the requirements of packaged ceramics.

The black pigment prepared by the preparation method of the invention has uniform particle size, simple steps and easy realization.

Description of drawings

Fig. 1 is the x-ray diffraction figure of the black pigment for electronic package ceramics that the embodiment of the present invention 2 makes;

Fig. 2 is a scanning electron micrograph of the black pigment for electronic packaging ceramics prepared in Example 3 of the present invention.

3 is a scanning electron micrograph of an alumina packaging ceramic substrate added with a black pigment for electronic packaging ceramics prepared in Example 3 of the present invention.

Detailed ways

The present invention will be described in detail below in conjunction with the accompanying drawings and specific embodiments.

A black pigment for electronic packaging ceramics and a preparation method thereof according to the present invention is composed of the following raw material components according to the weight percentage: Fe ₂ O ₃ 20%-30%, Cr ₂ O ₃ 30%-35%, MnCO ₃ 25% ~ 35%, CoO 0% ~ 5%, SiO ₂ 1% ~ 2%, TiO ₂ 1.5% ~ 2.5%, MgO 0.5% ~ 2.5%, the sum of the weight percentages of the above components is 100%.

Fe ₂ O ₃ , Cr ₂ O ₃ , MnCO ₃ (MnO after calcination), CoO and TiO ₂ are colored oxide materials, which usually partly volatilize during sintering, and after high temperature sintering, different types of The crystal structure compound can effectively reduce the volatility of the prepared black pigment and ensure a good color rendering effect. In addition, MnCO ₃ and TiO ₂ in colored oxides can reduce the sintering temperature of alumina ceramics during the sintering process of alumina ceramics. This is because the lattice constants of TiO ₂ and MnO are similar to those of Al ₂ O ₃ , and they are variable-valence elements that can form different types of solid solutions with Al ₂ O ₃ . This variable-valence effect increases the lattice defects of Al ₂ O ₃ , The lattice is activated, thereby reducing the sintering temperature. Furthermore, SiO ₂ and MgO are glass-forming phases. During the sintering process of the black pigment for electronic packaging ceramics, the formation of the glass phase can inhibit the volatilization of the pigment, and can also appropriately reduce the firing temperature of the ceramic material. During the sintering process, MgO can also interact with colored oxides such as Fe ₂ O ₃ , Cr ₂ O ₃ , and MnO to form more complex spinel compounds, which can inhibit the volatilization of black pigments.

In the black pigment prepared by the present invention, Mn ²⁺ , Fe ³⁺ , Cr ³⁺ , etc. are transition metals of the fourth period in the periodic table of elements, and their outermost layers all contain unpaired electrons, ground state and excited state energies Relatively close, it produces strong selective absorption of visible light, and its spectral absorption can mutually inhibit the light transmittance of its ions. When their ion concentrations are adjusted properly, their spectral curves can be superimposed to complement the full absorption of visible light and appear black. In order to obtain pure black pigment, it is required that the lightness L ^* value should be as small as possible, and the color a ^* and b ^* values should be less than 5. The chromaticity index of the color material prepared by the process is: L ^* : 17.03, a ^* : 1.30, b ^* : 0.98, showing a good black effect.

Example 1

Step 1. Put Fe ₂ O ₃ , Cr ₂ O ₃ , MnCO ₃ , CoO, SiO ₂ , TiO ₂ , MgO and other solid powders into ethanol and clean them in an ultrasonic cleaning machine. The cleaning time is 10 minutes to remove surface impurities and open large aggregates to disperse them; pass the cleaned raw materials through a 300-mesh sieve, place them in a drying oven, and dry them at 100°C for 2 hours.

Step 2. Among the raw materials obtained in step 1, weigh: Fe ₂ O ₃ 20g, Cr ₂ O ₃ 35g, MnCO ₃ 35g, CoO 5g, SiO ₂ 2g, TiO ₂ 2.5g, MgO 0.5g.

Step 3. After mixing the raw materials weighed in step 2, add an appropriate amount of ethanol, and place in a ball mill for ball milling for 5 hours, so that the components are fully mixed and the particles are further refined. During ball milling, the ball mill used is a planetary ball mill, and the ball mill used is corundum ceramic ball mill, zirconia ceramic ball mill, aluminum nitride ceramic ball mill, nylon ball mill or polyurethane ball mill, and the balls used are corundum ceramics Grinding balls, zirconia ceramic grinding balls, aluminum nitride ceramic grinding balls or agate grinding balls.

Step 4: Put the material obtained in Step 3 into a drying oven, and dry at 100° C. for 3 hours.

Step 5: Put the material obtained in Step 4 into a crucible, heat it to 1200° C. in a high-temperature sintering furnace, and keep it warm for 2 hours.

Step 6: After pulverizing the material obtained in step 5 with a mortar, pass the pulverized material through a 300-mesh sieve, add an appropriate amount of ethanol, and place it in a ball mill for ball milling for 5 hours. During ball milling, the ball mill used is a planetary ball mill, and the ball mill used is corundum ceramic ball mill, zirconia ceramic ball mill, aluminum nitride ceramic ball mill, nylon ball mill or polyurethane ball mill, and the balls used are corundum ceramics Grinding balls, zirconia ceramic grinding balls, aluminum nitride ceramic grinding balls or agate grinding balls.

Step 7: put the material obtained in Step 6 into a drying oven, and dry at 100° C. for 3 hours to prepare a black pigment for electronic packaging ceramics with a spinel structure.

Example 2

Step 1. Put Fe ₂ O ₃ , Cr ₂ O ₃ , MnCO ₃ , CoO, SiO ₂ , TiO ₂ , MgO and other solid powders into pure water and clean them in an ultrasonic cleaning machine. The number of ultrasonic cleaning is 1 time. The time is 20 minutes to remove surface impurities and open large aggregates to disperse them; pass the cleaned raw materials through a 300-mesh sieve, place them in a drying oven, and dry them at 120°C for 1 hour.

Step 2. Among the raw materials obtained in step 1, weigh: Fe ₂ O ₃ 30g, Cr ₂ O ₃ 30g, MnCO ₃ 34g, SiO ₂ 1.5g, TiO ₂ 2g, MgO 2.5g;

Step 3. After mixing the raw materials weighed in step 2, add an appropriate amount of pure water, and place in a ball mill for ball milling for 8 hours, so that the components are fully mixed and the particles are further refined. During ball milling, the ball mill used is a planetary ball mill, and the ball mill used is corundum ceramic ball mill, zirconia ceramic ball mill, aluminum nitride ceramic ball mill, nylon ball mill or polyurethane ball mill, and the balls used are corundum ceramics Grinding balls, zirconia ceramic grinding balls, aluminum nitride ceramic grinding balls or agate grinding balls.

Step 4: Put the material obtained in Step 3 into a drying oven, and dry at 120° C. for 1 hour.

Step 5: Put the material obtained in Step 4 into a crucible, heat it to 1350° C. in a high-temperature sintering furnace, and keep it warm for 1 hour.

Step 6: After pulverizing the material obtained in step 5 with a mortar, pass the pulverized material through a 300-mesh sieve, add an appropriate amount of pure water, and place it in a ball mill for ball milling for 3 hours. During ball milling, the ball mill used is a planetary ball mill, and the ball mill used is corundum ceramic ball mill, zirconia ceramic ball mill, aluminum nitride ceramic ball mill, nylon ball mill or polyurethane ball mill, and the balls used are corundum ceramics Grinding balls, zirconia ceramic grinding balls, aluminum nitride ceramic grinding balls or agate grinding balls.

Step 7: Put the material obtained in Step 6 into a drying oven, and dry it at 110° C. for 2 hours to prepare a black pigment for electronic packaging ceramics with a spinel structure. As shown in FIG. 1 , it is an x-ray diffraction pattern of the black pigment for electronic packaging ceramics prepared in this embodiment. It can be seen from the figure that the crystal structure of the prepared black pigment is a spinel structure, and its structural formula is (Mn, Fe)Cr ₂ O ₄ , and Mn and Fe are surrounded by four oxygen ions, forming [ AO ₄ ] tetrahedron, Cr is surrounded by six oxygen ions, forming [BO ₆ ] octahedron.

Example 3

Step 1. Put Fe ₂ O ₃ , Cr ₂ O ₃ , MnCO ₃ , CoO, SiO ₂ , TiO ₂ , MgO and other solid powders into toluene and clean them in an ultrasonic cleaning machine. The cleaning time is 15 minutes to remove surface impurities and open large aggregates to disperse them; pass the cleaned raw materials through a 300-mesh sieve, put them in a drying oven, and dry them at 110°C for 2 hours.

Step 2. Among the raw materials obtained in step 1, weigh: Fe ₂ O ₃ 27g, Cr ₂ O ₃ 33g, MnCO ₃ 30.5g, CoO 5g, SiO ₂ 1g, TiO ₂ 1.5g, MgO 2g;

Step 3. After mixing the raw materials weighed in step 2, add an appropriate amount of toluene, and place in a ball mill for ball milling for 4 hours, so that the components are fully mixed and the particles are further refined. During ball milling, the ball mill used is a planetary ball mill, and the ball mill used is corundum ceramic ball mill, zirconia ceramic ball mill, aluminum nitride ceramic ball mill, nylon ball mill or polyurethane ball mill, and the balls used are corundum ceramics Grinding balls, zirconia ceramic grinding balls, aluminum nitride ceramic grinding balls or agate grinding balls.

Step 4: put the material obtained in step 3 into a drying oven, and dry at 110°C for 2 hours;

Step 5: Put the material obtained in Step 4 into a crucible, heat it to 1300°C in a high-temperature sintering furnace, and keep it warm for 1.5h;

Step 6: After pulverizing the material obtained in step 5 with a mortar, pass the pulverized material through a 300-mesh sieve, add an appropriate amount of ethanol, and place it in a ball mill for ball milling for 4 hours. During ball milling, the ball mill used is a planetary ball mill, and the ball mill used is corundum ceramic ball mill, zirconia ceramic ball mill, aluminum nitride ceramic ball mill, nylon ball mill or polyurethane ball mill, and the balls used are corundum ceramics Grinding balls, zirconia ceramic grinding balls, aluminum nitride ceramic grinding balls or agate grinding balls.

Step 7: put the material obtained in Step 6 into a drying oven, and dry at 100° C. for 3 hours to prepare a black pigment for electronic packaging ceramics with a spinel structure.

As shown in Fig. 2, the black pigment particles for electronic packaging ceramics prepared by the present invention have good shape, moderate average particle size and uniform particle size distribution. The amount of black pigment for electronic packaging ceramics prepared in this embodiment is 4% of the total weight of the ceramic material, the amount of the sintering aid is 6% of the total weight of the ceramic material, and the rest is aluminum oxide. SEM photographs of alumina-encapsulated ceramic substrates sintered at °C. As can be seen from Fig. 3, the alumina ceramics after adding the black pigment for electronic packaging ceramics of the present invention and the sintering aid have little influence on the morphology of the alumina ceramic particles, the pigment is evenly dispersed and distributed, and part of the pigment is passed through After melting at high temperature, it is coated on the surface of alumina particles.

Example 4

Step 1. Put Fe ₂ O ₃ , Cr ₂ O ₃ , MnCO ₃ , CoO, SiO ₂ , TiO ₂ , MgO and other solid powders into acetone and clean them in an ultrasonic cleaner. The time is 30 minutes to remove surface impurities and open large aggregates to disperse them; pass the cleaned raw materials through a 300-mesh sieve, place them in a drying oven, and dry them at 100°C for 2 hours.

Step 2. Among the raw materials obtained in step 1, weigh: Fe ₂ O ₃ 30g, Cr ₂ O ₃ 35g, MnCO ₃ 25g, CoO 4.5g, SiO ₂ 1.5g, TiO ₂ 2g, MgO 2g;

Step 3. After mixing the raw materials weighed in step 2, add an appropriate amount of acetone, and place in a ball mill for ball milling for 10 hours, so that the components are fully mixed and the particles are further refined. During ball milling, the ball mill used is a planetary ball mill, and the ball mill used is corundum ceramic ball mill, zirconia ceramic ball mill, aluminum nitride ceramic ball mill, nylon ball mill or polyurethane ball mill, and the balls used are corundum ceramics Grinding balls, zirconia ceramic grinding balls, aluminum nitride ceramic grinding balls or agate grinding balls.

Step 4: put the material obtained in step 3 into a drying oven, and dry at 100°C for 3 hours;

Step 5: Put the material obtained in Step 4 into a crucible, heat it to 1350°C in a high-temperature sintering furnace, and keep it warm for 1 hour;

Step 6: After pulverizing the material obtained in step 5 with a mortar, pass the pulverized material through a 300-mesh sieve, add an appropriate amount of ethanol, and place it in a ball mill for ball milling for 4 hours. During ball milling, the ball mill used is a planetary ball mill, and the ball mill used is corundum ceramic ball mill, zirconia ceramic ball mill, aluminum nitride ceramic ball mill, nylon ball mill or polyurethane ball mill, and the balls used are corundum ceramics Grinding balls, zirconia ceramic grinding balls, aluminum nitride ceramic grinding balls or agate grinding balls.

Step 7: put the material obtained in Step 6 into a drying oven, and dry at 120° C. for 1 hour to prepare a black pigment for electronic packaging ceramics with a spinel structure.

Claims (5)

1. an Electronic Packaging pottery is used black pigment, it is characterized in that, according to weight percent, is made up of following feed composition: Fe ₂O ₃20%～30%, Cr ₂O ₃30%～35%, MnCO ₃25%～35%, CoO 0%～5%, SiO ₂1%～2%, TiO ₂1.5%～2.5%, MgO 0.5%～2.5%, more than each weight percentages of components sum be 100%.

2. Electronic Packaging pottery is characterized in that with the preparation method of black pigment concrete steps are following:

Step 1, with Fe ₂O ₃, Cr ₂O ₃, MnCO ₃, CoO, SiO ₂, TiO ₂, the MgO solid material puts into solvent respectively and cleans at Ultrasonic Cleaners, the raw material after cleaning is crossed screen cloth respectively after, place the loft drier inner drying;

In step 2, the raw material that in step 1, obtains, take by weighing respectively according to weight percent: Fe ₂O ₃20%～30%, Cr ₂O ₃30%～35%, MnCO ₃25%～35%, CoO 0%～5%, SiO ₂1%～2%, TiO ₂1.5%～2.5%, MgO 0.5%～2.5%, more than each weight percentages of components sum be 100%;

After step 3, the raw materials mix that step 2 is taken by weighing, add an amount of solvent, place ball mill ball-milling processing 4h～10h;

Step 4: the material that step 3 obtains is put into loft drier, dry 1h～3h under 100 ℃～120 ℃ temperature;

Step 5: the material that step 4 is obtained places crucible, is heated to 1200 ℃～1350 ℃ in the high temperature sintering furnace, insulation 1h～2h;

Step 6: after the material that obtains in the step 5 pulverized, cross 300 eye mesh screens, add an amount of solvent, place ball mill ball-milling processing 3h～5h;

Step 7: the material that step 6 obtains is put into loft drier, and dry 1h～3h under 100 ℃～120 ℃ temperature promptly makes.

3. according to the preparation method of the said Electronic Packaging pottery of claim 2 with black pigment, it is characterized in that in the step 1, the ultrasonic cleaning number of times is 1～2 time, each scavenging period is 10min～30min.

4. according to the preparation method of the said Electronic Packaging pottery of claim 2, it is characterized in that in step 1, step 3 and the step 6, employed solvent is pure water, ethanol, acetone or toluene with black pigment.

5. according to the preparation method of the said Electronic Packaging pottery of claim 2 with black pigment; It is characterized in that; In step 3 and the step 6, during ball-milling processing, institute uses ball mill to be planetary ball mill; The ball grinder that uses be corundum ceramic ball grinder, zirconia ceramics ball grinder, aluminium nitride ceramics ball grinder, nylon ball grinder or urethane ball grinder, the abrading-ball that uses be corundum ceramic abrading-ball, zirconia ceramics abrading-ball, aluminium nitride ceramics abrading-ball or agate abrading-ball.

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