TW460430B - Low-fire, low-dielectric-constant and low-loss ceramic compositions - Google Patents

Abstract

A ceramic composition for forming a multilayer ceramic substrate which can be densified up to 95% at 800-1000 DEG C within 15-60 min. The ceramic composition comprises a mixture of finely divided particles of 30-90 vol% Ca-Pb-Zn borosilicate glass and 10-70 vol% oxide. The multilayer ceramic substrate composition can be used with organic solvents, polymeric binder and plasticizer to produce an unfired green tape which is cofirable with high electrical conductivity metallurgies such as gold, silver, silver-palladium and copper.

Description

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V. Description of the invention (1) [Field of the invention] 'Especially for application' The characteristic that this ceramic component can be electrically lost. The invention relates to the composition of the dielectric ceramic material and the ceramic material required for the laminated ceramic substrate or component is dense at low temperature and has a low dielectric constant and a low dielectric. [Background of the Invention] With the development of thinner and shorter electronic systems, the body circuit (VLSI) towards a high accumulation density and high speed]: = Integrity, high reliability and other characteristics. Brother speed train, the south line is closely related to electrical properties. In order to improve the signal transmission rate, the conductor material in the construction is weakened. It is best to use high conductivity and health: genus, such as silver, silver-palladium alloy, gold, copper ^ ^ ^ ^ ^ &Amp; ^ 〇〇〇: c In addition, because the signal delay (td) and the substrate material (k) have a T column relationship: 丨 electricity * number

td = k1 / 2 L / C C is the speed of light and L is the length of the line. Therefore, reducing the dielectric constant of the substrate material can reduce the signal delay time. At the same time, the dielectric loss (tan (5)) of the substrate material can be reduced to prevent mutual interference between signals, and the density of the lines on the substrate. In terms of reliability, 'with the size of the wafer, it has increased by 80%. The left and right chips use surface mount technology (SMT) to directly bond the chip and the substrate material together; in order to reduce the thermal stress caused by the difference in thermal expansion between the two, the substrate and the crystal

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V. Description of the invention (2) The chip is cracked or peeled off, and the base sheet is close to improve the reliability and high-speed operation of the system. As a result, the electronic components on the substrate will be damaged, which means higher thermal conductivity. . The conditions that this material must have. Therefore, when choosing a ceramic structure, it is necessary to have a low dielectric constant, a low dielectric constant, and a sintering temperature of 1000 to metal conductors such as gold, gold, copper and the like, and appropriate mechanical strength. The thermal expansion coefficient of the material must be as close as possible to the crystallinity. Because electronic components have a large amount of heat, in order to prevent the substrate material from overheating, it must have good heat dissipation. In addition to good mechanical properties, it is also necessary to consider the material composition loss when the thermal expansion coefficient can be matched with silicon. Dielectric materials that can be densely sintered with silver and silver-palladium, have high thermal conductivity and a low η dielectric constant, and can also use components above 300 MHz and microwave (GHz) range because of the resonance of the dielectric material The frequencies are very quotient 'and are therefore suitable high frequency materials. The present invention is made in response to the above-mentioned development trend, and the purpose is to develop a low-temperature, low-dielectric-constant, and low-dielectric-loss dielectric ceramic composition. The temperature required for sintering is between 800-1 00 (TC, and can be between 1 The compaction is completed in 〇_60 minutes, so that it will be compatible with traditional thick film processes and use its existing equipment. [Previous technology] Low-dielectric ceramic composition oxide stone eve and 20-60wt% in US patent 4 No. 6 4 21 4 8 mentions that it contains 10-75wt% alumina and 5-70wt% amorphous borosilicate glass. This dielectric system has a dielectric constant of 4, 8-9, 6 in US Patent No. 4,672,152. The low-dielectric Taurman composition shown contains 50-95wt% crystallized glass and 5-50wU ceramic material. This dielectric system has

C: \ ProgramFiles \ Patent \ 0582-4179-E. Ptd page 6 460430 Description of the invention (3) There are 5.1-6.0 dielectric meter numbers. Deshi

Rn w s π A The next day's breakage composition is 5-20wt% lithium oxide, 60-9〇Wt% oxygen cutting, reducing% oxidation, and other basic gold group oxides except oxide. Pottery materials include oxide oxide and oxidation second. The low-dielectric ceramic composition shown in U.S. Patent No. 3926648 contains only crystallizable glass' & glass forms a cordierite crystal phase during sintering and has a dielectric constant of 5 2 and a line of 1-2 x 1 0-61 Thermal expansion coefficient. The low-dielectric ceramic composition shown in U.S. Patent No. 4,755,490 contains U-50 wt% oxide, 0-30 wt% amorphous silicon oxide, and 50-60 wt% glass. The glass composition contains 4wt% calcium oxide, 12wt% magnesium oxide, 29wt% boron oxide, and 42wt% silicon oxide. The sintering temperature is lower than 1000t, and the dielectric coefficient is between 4.5 and 6.1. The linear thermal expansion coefficient is between 3.94, 2 x 10 and 丨. The low-dielectric ceramic composition shown in Japanese Patent No. 4788046 contains quartz and glass. To increase the density of the dielectric system, the quartz powder is first coated with glass and then mixed with the glass powder. This dielectric material has a dielectric coefficient of 4.5 and a linear thermal expansion coefficient greater than 5 · 5 XI 0-6 κ-1. The low-dielectric ceramic composition shown in U.S. Patent No. 4,878,261 contains 70-85 wt% silicon oxide and 15-3 0 ^% borozinc glass. The sintering temperature of this system is lower than 1065 ° C and the dielectric constant is 5 -5. 5 rooms. ° [Objective of the Invention] It is known from the foregoing prior art that the industrial community urgently needs a dielectric ceramic material having a low temperature sintering and a low dielectric constant. In view of this, the main object of the present invention is to provide a low-temperature-wound dielectric ceramic composition 'which has a dielectric constant lower than 10 and a low dielectric loss. Another object of the present invention is to provide a composition of a dielectric substrate or element,

C: \ Prograni Files \ Patent \ 0582-4179-E, ptd page 7 " ". 460430 V. Description of the invention (4) Can be sintered at low temperature and short time, such as 80 0_100〇 ° C, 10-60 More than 95% densification is achieved in minutes. Another object of the present invention is to provide a method for manufacturing a ceramic finished product, which is characterized in that a ceramic finished product is manufactured by using the ceramic component described above, and the obtained ceramic finished product has a dielectric constant lower than 10 and a low dielectric loss. [Detailed description of the invention] The main feature of the present invention is to mix two ceramic materials including low-temperature glass and high-temperature ceramic phases in different proportions, and then lightly sintered at low temperature (800 ~ 100 00X :). The ceramic mixture can be used in The densification of more than 95% can be achieved in 15 to 60 minutes. The proportion of a ceramic material is not particularly limited, and it is mainly adjusted according to the properties of the desired finished product. " Low temperature glass "is defined in the present invention as an amorphous glass such as calcium lead zinc butterfly silica glass, whose glass softening point is between 600 ~ 800 ° C, and its main component is -40 ~ 55wt% silicon oxide, 5 ~ 15wt% alumina, 20 ~ 30wt% oxidation dance, 2 ~ 8wt% boron oxide, 2 ~ 8wt% lead hafnium, and 2 ~ 8wt% zinc oxide. &Quot; Thermal ceramic phase M is defined as a high melting point in the present invention. Or crystalline or non-crystalline oxides with high softening point, such as osmium sulfide or oxidized oxide, etc. Other oxides including anorthite, mullite, cordierite, calcium oxide, and magnesite are also suitable for the inventors. According to the composition of the dielectric ceramic of the present invention, calcium lead-zinc-borosilicate glass accounts for about 30 to 90 v ο 1%, and oxides accounts for about 70 to 100 〇1%; the better of which is calcium Lead-zinc butterfly acid glass accounts for about 50 ~ 70 v ο 1%, and oxide accounts for about 50 ~ 3 0vo 1% 〇 The present invention is mainly applied to laminated ceramic substrates and components, so the above ceramics

C: \ PrograraFiles \ Patent \ 0582-4179-E.ptd No. 8 Lu 460430 V. Description of the invention (5) Porcelain materials must be mixed with organic solvents such as methylbenzene and ethanol, and organic binders such as polyvinyl butyral (Polyvinyl butyral; PVB), and plasticizers such as Dibutyl Phthalate (DBP) are mixed to form a polymer material, which is formed by a doctor blade to produce green embryo flakes, and then screen printed conductor paste such as silver or gold, laminated, co-fired Finished. The manufacturing method of the laminated ceramic element of the present invention includes the following steps: (a) mixing 70-85 wt% of the ceramic component with 30-15 wt% of the organic carrier to form a slurry required for a doctor blade forming process; wherein the above-mentioned ceramic component includes · · 30-9 0vol% calcium-lead-zinc-borosilicate glass and 70-10vol% oxide; (b) using a doctor blade forming process, the above slurry is made into a green embryo sheet; (c) the green embryo sheet is printed online Out of the conductor circuit; (d) the green embryo sheet with the conductor circuit printed on the screen is laminated to form a laminated ceramic green embryo; and (e) the laminated ceramic green embryo is degreased and co-fired in an air atmosphere to complete densification. In order to make the above and other objects, features, and advantages of the present invention more comprehensible, a preferred embodiment is hereinafter described in detail as follows: [Example 1] Weigh 625g of calcium lead zinc borosilicate glass powder After adding 500 gram alumina grinding balls and 775c.c. isopropyl alcohol (2-propyl alcohol) in a 5 liter alumina ball mill tank, add the ball mill to a 3 2 5 raesh screen. , Placed in an oven, dried at 80 ° C for 16 hours, and then ground with a mortar and pestle. The particle size (D5D) of the obtained powder was 1 to 5 " m, and was measured by XRD (R i gaku D / Max I IB) judged that the powder was an amorphous phase. 0 # m。 Selected commercial alumina ceramic powder with a particle size (D5.) Of 0. 6 ~ 5. 0 # m. In this embodiment, ‘recycled acid glass and 50 vol%

C: \ Prograin Files \ Patent \ 0582-4179_E.ptd page 9 * 460430 V. Description of the invention (6) Mix the emulsified product with 5 wt% polyethylene glycol (ρ ο 1 yethy 1 ene giycol 200; PEG 200) and 50% by weight of n-propanol, mixed with a three-dimensional space cantilever mixer for 2 hours, the uniformly mixed slurry was dried and sieved to obtain a dry powder, and the powder was then dried under a pressure of 1 300 0 psi to obtain a high 0. . 3 cm, green embryos with a diameter of 3 cm. The prepared raw embryos were divided into three groups and sintered at 850 ° C (1A to 1C), 875 ° C (1D to IF), and 900 ° C (1G to II) for 1, 5, 30, and 60 minutes. The sintering process is mainly divided into two stages. The first stage is degreasing. Under the heating speed of 5 ° C / min, the embryos were slowly removed from the embryos to completely remove them. The temperature stayed at 500 t for one hour. The second stage is from 500 X at 5 ° C / min: warm up to 850 ~ 900 t, and then stay for 15 ~ 60 minutes for densification. The density of the sintered body was measured using the Archimedes principle. The results obtained in this example are shown in Table 1. The relative sintering densities of less than 95% were obtained at three different sintering temperatures and times. This result is also confirmed by scanning electron micrographs of the fracture surface of the sintered body. X-r a y diffraction analysis revealed the presence of oxidized crystals and anorthite crystal phases in the sintered body. And as the sintering temperature and time increase, the alumina crystal phase decreases, and the anorthite crystal phase increases to 875 ° C for 15 minutes to reach saturation. [Example 2] In this example, except that the ceramic composition is changed to 60 vo 1% calcium lead zinc boron acid glass and 40 vol% alumina, the rest of the manufacturing process and measurement procedure are the same as those in the first embodiment. The prepared raw embryos were still at 850 ° C (2A ~ 2C) and 875, respectively. (: (2D ~ 2F), 90 0 ° C (2G ~ 21) sintered for 15, 30, 60 minutes. The sintered density results are also listed in Table 1. Three different sintering temperatures and times were obtained.

C: \ ProgramFiles \ Patent \ 0582-4179-E.ptd page 10 4 6 0 4 3 0 V. Description of the invention (7) The sintered density is less than 95%. This result is also the scanning type of the fracture surface of the sintered body. The electron micrograph was confirmed. X-ray diffraction analysis revealed the presence of alumina and anorthi te crystalline phases in the sintered body. And with the increase of sintering temperature and time, the crystal phase of alumina decreases, and the crystal phase of anorthite is increased to 875 ° C for 15 minutes to reach saturation. [Embodiment 3] In this embodiment, except that the ceramic composition is changed to 70 vo 1% calcium lead zinc borosilicate slope wall and 30 v 001% alumina, the rest of the manufacturing process and measurement procedure are the same as those in the first embodiment. The prepared raw embryos were still sintered at 850 ° C (3A ~ 3C), 875 ° C (3F 3F), and 900 ° C (3G ~ 31) for 15, 30, and 60 minutes, respectively. The sintered density results and dielectric properties are also shown in Table 1. The relative sintering densities were higher than 95% at three different sintering temperatures and times. This result was also confirmed by the scanning electron micrograph of the fracture surface of the sintered body. X — j · ay diffraction analysis ~ It was found that the oxidized Is and 1¾ anorthite crystal phases existed in the sintered body. As the sintering temperature and time increased, the alumina crystal phase decreased, and the anorthite crystal phase increased to 8 Sinter at 75 ° C for 15 minutes to reach saturation. The dielectric constant is in the range of 7.95 to 8.19 (1 MHz) and the dielectric loss is in the range of 0.07 to 0.18% (1 MHz).

C: \ Program Files \ Patent \ 0582_4179-E.ptd page 11 460430 V. Description of the invention (8) Table 1 Examples of sintering temperature (° C) Sintering time (min) Relative density (%) Dielectric coefficient ( @ 1ΜΗζ) Dielectric loss (@ 1ΜΗζ) 1A 850 15 72.85 XX 1B 850 30 73.34 XX 1C 850 60 7 2.85 XX 1D 875 15 73.83 XX 1E 875 30 73.40 XX 1F 875 60 73.20 XX 1G 900 15 74.03 XX 1H 900 30 73.48 XX 11 900 60 74.52 XX 2A 850 15 91.70 XX 2B 850 30 91.31 XX 2C 850 60 90.92 XX 2D 875 Ϊ5 91.40 XX 2E 875 30 91.55 XX 2F 875 60 91.28 XX 2G 900 15 91.61 XX 2H 900 30 91.22 XX 21 900 60 91.07 XX 3A 850 15 97.64 8.17 0.0018 3B 850 30 98.17 8.19 0.0012 3C 850 60 96.80 8.10 0.0009 3D 875 15 96.21 8.05 0.0011 3E 875 30 96.21 8.01 0.0008 3F 875 60 96.02 8.04 0.0007 3G 900 15 96.55 8.08 0.0010 3H 900 30 96.05 8.04 0.0 0 08 31 900 60 95.01 7.95 0.0009

HHI C: \ ProgramFiles \ Patent \ 0582-4179-E.ptd page 12 460430 V. Description of the invention (9) -----. The ceramic components in the third embodiment can be densified more than 95% at a low temperature (85-900 C) and in a short time (15-60 minutes), and the sintering is completed in an air atmosphere. Since the sintering temperature required for high densification is compatible with low melting point, low impedance conductors such as gold and silver, all dielectric components can be co-fired with gold or silver conductors in the embodiment. In addition, the dielectric components in the examples all have a low dielectric constant (7.95 to 8.19) and a low dielectric loss (07 to 0.018%). The thermal expansion coefficients of all components are in the range of 5. 2 ~ 6. 2 p p m / ° C. In the above embodiments, all the dielectric components can be co-fired with a low melting point, low impedance conductor such as silver to form a laminated substrate or element. In the manufacturing process, the above-mentioned dielectric components must be mixed with an organic solvent such as methylbenzene and ethanol, an organic binder such as Polyvinyl butyal (PVB), and a plasticizer such as Dibutyl Phthalate (DBP) to form a slurry, which is formed by a doctor blade to produce a thickness. A green embryo sheet of about 125 microns was punched into a 10 cm square green embryo sheet. Holes were punched in the raw embryo flakes using a mold with a hole diameter of about 25 microns, and a conductor paste such as silver was filled into the holes by screen printing. In addition, the conductor lines on the green embryo sheet are also made by screen printing. The screen-printed and hole-filled raw embryo flakes were stacked in order and laminated to produce laminated ceramic embryos. The conditions for lamination were r ^ 1 000-3000 pS1 〇 ^ ^ ^ ^ Λ 7 after degreasing and co-firing (800- 900 ° C). The dielectric components in the embodiments can also be made into ceramic bodies of various shapes and uses through traditional processes such as dry pressing, cold equalizing, and hot equalizing. Taking dry pressing as an example, ceramic powder can be mixed with water and a binder such as Polyvinyl alcohol (PVA). After spray granulation, the powder's fluidity can be improved.

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Claims (1)

460 Public ♦ Q847 6. The scope of the patent application 1. A dielectric ceramic composition comprising: 30-9Ovol% calcium lead zinc borosilicate glass; and 70-10vol% oxide; wherein the calcium lead zinc zinc boron The main ingredients of silicate glass include: 5-15wt% oxide; 20-30wt% good oxidation; 2-8wt% lead oxide; 2-8wt% zinc oxide; 2-8wt% boron oxide; and 40-55wt% silicon oxide Silica and the oxide is selected from the group consisting of alumina, calcium oxide feldspar, mullite, cordierite, calcium oxide, and magnesium olive 2. Dielectric as described in item 1 of the scope of patent application A ceramic composition including: 50-70 vol% calcium lead zinc borosilicate glass; and 50-30 vol% oxide. 3. The dielectric ceramic composition according to item 1 of the scope of patent application, wherein the oxide is alumina. 4. A method for manufacturing a laminated ceramic element, comprising the following steps: U) mixing 70-85% by weight of a ceramic component with 30-15% by weight of an organic carrier to form a slurry required for a doctor blade forming process; wherein the ceramic component includes: 30-90v〇U calcium-lead-zinc-borosilicate glass and 701〇ν〇ι ％ oxide; yb) using a doctor blade forming process, the polymer is made into a green embryo sheet; (c) & 1¾ & & Sheet printed conductor lines on the Internet; Ι ^ ϋΙ IHBHH Page 15 460430 __Abandoned No. 87120847_Year Month Day __Amendment ____ 6. Scope of Patent Application (d) The embryos with conductor lines printed on the screen The sheet is laminated to form a laminated ceramic green body; and (e) the laminated ceramic green body is densified and co-fired in an air atmosphere to complete densification, wherein the sintering temperature is 800-1000 ° C. 5. The manufacturing method according to item 4 of the scope of patent application, wherein step (a) the ceramic powder comprises: 50-70 vol% calcium lead zinc borosilicate glass; and 50-30 vol% oxide. 6. The manufacturing method as described in item 4 of the scope of patent application, wherein in step (a) the main components of the calcium-lead-zinc-borosilicate glass include: 5- 15wt% tritium chain; 20-30wt% oxidation feed; 2- 8 wt% lead hafnium; 2-8 wt% zinc oxide; 2-8 wt% boron halide; and 40-55 wt% stone oxide. 7. The manufacturing method as described in item 4 of the scope of patent application, wherein step (a) the oxide is oxide. 8. The manufacturing method as described in item 4 of the scope of patent application, wherein step (a) the oxide is selected from the group consisting of alumina, silica, anorthite, mullite, cordierite, calcium oxide , And forsterite. 9. The manufacturing method as described in item 4 of the scope of patent application, wherein step (a) the organic vehicle comprises: an organic solvent, an organic binder, and an organic plasticizer. 10. The manufacturing method as described in item 4 of the scope of patent application, wherein No. 16yin 460430 _ case number 87120847_ year month day amendment _ six, patent application scope (e) the sintering time is 15-60 minutes. 11. The manufacturing method according to item 4 of the scope of patent application, wherein the dielectric coefficient (@ 1ΜΗζ) of the multilayer ceramic element is between 7.95-8. 19, and the dielectric loss (@ 1ΜΗζ) is 0.07-0. 18% of The thermal expansion coefficient is between 5.2-6. 2ppm / ° C. 0582-4179-EFl.ptc Page 17…; a p7 j έ θ: ί Amendment # Application date: Public case board: 87120847 | J Category:-(CoΗ 6 ^ j ^ -LL j .., ( The above columns are filled by this bureau) Invention Patent Specification 460430 Chinese Low Temperature Sintering Low Dielectric Constant and Low Dielectric Loss Ceramic Composition, Invention Name English Low-Fire, Low-Dielectric ~ Constant and Low-Loss Ceramic Compositions Name (Chinese ) 1. Lin Shichang 2. Jian Chao and the name of the inventor (English) 1. 2. Nationality 1. Republic of China 2. Residence and residence of the Republic of China 1. 2nd floor, No. 157, Jianguo Road, Xindian City, Taipei County 2. Shuangqiao City, Taipei County Name (Name) C, 11th Floor, No. 48, Section 2, Shi Road 1. Name (Name) (English) of Tak Electronic Industry Co., Ltd. 1. Nationality 1. Residence, Residence (Office) of the Republic of China Applicant 1. Taipei County Banqiao Emperor; No. 52, Section 2, Ji 12 Name of Representative (Chinese) 1. Name of Representative of Guo Chunling (English) 1. 0582-4179-EFLptc Page 1 4 eM% ° Amendment No. 87 丨 b〇847 IV Abstract of Chinese Invention (Name of the invention: low temperature sintering ceramic composition with low dielectric constant and low dielectric loss) A ceramic material composition with low temperature sintering, low dielectric constant and low dielectric loss characteristics It is more than 95% densified within 15 to 60 minutes at 〇OO ~ 1000 ° C. Its composition includes 30 ~ 90v〇1% calcium button 77 borosilicate glass and 70 ~ 10vol% oxide and can be mixed with organic solvents, binders, and plasticizers, and formed into a green embryo sheet by doctor blade forming. Then, through screen printing and lamination, it can be co-fired with copper to produce laminated ceramic substrates or components with high conductivity, low melting point metals such as gold, silver, and silver. English Abstract of Invention (Name of the invention: Low-Fire, Low-Dielectric-Constant and Low-Loss Ceramic Compositions) A ceramic composition for forming a multilayer ceramic substrate which can be dens ifi ed up to 95% at 800 ~ 1 000 ° C within 15-60 min. The ceramic composition includes a mixture of finely divided particles of 30 ~ 90vol% Ca-Pb-Zn borosilicate glass and 10 ~ 70vol% oxide. The multi layer ceramic substrate composition can be used with organic solvents, polymeric binder and plasticizer to produce an unfired green tape which is co fi rab1e with high electrical conductivity metallurgies 0582-4179-EFl.ptc Page 2 0582-4179- ^ 1 ^ 10 Page 3 of 460 ♦ The original Q847 6. The scope of the patent application 1. A dielectric ceramic composition comprising: 30-9Ovol% calcium lead zinc borosilicate glass; and 70- 10vol% oxide; the main components of the calcium-lead-zinc-borosilicate glass include: 5-15wt% oxide; 20-30wt% good oxidation; 2-8wt% lead oxide; 2-8wt% zinc oxide; 2-8wt % Boron oxide; and 40-55 wt% silica; silica and the oxide is selected from the group consisting of alumina, calcia feldspar, mullite, cordierite, calcium oxide, and magnolia 2. The dielectric ceramic composition according to item 1 of the scope of the patent application, which comprises: 50-70 vol% calcium-lead-zinc-borosilicate glass; and 50-30 vol% oxide. 3. The dielectric ceramic composition according to item 1 of the scope of patent application, wherein the oxide is alumina. 4. A method for manufacturing a laminated ceramic element, comprising the following steps: U) mixing 70-85% by weight of a ceramic component with 30-15% by weight of an organic carrier to form a slurry required for a doctor blade forming process; wherein the ceramic component includes: 30-90v〇U calcium-lead-zinc-borosilicate glass and 701〇ν〇ι ％ oxide; yb) using a doctor blade forming process, the polymer is made into a green embryo sheet; (c) & 1¾ & & Sheet printed conductor lines on the Internet; Ι ^ ϋΙ IHBHH Page 15