TW391951B - Low-fire and low-dielectric-constant ceramic compositions - Google Patents

Abstract

A ceramic composition for forming a multilayer ceramic substrate which can be densified up to 95% at 800-1000DEG C for 240 min. The ceramic composition comprises a mixture of finely divided particles of 30-60vol% borosilicate glass (BSG), 40-70vol% titanium silicate glass (TSG) and 0.5-30 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 metals such as gold, copper and silver-palladium.

Description

V. Description of the invention (1) [Field of the invention] The present invention is to sinter a multilayer ceramic substrate at a low temperature. [Background of the invention] Due to the characteristics of the electronic body circuit (VLSI structure substrate material guilty degree, etc.) during the electrical transmission process, Such as: silver and silver co-firing, the substrate must be in addition, due to the relationship between the signal and the dielectric ceramic luxury; bf · pole, board or component m 相关 is related to the dollar points, especially for the application of compact, variable, this ceramic The components can: Have a low dielectric constant and a low dielectric loss. The system is designed to be light, thin, short, and have a high accumulation density, in: in conjunction with the ultra-large product, the transmission rate between the two and eight wires, the high line density, and the plane. In order to improve the signal transmission rate, In order to avoid the weakening of strong signals, the conductive materials in the construction need to use the highly conductive metal Zhao σ gold 'gold, steel, etc .; and in order to be able to sinter dense with the above metals at 800-1 0 0 (TC. Number delay (td) and The dielectric constant (k) of the substrate material has the following

td = k1 / 2 L / C where 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, reducing the dielectric loss (tan6) of the base material can avoid mutual interference between signals, thereby improving the circuit density on the substrate. In terms of guilt, as the size of the wafer continues to increase, and about 80% of the wafers are bonded directly to the substrate material by Surface Mount Technology (SMT).

C: \ path \ 0582-4215-E. Ptd Page 5 V. Description of the invention (2) The thermal stress problem caused by the difference in thermal expansion between the two will cause; the excessive stress will cause the substrate and wafer to crack or peel off: board; Electronic-free components will be large under high integration and high-speed operation. In addition, in order to prevent damage to electronic components on the substrate due to overheating, it can also be a condition that the substrate material must have. Good mechanical properties In general, when selecting ceramic substrate materials, the characteristics include: low dielectric constant, low dielectric loss *, thermal expansion: I / I? The junction temperature is 10,000. . In the following, it can be co-fired with silver, silver-her, two ,,, >, copper and other metal conductors, and has high heat and mechanical strength. In addition, since the resonance frequency of the dielectric material is very high, it can be used as a high-frequency material for making components in the range of more than 300MHz to the microwave (GHz). In order to develop a low-temperature, low-dielectric-constant, and low-dielectric-loss dielectric ceramic composition, the sintering temperature is 950 to 1 00. . It can be completed in 24 minutes. It will be compatible with traditional thick film processes and use its existing equipment. [Prior art] The low-dielectric ceramic component mentioned in US Patent No. 46 421 48 contains 10-75 wt% alumina, 5-70 wt% amorphous silicon oxide, and 20-60% by weight Glass, this dielectric system has a dielectric constant of 4 · 8_9.6. The low dielectric ceramic composition shown in U.S. Patent No. 46 72 1 52 contains

V. Description of the invention (3) There are 50-9 5wt% crystallized glass and 5_5〇w right 1-r η 人 person & J Youcai 枓 This dielectric system has two = / qi :: coefficient. The crystalline glass-breaking composition is 5, Erhuazhong, alkali gold group oxygen. Second, Wt% oxide and "Wt%" materials except oxide bell include oxide oxide and silicon oxide. Containing ί: 2Γ926648 low-dielectric Tao Yao component only ί 5 2 / Λ: glass forms cordierite, crystalline phase and has 5.2 in firing and junction; 丨 electric coefficient and BU 2χ1 〇_6 The linear thermal expansion coefficient of κ_ !. There are two low-dielectric ceramics shown in the "United States" patent / ⑷55490, which contains 2 (0-50 wU oxide oxide, 0-30wt% amorphous oxide stone, and 5600wt% glass. Ϊ ^ It contains 4Wt% calcium oxide, 12WU magnesium oxide, 4.5wt% oxygen, and the linear thermal expansion coefficient is between 3.9-4. 2x1 〇- < boron and 42wt% silicon oxide. Sintering temperature is low s1〇〇 { rc, dielectric coefficient ^ C Ί 198, above t... 'K-1 contains quartz and glass in the low dielectric ceramic composition shown in US Patent No. 4,878,046. To improve the density of the dielectric system, first Quartz powder is coated with glass, and then mixed with the glass powder. This dielectric material has a dielectric constant of 4.5 and a linear thermal expansion coefficient greater than 5.5 × 1 o-iM. Low as shown in US Patent No. 4,898,261 The composition of dielectric ceramic tincture contains 70-85wt% silicon oxide and i5-30wt% boro-zinc glass. The sintering temperature of this system is lower than 1065 ° C and the dielectric coefficient is between 5-5.5. [Objective of the Invention] From the previous It is known from the technology that the industrial community urgently needs a dielectric ceramic material that can be sintered at a low temperature and has a low dielectric constant. The main object of the present invention is For low temperature sintered dielectric ceramic

Minutes, which has a dielectric coefficient and a low dielectric loss of between 4.4 and 5.2. Another object of the present invention is to provide a composition of a dielectric substrate or a component, which can be sintered at a low temperature, for example, to achieve a density of 95% in 800-1 00c, 24 minutes. [Detailed description of the invention] The main feature of the present invention is that three ceramic materials including low-temperature glass and high-temperature ceramic phases are mixed in different proportions. After low-temperature sintering (800,000.00) process, the ceramic mixture can reach a density of more than 95% in 240 minutes. There is no particular limitation on the proportion of materials, mainly depending on the nature of the finished product ^

whole. n J " Low temperature glass " is defined in the present invention as a low softening point non-crystalline glass such as borosilicate glass (600 ~ 80 (rc), the main component is 19_30 wt% boron, 60-80 wt% Silicon oxide, aluminum oxide, 0.5 wt% calcium, and 0.4 wt% alkali metal oxides such as lithium oxide, sodium oxide, and potassium halide " high-temperature ceramic phase " are defined as high softening points in the present invention. Said t. 7 factory, Ό white Θ glass such as titanosilicate glass (> 140,000), the main components are 20% titanium oxide resistant, 80-9-9wt% silicon oxide; and high melting point crystal Or non-crystalline oxides such as germanium or silicon oxide, etc. Other oxides include feldspar, mullite, cordierite, calcium oxide, magnesite and mixtures of the above two oxides are also suitable for use in the present invention. According to the composition of the dielectric ceramic according to the present invention, borosilicate glass accounts for about 30-60 vol%, chin-acid glass accounts for about 40-70%, and oxides account for about 0.05%.

V. Description of the invention (5) 3 Ονο 1% The present invention is mainly applied to laminated ceramic substrates and components. Therefore, the above-mentioned ceramic material mixture must be mixed with organic solvents such as toluene and ethanol, and organic binders such as polyvinyl butyral (polyvinyl butyral). , PVB), and plasticizers such as dibutyl phthalate (D ibuty 1 phthalate 'DBP) are mixed to form a polymer material. The raw embryo flakes are formed by doctor blade molding, and the conductor paste such as silver-silver or gold is finally laminated by screen printing. Compression and co-firing into finished products. < The method for manufacturing a laminated ceramic element of the present invention includes the following steps: (a) mixing 70-85wt% of ceramic powder with 30-15% by weight of an organic carrier to form a slurry required for a cutting blade forming process; wherein, the above The composition of the ceramic powder includes: 30-60voU borosilicate glass, 40-70vol% titanosilicate glass, and 0.5-30voi% oxide; (b) a scraper forming process is used to make the above materials A raw embryo sheet; (c) printed conductor lines on the raw embryo sheet; (d) a green embryo sheet with a conductor line printed on the screen, and laminated to form a laminated ceramic embryo; and (e) a laminated ceramic embryo on Densification and co-firing are performed in the air atmosphere to complete densification. In order to make the above description and other objects, features, and advantages of the present invention more comprehensible, a preferred embodiment is hereinafter described in detail as follows: [Example 1] Measure borosilicate acid and titanosilicate glass powder 6 2 5g, respectively add 5000g of oxidized oxide grinding balls' and 775cc. 2-propyl alcohol in a 5 liter alumina ball mill tank, ball mill the slurry after passing through the 325 mesh division mesh. Oven, dry at 80 ° C for 16 hours, and then grind with mortar and pestle

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Fencai, -i 2 = Qin Shu's particle size (0 50) is i ~ 5 from 111, after x_ray diffraction: the powder is judged to be an amorphous phase. Selected commercial germanium oxide ceramic powder has a particle size (D50) of 0.6 to 50. In this example, press 20 vol ° /. Borosilicate glass, 75vol% titanosilicate glass and 5v〇1% germanium oxide are mixed and then mixed with 5wt% polyethylene glycol j ° ^ yethylene Wycol 200 (PEG 200) and 50wt% n-propanol. Degree space cantilever mixer for 2 hours. The uniformly-mixed Nissan was dried and sieved to obtain a dry powder, and the powder was then dry-pressed to obtain a green embryo with a diameter of 0.3 cm and a diameter of 1.3 cm. The prepared raw embryos were divided into five groups, which were sintered at 90 (TC (1A), 925 ° C (1B), 95 0 t: (lC), 975 ° C (1D), and 〇00〇C (1E), respectively. 24 minutes. The sintering process is mainly divided into two I% # again. The first stage is degreasing. The green embryos' slowly remove the organic binder in the green embryos at a heating rate of 5 ° c / min, and it is completely cleared. 1 temperature It stays at 500 ° C for one hour. The second stage is heated from 500 ° C to 900-1 000 ° c 'at 500 ° C / min, and then stays for 240 minutes for densification. Measured by Archimedes' principle The density of the sintered body. The results obtained in this example are listed in Table 1. The relative sintered density was less than 95% at five different sintering temperatures. This result is also obtained from the scanning electron micrograph of the fracture surface of the sintered body. This is confirmed by X-ray diffraction analysis. The germanium oxide crystal phase is found in the sintered body. With the increase of the sintering temperature, there is no obvious crystal phase. [Example 2] In this example, except that the ceramic component is changed to 30 vol% borosilicate Acid glass, 65

V. Description of the invention (7) Except for v ο 1% titanosilicate glass and 5 v ο 1% oxidation record, the remaining processes and measurement procedures are the same as those in the first embodiment. The prepared raw embryos are still sintered at 900 ° C (2A), 925 ° C (2B), 9 50 ° C (2C), 975 ° C (2D), and 100 (TC (2E)) for 240 minutes. The Mead principle was used to measure the density of the sintered body. The results obtained in this example are shown in Table 1. The relative sintered density was less than 9 5% at five different sintering temperatures. This result is also scanned by the fracture surface of the sintered body. This type of electron micrograph has been confirmed. X-ray diffraction analysis found that the germanium oxide crystal phase exists in the sintered body. And with the increase of sintering temperature, there is no obvious crystal phase change. [Example 3] This example except ceramic components Except 40v〇1% borosilicate glass, 55 vol% titanosilicate glass and 5vol% germanium oxide, the remaining processes and measurement procedures are the same as in Example 1. The prepared raw embryos are still at 900 ( 3A), 925 ° C (3B), 950 ° C (3C), 975 ° C (3D), 100 ° C (3E) for 240 minutes. The sintered density results are also listed in Table 1 e 95. The relative sintering density of more than 95% can be obtained at the sintering temperature of _1〇00〇c. This result is also obtained from the scanning electron micrograph of the fracture surface of the sintered body. The x_ray diffraction analysis found that the germanium oxide crystal phase existed in the sintered body, and the germanium oxide crystal phase did not change significantly with the increase of the sintering temperature. A dense test piece was sintered at 95 ° C, and its dielectric properties were measured. The coefficient of thermal expansion is as shown in Table 2. The dielectric coefficient and dielectric loss at 1 MHz are 4 46 and 〇28%, and the coefficient of thermal expansion is 2.03 ppm / t.

Page 11 V. Description of the invention (8) Table 1 Exemplary composition Relative density (%) ⑲ Different temperatures fC) Sintering 240 minutes 分 BSG TSG GaA 900 (A) 925 (B) 950 (C) 975 (D) 1000 (E) 1 20 75 5 70 73 75 92 92 2 30 65 5 77 S3 84 94 95 3 40 55 5 90 93 97 98 98 4 40 50 10 89 92% 97 98 5 40 40 20 89 91 95 96 96 6 40 30 30 80 82 88 91 92 Table 2 Examples of electrical and thermal properties of the composition test piece @ 95 (TC, 240 entries sintered BSG TSG Ga203) Relative density (%) Dielectric constant (k) Dielectric loss (% ) Thermal inflation coefficient (ppmiC) 3 40 55 5 97 4.46 0.28 '2.03 4 40 50 10 96 4.69 0.20 1.23 5 40 40 20 95 5.18 0.15 2.32 1111_ Page 12 C: \ path \ 0582-4215-E. Ptd 5 Explanation of the invention (9) [Example 4] In this example, except that the ceramic composition is changed to 40 vol% borosilicate glass, 50 vo 1% titanosilicate glass and 10 vol% 1% germanium oxide, the rest of the process and measurement The procedures are the same as in Example 1. The prepared raw embryos are still at 900 ° C (4A), 925 ° C (4B), 95 (TC (4C), 97 5 ° C (4D), 100 (TC (4E)). ) Sintering for 240 minutes. The results of sintering density are also listed in Table 1. 9 5 Relative sintering density higher than 95% can be obtained at a sintering temperature of -1 00 ° C. This result is also confirmed by the scanning electron micrograph of the fracture surface of the sintered body. X-ray diffraction analysis found that the sintered body has a memory In the crystalline phase of germanium oxide, and with the increase of the sintering temperature, the crystalline phase of germanium oxide has not changed significantly. Take the sintered compact test piece at 95 ° C and measure its dielectric properties and coefficient of thermal expansion. Results As shown in Table II, the dielectric coefficient and dielectric loss are 4.69 and 0.20% at 1MHz, respectively, and the coefficient of thermal expansion is 1.23ρριπ / ° (: [Example 5] This example removes VO 1% titanium The silicate glass is 925 ° C (5B) and 950 minutes in the first example. The sintering temperature can obtain a high sintered body fracture surface analysis and found that the increase in sintering, the chemical composition is changed to 4. ν〇ι% borosilicate glass, 40 and 2Ovol% germanium oxide, the remaining processes and measurement procedures. The prepared raw embryos were still sintered at 90 ° (rc (5A), CC5C :), 97 5 ° C (5D), and 1000 ° c (5E). The results are also listed in Table-. The sintering of 950-1001c = a relative sintering density of more than 95%. This result is also confirmed by known concealed electron micrographs. X-r a y around = there is a crystal phase of germanium oxide, and the crystal phase does not change significantly with the sintering temperature. Take 950. (: Caused by sintering

C: \ path \ 0582-4215-E_ptd The dense test piece on page 13 was used to measure its dielectric properties and coefficient of thermal expansion. The results are as shown in Table 2. The dielectric coefficient and dielectric loss are 5.18 at 1 MHz. And 0.15%, and the coefficient of thermal expansion is 2.32ppm / t :. [Example 6] In this example, except that the ceramic composition is changed to 40 v ο 1% borosilicate glass, 30 v〇U titanic acid glass and 3 (^ 〇1% germanium oxide), the remaining processes and measurement procedures All are the same as in Example 1. The prepared raw embryos are still at 900 t (6 A), 925 1 (6B), 950 ° C (6C), 975 ° C (6D), and 1000 t ( 6E) Sintering for 240 minutes. The density of the sintered body was measured using the Archimedes principle. The results obtained in this example are shown in Table 1. Relative sintering densities of less than 9 5% were obtained at five different sintering temperatures. Scanning electron micrographs of the fractured surface of the sintered body have also been confirmed. X-ray diffraction analysis found that the crystalline phase of germanium oxide is present in the sintered body. With the increase of the sintering temperature, there is no obvious change in the crystal phase. The ceramic components in the third, fourth, and fifth embodiments described above can all achieve a density of more than 95% at a low temperature of 50 1 0 0 C) and 240 minutes, and the sintering is completed in an air atmosphere. Since the sintering temperature required to complete high densification is compatible with both low melting point and low-impedance conductors such as gold and silver-, all the dielectric components in Examples 3-5 can be compatible with gold or silver- Co-fired palladium conductor. In addition, the dielectric components in the examples all have a low dielectric coefficient (4. 46 low dielectric loss (0.15.0.28%). The thermal expansion coefficients of all the components are in the range of 1.23-2.32 ppm / ° C. In the third to fifth embodiments described above, all the dielectric components can be co-fired with low-impedance conductors such as silver_palladium or gold to make multilayer substrates or elementary alloys. First, the above-mentioned dielectric components must be mixed with an organic solvent such as methyl alcohol, an organic binder such as polyvinyl butyal (ρνβ), and plasticized product = mhthaiate (dbp) to form a slurry, which is scraped to a degree of about 125 microns. After the green embryo sheet 1 was punched, two micro halves were punched. The green embryo sheet was punched with a mold with a hole diameter of about 125-micron, and the conductor paste such as silver-palladium was filled into the hole by screen printing. In addition, the good It is also made by screen printing technology. Screen printing and hole-filling cymbals are sequentially stacked, and laminated ceramic green embryos are made by lamination, and the lamination conditions are 60- 100. 00; and 1 00 0__30〇 () Rabbit Health Embryo &: Burning (9 50,00 t) to complete the densification. Pressing can be done through traditional processes such as dry pressing and cold equalizing. 'Ceramic powder can be bonded with water and: The body can be made into a finished product by drying, degreasing and sintering. For example, the fluidity of the body can be made by dry pressing. Although the present invention has been described in a preferred embodiment, & It is not intended to be used within the scope '. Various changes can be made. Without departing from the spirit of the present invention, the scope of patents attached to it should be considered;

Claims (1)

391951 VI. Scope of patent application 1. A dielectric ceramic composition whose composition includes: 3 0-60 v v 1% shed; ε evening acid glass .; 40-70vol% titanium stone evening acid glass; and 0.5-30vol% Oxide. 2. If the patent application of Fanyuan No. 1 is raised-described in the following: Zhongdian, Tao, and Jinghuafen, the main components of the borosilicate glass include: '~ 19-30wt% boron oxide, 60-8 廿 wt% Oxide stone '〇1_4wt% alumina, 0.)-4wt% calcium oxide, and 0.1-4wt% are selected from the 验 test of sodium sulfide and potassium oxide-gold group oxide. 3. Among them, the dielectric ceramic composition described in item 1 of the scope of the patent application, the main components of the titanium acid glass include: 1-2 0 wt% titanium oxide; and ω-9 9 wt%-oxide stone Plant 4. The dielectric ceramic described in item 1 of the scope of patent application replaces the oxide with germanium oxide. For each of the feldspars, more than one kind of oxygen β5., Such as Shen. 谞 Patent Patent., Wai. No.1.-Description-Description ..... The dielectric ceramics, Wei composition should The oxide escapes from the following groups: oxidized stone eve 77 to stone cordierite., _ Oxygen. Chemical dance, .. flag, withdrawal stone, and a mixture of the above. 6. "A method of manufacturing a ceramic finished product, including the following steps. (Bow) 7 0-8 5wt% of" Tao straight powder and 1 5- to form the slurry slant required for the blade forming process "The L component includes: 30-60 vol >, silicate glass, 40-7n and d. / Glass, and 0. ~ 5 2 30 vo 1¾ 'oxide; ~ (\) using a doctor blade forming process, the slurry 匍 7 springs or a raw embryo sheet; C: \ path \ 0582-4215-E. Ptd 39I95i 6. The scope of patent application (C) Print the conductor circuit on the green embryo sheet; (d) 'The green embryo sheet printed with the conductor circuit on the screen is laminated to a ceramic green embryo; and (e) The laminated pottery embryo is densified in air atmosphere and densified by co-firing. 7. The manufacturing method described in item 6 of the scope of the patent application, wherein the main components of the deleted silicate glass include: 19-3 0wt% oxidized township, .6q_8. 〇.wt% _ oxidized crushed milk ... Ming, 0.1 to 4% by weight of calcium oxide, and 0 ;; 1 to 4% by weight is selected from the basic oxides of lithium oxide, sodium oxide and potassium oxide. 8. The manufacturing method as described in the scope of the patent application-item 6, wherein the main components of the cyanosilicate glass include: l-20wti emulsified cyanide and oxygen ~ chemical ~ broken. · 9. The manufacturing method according to item 6 of the scope of patent application, wherein the oxide is germanium oxide. 10. The manufacturing method as described in item 6 of the scope of patent application, wherein the oxide ^ is selected from the group consisting of silicon oxide, feldspar, mullite, cordierite, ',.撖 ~ Lambolite and a mixture of two or more of the above oxides. '11. Know the manufacturing method described in item 6 of the Quarry range, wherein the steps (& If the organic substance includes: organic solvents, organic binders, and organic plastics. 12. As described in item 6 of the scope of patent applications Manufacturing method, wherein the sintering temperature of step impurity (e) is 8 00- 1 00, and the maintained time is 240 minutes. I] Page 17 C: \ path \ 0582-4215-E. Ptd _391951_ VI. Application scope 1 3. The manufacturing method described in item 6 of the scope of patent application, wherein the dielectric coefficient of the accumulated ceramic element is 4.46- Between 5.18, the dielectric loss (1MHz) is between 0—. 丄 5-1 28%, and the coefficient of thermal expansion is between 1.2-2. 3ppm / ° C. C: \ path \ 0582-4215-E. Ptd page 18