Laminated ceramic electronic component
09972438 ยท 2018-05-15
Assignee
Inventors
Cpc classification
H05K3/1291
ELECTRICITY
H05K3/4664
ELECTRICITY
H05K3/4629
ELECTRICITY
International classification
C03B29/00
CHEMISTRY; METALLURGY
H01G4/20
ELECTRICITY
Abstract
A method for manufacturing a laminated ceramic capacitor having a laminated body including a plurality of stacked ceramic layers and internal electrodes located between the ceramic layers. The laminated body has a pair of mutually opposed principal surfaces extending in the direction in which the ceramic layers extend, a pair of mutually opposed side surfaces and a pair of mutually opposed end surfaces which respectively extend in directions orthogonal to the principal surfaces. The internal electrodes are 0.4 m or less in thickness, and are located in an area defined by a width-direction gap of 30 m or less interposed with respect to each of the pair of side surfaces and an outer layer thickness of 35 m or less interposed with respect to each of the pair of principal surfaces.
Claims
1. A method for manufacturing a laminated ceramic electronic component, the method comprising: providing a first plurality of ceramic green sheets; printing conductive paste films on the first plurality of ceramic green sheets in a thickness that results in internal electrodes of 0.4 m or less in thickness after firing; providing a second plurality of ceramic green sheets without conductive paste films thereon; stacking the first plurality of green sheets with the conductive paste films thereon and the second plurality of ceramic green sheets to form an unsintered body; and firing the unsintered body at a temperature greater than 1000 C. to form a laminated body that includes a plurality of stacked ceramic layers and a plurality of internal electrodes located between the ceramic layers, a pair of mutually opposed principal surfaces extending in a direction in which the ceramic layers extend, a pair of mutually opposed side surfaces and a pair of mutually opposed end surfaces, the side surfaces and the end surfaces respectively extending in directions orthogonal to the principal surfaces, the plurality of internal electrodes including a first set of internal electrodes that extend to a first end surface of the pair of end surfaces and a second set of internal electrodes that extend to a second end surface of the pair of end surfaces, the plurality of internal electrodes being distributed in an area defined by a width-direction gap interposed with respect to each of the pair of side surfaces and an outer layer thickness interposed with respect to each of the pair of principal surfaces, the coverage of the internal electrodes is 75% or more, and at least one of (1) the width-direction gap is 30 m or less and (2) the outer layer thickness is 35 m or less.
2. The method for manufacturing a laminated ceramic electronic component according to claim 1, wherein both the width-direction gap is 30 m or less and the outer layer thickness is 35 m or less.
3. The method for manufacturing a laminated ceramic electronic component according to claim 1, wherein the plurality of internal electrodes are no less than 0.05 m in thickness after firing.
4. The method for manufacturing a laminated ceramic electronic component according to claim 3, wherein the width-direction gap is no less than 5 m.
5. The method for manufacturing a laminated ceramic electronic component according to claim 4, wherein the outer layer thickness is no less than 5 m.
6. The method for manufacturing a laminated ceramic electronic component according to claim 1, wherein the width-direction gap is no less than 5 m.
7. The method for manufacturing a laminated ceramic electronic component according to claim 1, wherein the outer layer thickness is no less than 5 m.
8. The method for manufacturing a laminated ceramic electronic component according to claim 2, wherein the plurality of internal electrodes are no less than 0.05 m in thickness after firing.
9. The method for manufacturing a laminated ceramic electronic component according to claim 8, wherein the width-direction gap is no less than 5 m.
10. The method for manufacturing a laminated ceramic electronic component according to claim 9, wherein the outer layer thickness is no less than 5 m.
11. The method for manufacturing a laminated ceramic electronic component according to claim 2, wherein the width-direction gap is no less than 5 m.
12. The method for manufacturing a laminated ceramic electronic component according to claim 2, wherein the outer layer thickness is no less than 5 m.
13. The method for manufacturing a laminated ceramic electronic component according to claim 1, wherein the conductive paste contains Ni.
Description
BRIEF EXPLANATION OF THE DRAWINGS
(1)
(2)
(3)
(4)
DETAILED DESCRIPTION OF THE INVENTION
(5) The structure of a laminated ceramic capacitor 1 as an example of a laminated ceramic electronic component obtained by applying this invention will be described with reference to
(6) The laminated ceramic capacitor 1 includes a laminated body 2 as a component main body. The laminated body 2 includes a plurality of stacked ceramic layers 3 and a plurality of internal electrodes 4 and 5 located between the ceramic layers 3. The internal electrodes 4 and the internal electrodes 5 are arranged alternately in the stacking direction.
(7) The laminated body 2 forms a cuboidal shape or a substantially cuboidal shape which has a pair of mutually opposed principal surfaces 6 and 7 extending in the direction in which the ceramic layers 3 extend, as well as a pair of mutually opposed side surfaces 8 and 9 and a pair of mutually opposed end surfaces 10 and 11 which respectively extend in directions orthogonal to the principal surfaces 6 and 7.
(8) The end surfaces 10 and 11 of the laminated body 2 respectively have the plurality of internal electrodes 4 and 5 extracted thereto, and the respective ends exposed thereto, and external electrodes 12 and 13 are formed respectively so as to electrically connect the respective ends of the internal electrodes 4 to each other and the respective ends of the internal electrodes 5 to each other.
(9) The internal electrodes 4 and 5 are, as shown in
(10) This laminated ceramic capacitor 1 according to this invention meets the first condition that the internal electrodes 4 and 5 each have a thickness C of 0.4 m or less, and the second condition that the width-direction gap A is 30 m or less or the outer-layer thickness B is 35 m or less.
(11) More preferably, as for the second condition, the capacitor is adapted to meet both the width-direction gap A of 30 m or less and the outer-layer thickness B of 35 m or less. In this preferred embodiment, more preferably, the capacitor is adapted to meet the third condition that the coverage for the internal electrodes 4 and 5 is 75% or more.
(12) It is to be noted that because of actual manufacturing problems, it is expected that the thickness C for each of the internal electrodes 4 and 5 has a lower limit on the order of 0.05 m, the outer-layer thickness B has a lower limit on the order of 5 m, and the width-direction gap A has a lower limit on the order of 5 m.
(13) For manufacturing this laminated ceramic capacitor 1, ceramic green sheets to serve as the ceramic layers 3 are first prepared, and conductive paste films to serve as the internal electrodes 4 and 5 are formed by printing onto the ceramic green sheets. Next, the multiple ceramic green sheets are stacked to prepare an unfired laminated body to serve as the laminated body 2, which includes a plurality of unfired ceramic layers and the conductive paste films located between the unfired ceramic layers.
(14) Then, a firing step is carried out for making the unfired laminated body sintered. Then, the external electrodes 12 and 13 are respectively formed on the end surfaces 10 and 11 of the sintered laminated body 2, thereby completing the laminated ceramic capacitor 1.
(15) When the thickness C for the internal electrodes 4 and 5 is reduced to 0.4 m or less in order to meet the first condition mentioned above, it is not easy to meet the third condition that the coverage is kept at 75% or more. For example, when the firing temperature is lowered, it is easy to keep the coverage at 75% or more, whereas the ceramic is somewhat insufficiently sintered.
(16) In order to solve this problem, it is effective to carry out, in the firing step, a heat treatment step in which a temperature profile is applied at an average rate of temperature increase of 40 C./second or more, preferably 100 C./second or more up to a maximum temperature, and further desirably to carry out cooling without keeping the maximum temperature after reaching the temperature in order to reduce the heat quantity. When the firing step is carried out under this condition, the coverage for the internal electrodes 4 and 5 can be kept high while making the ceramic sufficiently sintered.
(17) In addition, the unfired laminated body is preferably subjected to a degreasing treatment before the heat treatment step described above in the firing step.
(18) When the internal electrodes 4 and 5 contain a base metal such as Ni as a conductive constituent, the heat treatment step may be carried out in an atmosphere supplied with an atmosphere gas which is oxidative with respect to the equilibrium oxygen partial pressure of the base metal.
(19) When this invention is directed to the laminated ceramic capacitor 1 shown in
(20) In addition, while the laminated ceramic capacitor 1 shown in
(21) Experimental examples will be described below which were carried out for confirming the advantageous effects of this invention.
Experimental Example 1
(1) Preparation of Samples
(22) Ceramic green sheets including: ceramic powder containing barium titanate as its main constituent; and an organic binder were formed on base films so as to be 1 m in thickness after firing. Then, conductive paste films to serve as internal electrodes were formed by screen printing onto the ceramic green sheets, so as to achieve the thickness shown in the column Thickness of Internal Electrode in Tables 1 and 2 after the firing. In this case, the dimensions of the printing pattern for the conductive paste films were adjusted so that internal electrodes were distributed in a region located with a width-direction gap interposed as shown in the column Width-Direction Gap in Tables 1 and 2, in laminated bodies obtained through subsequent cutting step and firing step.
(23) Next, the green sheets with the conductive paste films formed thereon were stacked a predetermined number of times so as to alternate the sides to which the conductive paste films were extracted, and further so as to sandwich these sheets, green sheets for an outer layer section without any conductive paste films formed were stacked a predetermined number of times, and heated and pressed to prepare laminated body blocks. In this case, the number of stacked green sheets for an outer layer section was adjusted so as to achieve the Outer Layer Thickness in Tables 1 and 2 after the firing.
(24) Next, the laminated body blocks were cut with a dicing saw to obtain unfired laminated bodies.
(25) Next, the unfired laminated bodies obtained were subjected, for degreasing, to a heat treatment with a maximum temperature of 240 C. in N.sub.2 stream. Continuously, the laminated bodies were subjected to firing with a maximum temperature of 1180 C. under an atmosphere with an oxygen partial pressure of 10.sup.9.5 MPa in N.sub.2H.sub.2OH.sub.2 stream.
(26) For the sintered laminated bodies obtained in this way, external electrodes were formed on the end surface sections with the internal electrodes extracted thereto. More specifically, a conductive paste containing copper as its main constituent was applied, and subjected to baking at 800 C. to form base layers, and Ni plating films and Sn plating films were formed thereon by wet plating.
(27) Laminated ceramic capacitors according to each sample were obtained in the way described above. The obtained laminated ceramic capacitors including the external electrodes achieved the external dimensions as shown in the Length-Direction Dimension, Width-Direction Dimension, and Thickness-Direction Dimension of Tables 1 and 2.
(28) Next, it was confirmed in the following way that the laminated ceramic capacitors obtained achieved the values in the Thickness of Internal Electrode, Outer Layer Thickness, and Width-Direction Gap as shown in Tables 1 and 2.
(2) Thickness of Internal Electrode
(29) Three laminated ceramic capacitors were prepared for each sample. These laminated ceramic capacitors were encased in a resin so as to barely present the end surfaces, and the end surfaces were polished in the length directions of the laminated ceramic capacitors to obtain polished cross sections at in the length directions. Next, these polished cross sections were subjected to ion milling to remove drops produced by the polishing. In this way, cross sections for observation were obtained.
(30) Next, the group of internal electrodes was divided into three equal parts with respect to the thickness direction of the sample, which were classified in three regions of: an upper area; a middle area; and a lower area. In addition, in the cross section, a perpendicular line was drawn which was orthogonal to the internal electrodes and divided the internal electrodes into two equal parts in the width direction. Then, twenty-five layers of internal electrodes were selected from each of the central parts of the three regions, and the thicknesses of these internal electrodes were measured on the perpendicular line.
(31) Thus, the thickness of the internal electrode was measured at 75 points for one sample, and the thickness of the internal electrode was obtained at 225 points in total for the three samples in total to figure out the average value of these thicknesses. However, the points with the defective internal electrodes were not counted.
(32) As a result, it was confirmed that the average value for the thickness of the internal electrode for each sample was nearly the targeted value as shown in the column Thickness of Internal Electrode of Tables 1 and 2.
(3) Width Direction Gap
(33) The cross sections for observation, obtained in the section (2), were used for figuring out the width direction gap. Seven layers of internal electrodes were specified which were located to divide the area with the internal electrodes present therein into six equal parts with respect to the thickness direction of the sample. In the locations of the five layers of internal electrodes after excluding the uppermost layer of internal electrode and the lowermost layer of internal electrode among these seven layers of internal electrodes, the width direction gap was measured at 10 points in total on both the right-hand side and left-hand side. Then, the value of the width-direction gap was obtained at 30 points in total for the three samples in total to figure out the average value of these values.
(34) As a result, it was confirmed that the average value for the width-direction gap for each sample was nearly the targeted value as shown in the column Width Direction Gap of Tables 1 and 2.
(4) Outer Layer Thickness
(35) First of all, the cross sections for observation, obtained in the section (2), were used for figuring out the outer layer thickness. Seven perpendicular lines were drawn which were orthogonal to the internal electrodes and divided the internal electrodes into six equal parts in the width direction. On the five perpendicular lines after excluding the two outermost perpendicular lines among these seven perpendicular lines, the outer layer thickness was measured at 10 points in total on both the upper side and lower side. Then, the outer layer thickness was first obtained at 30 points in total for the three samples in total.
(36) Secondly, three laminated ceramic capacitors were further prepared for each sample. These laminated ceramic capacitors were encased in a resin so as to barely present the side surfaces, and the side surfaces were polished in the width directions of the laminated ceramic capacitors to obtain polished cross sections at in the width directions. Next, these polished cross sections were subjected to ion milling to remove drops produced by the polishing. In this way, second cross sections for observation were obtained.
(37) In this second cross section, perpendicular lines were drawn which were orthogonal to the internal electrodes and divide the overlap region of the internal electrodes (the region except for the length-direction gaps) into six equal parts in the length direction. On the five perpendicular lines after excluding the two outermost perpendicular lines among these seven perpendicular lines, the outer layer thickness was measured at 10 points in total on both the upper side and lower side. Then, the outer layer thickness was further obtained at 30 points in total for the three samples in total.
(38) Thus, the average value was figured out for the outer layer thicknesses at 60 points in total for the six samples in total. As a result, it was confirmed that the outer layer thickness for each sample had nearly the targeted value as shown in the column Outer Layer Thickness of Tables 1 and 2.
(39) It is to be noted that the coverage for the internal electrodes was about 80% for all of samples 1 to 74 shown in Tables 1 and 2. As for the coverage, the laminated body was subjected to peeling, and then, the surface near the center of the internal electrode pattern at the peeled surface was observed under an optical microscope to figure out the ratio of the area with the internal electrode present therein, and regard this ratio as the coverage.
(5) Evaluation
(40) The laminated ceramic capacitors according to each sample were subjected to a thermal shock test as follows.
(41) The thermal shock test was carried out in which the laminated ceramic capacitors according to each sample were immersed for 2 seconds in a solder bath at a temperature of 500 C., and the presence or absence of structural defect generation was evaluated by optical microscopic observation. This evaluation was performed for hundred samples to figure out the ratio of the number of samples with structural defects generated. The results are shown in the column Defect Generation Ratio of Tables 1 and 2.
(42) TABLE-US-00001 TABLE 1 Thickness Length Width Thickness of Thickness Direction Direction Direction Internal of Outer Width Defect Sample Dimension Dimension Dimension Electrode Layer Direction Generation Number [mm] [mm] [mm] [m] [m] Gap [m] Ratio [%] 1 3.2 1.6 1.6 1.0 30 30 100 2 3.2 1.6 1.6 1.0 60 30 100 3 3.2 1.6 1.6 1.0 120 30 100 4 3.2 1.6 1.6 1.0 30 60 100 5 3.2 1.6 1.6 1.0 60 60 100 6 3.2 1.6 1.6 1.0 120 60 100 7 3.2 1.6 1.6 1.0 30 120 100 8 3.2 1.6 1.6 1.0 60 120 100 9 3.2 1.6 1.6 1.0 120 120 100 10 2.0 1.2 1.2 1.0 35 25 100 11 2.0 1.2 1.2 1.0 70 25 100 12 2.0 1.2 1.2 1.0 140 25 100 13 2.0 1.2 1.2 1.0 35 50 100 14 2.0 1.2 1.2 1.0 70 50 100 15 2.0 1.2 1.2 1.0 140 50 100 16 2.0 1.2 1.2 1.0 35 100 100 17 2.0 1.2 1.2 1.0 70 100 100 18 2.0 1.2 1.2 1.0 140 100 100 19 3.2 1.6 1.6 0.6 30 30 100 20 3.2 1.6 1.6 0.6 60 30 100 21 3.2 1.6 1.6 0.6 120 30 100 22 3.2 1.6 1.6 0.6 30 60 100 23 3.2 1.6 1.6 0.6 60 60 100 24 3.2 1.6 1.6 0.6 120 60 100 25 3.2 1.6 1.6 0.6 30 120 100 26 3.2 1.6 1.6 0.6 60 120 100 27 3.2 1.6 1.6 0.6 120 120 100 28 2.0 1.2 1.2 0.6 35 25 100 29 2.0 1.2 1.2 0.6 70 25 100 30 2.0 1.2 1.2 0.6 140 25 100 31 2.0 1.2 1.2 0.6 35 50 100 32 2.0 1.2 1.2 0.6 70 50 100 33 2.0 1.2 1.2 0.6 140 50 100 34 2.0 1.2 1.2 0.6 35 100 100 35 2.0 1.2 1.2 0.6 70 100 100 36 2.0 1.2 1.2 0.6 140 100 100
(43) TABLE-US-00002 TABLE 2 Thickness Length Width Thickness of Thickness Direction Direction Direction Internal of Outer Width Defect Sample Dimension Dimension Dimension Electrode Layer Direction Generation Number [mm] [mm] [mm] [m] [m] Gap [m] Ratio [%] 37 3.2 1.6 1.6 0.4 30 30 0 38 3.2 1.6 1.6 0.4 60 30 0 39 3.2 1.6 1.6 0.4 120 30 0 40 3.2 1.6 1.6 0.4 30 60 0 41 3.2 1.6 1.6 0.4 60 60 100 42 3.2 1.6 1.6 0.4 120 60 100 43 3.2 1.6 1.6 0.4 30 120 0 44 3.2 1.6 1.6 0.4 60 120 100 45 3.2 1.6 1.6 0.4 120 120 100 46 2.0 1.2 1.2 0.4 35 25 0 47 2.0 1.2 1.2 0.4 70 25 0 48 2.0 1.2 1.2 0.4 140 25 0 49 2.0 1.2 1.2 0.4 35 50 0 50 2.0 1.2 1.2 0.4 70 50 100 51 2.0 1.2 1.2 0.4 140 50 100 52 2.0 1.2 1.2 0.4 35 100 0 53 2.0 1.2 1.2 0.4 70 100 100 54 2.0 1.2 1.2 0.4 140 100 100 55 3.2 1.6 1.6 0.4 50 50 100 56 3.2 1.6 1.6 0.2 30 30 0 57 3.2 1.6 1.6 0.2 60 30 0 58 3.2 1.6 1.6 0.2 120 30 0 59 3.2 1.6 1.6 0.2 30 60 0 60 3.2 1.6 1.6 0.2 60 60 41 61 3.2 1.6 1.6 0.2 120 60 73 62 3.2 1.6 1.6 0.2 30 120 0 63 3.2 1.6 1.6 0.2 60 120 80 64 3.2 1.6 1.6 0.2 120 120 97 65 2.0 1.2 1.2 0.2 35 25 0 66 2.0 1.2 1.2 0.2 70 25 0 67 2.0 1.2 1.2 0.2 140 25 0 68 2.0 1.2 1.2 0.2 35 50 0 69 2.0 1.2 1.2 0.2 70 50 40 70 2.0 1.2 1.2 0.2 140 50 92 71 2.0 1.2 1.2 0.2 35 100 0 72 2.0 1.2 1.2 0.2 70 100 68 73 2.0 1.2 1.2 0.2 140 100 100 74 3.2 1.6 1.6 0.2 50 50 24
(44)
(45) In
(46) From Table 1 as well as
Experimental Example 2
(47) In Experimental Example 2, the relationship was evaluated between the coverage for internal electrodes and the defect generation ratio in a thermal shock test.
(48) Through essentially the same steps as in the case of Experimental Example 1, laminated ceramic capacitors according to each sample were obtained which had the external dimensions shown in Length Direction Dimension, Width Direction Dimension and Thickness Direction Dimension of Table 3. The laminated ceramic capacitors according to each sample were all adjusted to 0.4 m in the thickness of the internal electrode, 30 m in width direction gap, and 35 m in outer layer thickness. Then, the coverage for the internal electrodes was varied as shown in the column Coverage of Table 3, by controlling the maximum temperature in the firing step between 1100 C. and 1300 C.
(49) For each of the obtained samples, the Thickness of Internal Electrode, Width Direction Gap, and Outer Layer Thickness were measured in the same way as in Experimental Example 1 to confirm that nearly the targeted values were achieved as described above.
(50) In addition, the coverage for the internal electrodes was also nearly the targeted value.
(51) For each of the obtained samples, a thermal shock test was carried out in the same manner as in the case of Experimental Example 1, except that the temperature of the solder bath was set as shown in the column Solder Bath Temperature of Table 3, and the ratio of the number of samples with structural defects generated was figured out. The results are shown in the column Defect Generation Ratio of Table 3.
(52) TABLE-US-00003 TABLE 3 Width Thickness Length Direction Direction Direction Solder Bath Defect Sample Dimension Dimension Dimension Coverage Temperature Generation Number [mm] [mm] [mm] [%] [ C.] Ratio [%] 101 3.2 1.6 1.6 48 400 26 102 3.2 1.6 1.6 62 400 13 103 3.2 1.6 1.6 75 400 0 104 3.2 1.6 1.6 97 400 0 105 3.2 1.6 1.6 46 450 57 106 3.2 1.6 1.6 65 450 27 107 3.2 1.6 1.6 76 450 0 108 3.2 1.6 1.6 92 450 0 109 3.2 1.6 1.6 44 500 88 110 3.2 1.6 1.6 58 500 52 111 3.2 1.6 1.6 79 500 0 112 3.2 1.6 1.6 95 500 0
(53) From Table 3, it can be confirmed that meeting the condition that the coverage for the internal electrodes is 75% or more is more effective for the reduction in defect generation ratio.
(54) More specifically, in
(55) The Coverage is preferably higher against thermal shocks of higher temperatures, and more specifically, the Defect Generation Ratio is 0% with the Coverage of 76% or more in the case of the Solder Bath Temperature of 450 C., whereas the Defect Generation Ratio is 0% with the Coverage of 79% or more in the case of the Solder Bath Temperature of 500 C.
DESCRIPTION OF REFERENCE SYMBOLS
(56) 1 laminated ceramic capacitor 2 laminated body 3 ceramic layer 4,5 internal electrode 6,7 principal surface 8,9 side surface 10,11 end surface