TWI311768B - - Google Patents

Description

MODIFICATION ^11768 ^ '^ ---ΜΆ 9211861Q_年月五, invention description (1) Technical Field of the Invention The present invention relates to a composition of ultra-low temperature firing dielectric ceramic powder, which can be used for manufacturing temperature compensation type. Multilayer ceramic capacitors. The invention is more suitable for use in the EiCtronic Industry Association (referred to as t I. A.), and the temperature coefficient is NP〇, that is, the capacitor is at -55t~125. (Between: the temperature coefficient of the capacitance value (1/C) (△ [/ △ T) shall be within the range of 〇 ± 30ppm / ° C. [Prior Art] - the general ceramic capacitor is based on the composition of its porcelain powder The electrical constants can be divided into three categories: high dielectric constant type (Hi-Κ), dielectric constant type (Mid_K) and W degree compensation type (TC). High dielectric constant type has a dielectric constant of 4 〇〇〇~ 1 5000 'but its value varies greatly with temperature. The dielectric constant type = dielectric capacity is about 1400~3000, and the dielectric constant changes little with temperature but is often nonlinear. The dielectric constant of temperature compensation type is about 8~丨〇〇, the change of dielectric constant with temperature is the smallest and often linear change. The internal electrode of the multilayer ceramic capacitor and the ceramic dielectric layer must be co-fired together, so the ceramic powder composition of the common commercial multilayer ceramic capacitor is The firing temperature can be divided into two types: high temperature firing system and low temperature firing system. The firing degree of high temperature firing system is about 1 250 ° C ~ 1 3 0 0 t: because of the firing temperature. High, so the internal electrode generally needs to use a high melting point, and expensive palladium (pd) noble metal ° low temperature firing Since the firing temperature is below 1 150 t, the internal electrode can be reduced in cost by using a cheap silver-palladium alloy metal (Ag/pd) with a high silver content. The dielectric constant is about 8 100 ^ ', but the current technology is manufacturing a low capacitance npo product below 1 〇〇pF.

1311768 ---------------- Year, month and day correction ____ V. Invention description (2) When the layer of ceramic capacitors is used, if the dielectric constant of porcelain powder is higher, due to the number of layers Less often because process control is not easy, the capacitance value of ceramic capacitor often deviates from the specification value, so that the yield is low; if the ceramic powder with lower dielectric constant is used, the number of layers is higher. There are many, so that the cost of the internal electrode material is increased. Therefore, the current production of multilayer ceramic capacitors of 10 OpF or less is usually made of porcelain powder having a dielectric constant of 15 to 45, in order to obtain optimum economical production. Generally, low-temperature firing is a composition of dielectric porcelain powder, usually with a main component fired at a high temperature and then added various sintering aids such as glass, glass, frit or flux. In order to lower the firing temperature, generally the glass or glass frit contains a low melting point component such as Pb or Cd or Bi. Pb and Cd are harmful substances to the environment and ecology. In response to the trend of environmental protection, it is necessary to develop a dielectric powder composition containing no Pb or Cd. SUMMARY OF THE INVENTION A composition of a low-temperature-fired temperature-compensated ceramic capacitor is disclosed in U.S. Patent No. 4,506,026, the disclosure of which is incorporated herein by reference. The composition Pb0-Bi2 03 -Cd0-Zn0-Si02-B2 03 glass and the main component Ba0-Ti02-Zr02-Si02 and the subcomponent Pb0-Ti02-Zr02-Al2 03 -LiF- disclosed in No. 5, 599, 757 The composition of the Si02-B2 03 glass meets the NP 0 specification of E. I · A, but the firing temperature must be above 110 ° C and the composition of the porcelain powder contains Pb or Cd which is harmful to the environment. Therefore, the firing temperature is below 10 °C and adding BaO-Zn〇-Nb2〇5-Ti〇2 as the main component to add N t>2 〇5 - S i 〇2 - Μ η 0 - Ζ The composition of the ceramic powder of the multilayer ceramic capacitor containing no Pb, Cd or Bi of the η 0 - Bz 〇3 frit component has not yet appeared. The invention selects the appropriate principal component system to add the sintering without Pb and Cd.

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Case No. 92218619 V. Description of the invention (3) The auxiliary agent reduces the sintering temperature to less than 1 ,, and can be applied within 9〇% Ag/10% Pd which is cheaper than 7〇%Ag/3〇%Pd. Electrodes reduce costs to make more economical multilayer ceramic capacitors. The object of the present invention is to develop a laminated ceramic capacitor which can be fired at a low temperature in 丨0〇〇, and does not contain lead, cadmium, tellurium and the like, and the dielectric constant of the electrical property can reach 35 to 45 or more. The q value is more than 1〇〇〇/the temperature coefficient is in accordance with EIA's ΝΡ0 specification, ie 〇±30ppm/t, which is suitable for the dielectric porcelain powder used in the manufacture of temperature-compensated multilayer ceramic capacitors. For the purpose of the above, the composition of the dielectric porcelain powder of the ultra-low-temperature firing layered ceramic electric grid of the present invention is composed of 1 part by weight.

$33.0%, 1.5% SZnO$12.0%, 0.5% SNb205 $6.0%, 54.0% STi〇2$65.0% consisting of the first component 'combined with 0.5 to 16 parts by weight of the second component consisting of frit , wherein the composition of the glass frit is 〇$Nb2 05 $10%, 0% $Si02 $10%, 0% S

MnO $10%, 30% SZnO $8 0%, 2 0% SB2〇3 $6 0%. According to the above composition range, adding fr i t as a main component of Ba4Ti13〇3Q, BaTi4 09, Ba2Ti90 2〇, etc. to jointly reduce the sintering temperature to below 1 〇 〇 〇 °c and improve the compactness of the sintered body. Control the content ratio of different Ba4Tii3〇3Q, BaTi 4〇9 ’ Ba2Ti9 02Q, and adjust the temperature coefficient of capacitance; adding glass frit can increase the sintering density and improve the insulation resistance. In order to further disclose the technical content of the present case, please refer to the following embodiments: [Embodiment]

Page 7 1311768 Case No. 92181619__年月日日_Amendment_ V. Invention description (4) With B a C 03 (carbonic acid pin) ' Ζ η 0 (zinc oxide), N b2 05 (pentadium oxide), Ti 〇2 (titanium oxide) as the starting material, weighed according to the composition ratio shown in Table (1), wet mixed in ball mill for 16 hours, poured out and dried in the kiln at 1 0 50 ° After calcination for 2 hours at a high temperature of C, the crucible was finely ground to 1.2/zm or less as the first component of the present invention. The second component of the glass frit is based on zinc oxide (ZnO), antimony pentoxide (Nb2 05 ), manganese carbonate (MnC03 ), boric acid (Η3Β03), and cerium oxide (SiO 2 ). $Nb2 05 $ 10%, 〇% δ

Si02 $10% UMnO $10%, 3 0% SZnO $8 0%, 2 0% SB2〇3 $ 60% of the total composition of 100%, scaled, mixed, dried and simmered at 80 °C 5小时以下以下。 After 4 hours, finely ground to 1. 5 / m or less. Then, according to the weight ratio of Table 2, the frit of the first component and the second component were weighed and mixed in a ball mill for 16 hours, and the final formula powder was obtained after drying. The formula powder is further added with 20% of a solution containing 10% polyvinyl alcohol (PVA), and after granulation, it is pressed to a diameter of l〇mm, and a thickness of 1.5 mm/cm2. A round plate shaped green sheet of 5 min was sintered at about 10 °C for 2 hours. After the electrodes were sintered on both sides of the sintered body, the electrical properties and the sintered density were measured according to the following test conditions: frequency 丨 MHz, test voltage 1 Vrms, capacitance value measured, dielectric constant e and measured DF value (ie, escape factor) Tan <5 ); measuring the resistance value with a DC voltage of 500 V, charging for 1 minute, temperature 25 C '; measuring the temperature change of the capacitor at _55 °C and 1 2 5 °C with a capacitance value of 25 t Coefficient; the weight and volume of the sintered body were measured to calculate the density of the sintered body, and the microscopic structure of the structure was observed by an optical microscope (〇M): It is judged whether the composition is comprehensively judged by these materials. The sample formulation described above can be further fabricated into a multilayer ceramic capacitor,

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1311768 ^ __Case No. 92191619 V. Description of the invention (5) The method is as follows: 10 parts by weight of the formula powder, 10 parts of polymethyl methacrylate forging, 30 parts of methyl ethyl ketone / ethanol solvent, butyl benzyl hydrazine The organic binder consisting of 4 parts of the acid ester is uniformly mixed in a ball mill for 16 hours, and is made into a washing liquid. The porcelain pulp is placed in a coater to make the porcelain pulp. Evenly coated on the substrate, the thickness of the dielectric layer coated each time is about 2〇~30"^, after 8 (after rc is dried, the printed internal electrode material composition is 9〇%Ag/1〇%pd) After the internal electrode layer is repeated several times to the desired thickness and number of layers, the shaped body is cut into 2. 〇wmm size green embryo wafer, which is first degreased at less than 500 °C. After 8 hours of treatment, sintering at 1 2 for 2 hours, the size of the wafer after sintering is about 1.6LX0.8wmm, and after being baked by the external electrode, according to: f test strip: frequency 1MHz, test voltage丨^^, determine the df value and capacitance value and calculate the dielectric constant e value; to DC power 50V, charge 1 minute Ϊ insulation resistance value; at a rate of 1 〇〇V per second DC voltage, 疋 疋 其 其 其 其 其 其 其 其 其 ; ; ; ; ; ; ; ; ; ; ; ; ; ; ; ; ; ; ; ; ; ; ; ; ; ; ; ; ; ; ; ; ; 电容 25 25 25 25 Grid (ie - ΙνΜ介. Electrical constant redundancy ~ 45 'capacitance temperature system, number meets NP0 gauge ta) is " 0 ± 3 ° Qing), " value (ie dissipation factor U 9f 1 below, insulation resistance In the case of 1X1012 Ω or more, it is not possible to comply with the purpose of the present invention, and the sample can not meet the requirements of the present invention;

Case No. 92118619 Λ

1311768 V. INSTRUCTIONS (6) As shown in sample 1, when frit = 〇 by weight, the DF value is too low to be lower than the target value, as shown by sample 7, when fri t = 2〇 = f is sintered When the sintering density is lower than the target value, the temperature coefficient of the capacitor deviates from $h and the frit = l~15 parts by weight, the target value can be met, so f is wide, and the amount of addition is 〇. 5% Sfrit core 16. 〇 %. Rit optimum sample 8~25 is mainly used to adjust the Ba〇, Nb 〇, t rate of the first component to seek the best range 'in this range, test ^ i can 2 2 橾 electrical properties, sintered density, and microscope structure. 』付付 is shown in samples 8 to 15, when Ba〇 = 34.0 parts by weight or the temperature of the parts is more deviated from the target or has a D. F value too high ^ Ba〇2 goes =. 〇 weight or Τι〇2 = 65.5 When the parts are parts by weight, the temperature coefficient of the capacitance deviates from the target value. When the weight is 26.8~32.5 parts by weight, the properties are all satisfactory; and: the optimum range is 26.0%$"〇$33.0%, to ()^^, “〇54.〇%^Ti〇2^65.0% The optimum range for squeaking is shown in samples 16 to 21. When Zn0 = 〇 by weight, the df number deviates from the target value, when Zn〇 = 12.6 weight 5% 〇 12 12 12 12 12 12 12 12 12 12 12 12 12 12 12 12 12 12 12 12 12 12 12 12 12 12 12 12 12 12 12 12 12 12 12 12 12 12 12 12 12 12 12 12 12 12 12 12 12 12 12 12 12 12 12 12 12 12 12 12 12 12 12 12 12 12 12 12 12 12 12 12 12 12 12 12 12 12 12 12 12 12 12 12 12 12 12 12 12 12 12 12 12 12 12 〇%. 4 ^ From sample 22~25, when Nb2〇5 = 0 parts by weight: temperature coefficient is lower than the target value' when N b2 05 = 6.7 parts by weight, , Tian * after rainbow trout, ^ 2 05 = 1.2 and 4.6 parts by weight, each property satisfies the target value, so

The optimum range for Nb2〇5 is 〇. 5% $Nb2 05 S6. 〇%. Table (1) Proportion of the first ingredient of sample 1 3

1311768 Case No. 92218619_年月日日_ V. Invention description (7) Heavy weight (8) BaCO] 8.62kg BiO 26.8 NbA 0.5Skg NbA 2.3 ΖηΟ 2.00kg ZnO 8.0 TiO, 15.73kg TiO, 629 Table (2) Implementation Example composition table and test characteristics results sample composition is the second 戎 龟 菊 J J J J J J J J J J J J J J J J J J J J J J J J J J J J J J J J J J J J J J J J J J J J J J J J J J J J J J J J J J J J J J J J J J J J J J J J J J J J J J J J J J J J J J Absolute Turtle Resistance BiO ZnO TiOi Prison ε % -55C 125Π Ω ^/cm' 1 28 ΰ 2.3 8.4 613 0% 24 1.48 22S 130 107 4.16 This 2 280 2.3 8.4 613 1% 41 0.05 28 >10^ 4.53 3 28 D 2.3 8.4 613 2% 42 0.05 20 25 >\οη 4.53 4 28D 2.3 8.4 613 6% 40 0.05 -] -4 >10^ 4.43 5 289 3.0 7.7 60.4 39 0.05 -23 -34 >10'^ 4.36 6 33D 2.0 9.0 560 15/* 37 0.04 -23 -29 >10η 4.29 7 293 4.6 3.8 623 20% 34 0.04 •73 •S3 >10^ 4.05 Ben 8 34 JO 1.9 10.1 54 D 6% 36 0.24 52 45 >10'^ 4.39 Ben 9 33 D 3.9 10.1 530 2% 40 0.07 48 43 >10^ 4.51 Ben·0 325 2.8 9.7 550 6% 38 0.08 26 28 >10^ 4.37 •1 2ZB 2.4 8.6 60.1 6% 38 0.05 25 28 >104.42 : 2 2^B 2.3 8.3 616 i〇y〇38 0.05 -12 -20 >10^ 4.41 :3 26 S 2.3 8.0 629 6% 39 0.04 -13 -30 >10^ 4.4L :4 26 JO 1.9 6.6 655 10/〇40 0.04 -ΊΒ 45 >10'' 4.40 本:5 25.1 2.1 7.8 65D 2% 40 0.04 -41 •53 >1015 4.49 氺it搮表^ In the scope of the invention ( 2) Example of ingredient list and test characteristics (continued)

Page 11 1311768 Case No. 92181619 Amendment 5, invention description (8) m ts two components scare _ J*i ± first touch (10) thank you and <heavy _ minute> DF temperature ® 敎丨 ppm / ΰ) 铕 green奄 resistance WtJfa 密 Remarks b4〇Kb-jOs ZnC ΤιΟί 敁t % 55Ό ]25C Ω l/cm5 U 325 2.6 0 6SD 2 Received 0.:6 41 5C &gt;]〇14 4.23 Π 313 lS :.9 65D 10 A5 0.Q5 1C 7 &gt;]CT 4.36 IS 30.4 \:j 3.8 64.4 6 A2 0.Q5 3 2C &gt;]〇&quot; 4.41 19 28.7 3.0 6.1 622 10 A2 0.04 -19 8 &gt;]〇'' 4.43 20 273 2.3 10·! 598 6 AQ 0.04 ·% 3 &gt;]〇ls 4.51 2: 26.7 4.2 12 ή 10 舛0.Q5 •Tj -6S &gt;]0丨4 4.41 22 2S.7 0 62.7 10 Α5 3 .S3 \Γδ 65) &gt;]〇|!| 4.34 23 283 1.2 '5 63D 6 Α2 0.06 η 3 &gt;]〇15 4.47 24 25.4 4.6 4.2 619 2 40 0.Q5 1ί -7 &gt;]〇'* 4.47 2S 2^.7 6.^ 6.5 600 6 44 0.04 -75 -4: &gt;] Shanghai 4.43 Table (3) Electrical properties of laminated ceramic capacitors made of sample 3 and sample 13 and sample 18

!ί难号 3 13 IS mmmm 90Ag/10Pd 90Ag/lQPd 90Ag/10Pd Sintering temperature 100CC lOOOT: lOOOT: 燠 after film (_) 16 Ί 2 16 flat meat capacity 20ΡΓ 8pF lDpF DF 0.03°/c 0.04°/c 0卿铕缘驱i.5x 10'Ώ 3x 10'^ 4x 10ΠΩ Temperature Baoyi (Sink &gt; 7ρριη/ΐ^ -2Sppm/, C -12ρριη/ΐ]! Temperature (4) (12 redundancy) -UppiVC -27ppm/ 'C 4ppm/r: 甭 甭 40 3S 3S 莆 莆 2450V 2740V 2120V第12页

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Claims (1)

1311768 X. Patent application scope: . _: .... ( ι· A composition of ultra-low temperature firing dielectric porcelain powder, whose composition consists of ι00 smoked as follows. The first component is 26.0% S BaOS 33.0% , 1.5% ^Zn〇^ 12.0% , 0.5%^Nb2O5^ 6.0% &gt; 54.0%^ Ti〇2 Guest 65.0% and 0.5~16 parts by weight $% $ Nb2〇5 S 10%, 0〇/〇 $ Si〇2 $ ι〇〇/0,〇〇/〇$ MnO S 10%, 30% S ZnO S 80/g ' 20%$Β2〇3$60% of the second component of the glass frit combination The composition of the dielectric porcelain powder is as follows: 2. The ultra-low temperature firing dielectric ceramic powder composition as described in claim 1 wherein each component of the first component is BaC03 (carbon S text) ), ZnO (zinc oxide), Nb205 (antimony pentoxide), Tl〇2 (titanium oxide) as the starting material, wet mixing in a ball mill for 6 hours, poured out and dried in a kiln at 1〇 5 〇t above the high temperature simmer for 2 hours, the simmered material is finely ground to 12#m or less. 3' The ultra-low temperature firing system described in the first paragraph of the patent application category is: 6 Each component of the first component of Hai The ratio of Xuanyuan δ t, dried after 8 〇〇c 瑕 burned for 4 hours and then finely ground to less than 1,5 // m. The temperature-compensated type of ultra-low calcined system Laminated ceramic capacitor, the composition is composed of 26.0% s 11768 BaOS 33.0%, 1.5% S ZnOS 12.0%, 0.5% SNb205 S 6.0%, 54.0% STiO2S65.0% first component and 0.5~ 16 parts by weight of a composition of 0% SNb2O5S 10%, 0% SSiO2S 10%, 0% S lyinOS 10%, 30% SZnO $80%, 20% SB203S 60% of the second component of the glass frit, and then The organic binder is added and uniformly mixed in a ball mill to prepare a ceramic wrinkle for casting molding, and then the porcelain slurry is uniformly coated on the substrate and dried, and then the internal electrode material is printed, so that the laminated ceramic capacitor is repeated several times. A ceramic-structured ceramic capacitor having a desired ceramic structure. 5. A temperature-compensated multilayer ceramic capacitor made of a low-temperature firing dielectric dielectric powder composition as described in claim 4, wherein the organic The binder consists of polydecyl methacrylate, butanone/ethanol solvent, butyl benzyl phthalate, etc. 6. A temperature-compensated multilayer ceramic capacitor made of the ultra-low temperature fired dielectric ceramic powder composition according to claim 4, wherein the internal electrode material has a composition of 90% Ag/10 Electrode material within %Pd.