CN102956355A - Method for producing multilayer ceramic capacitor and equipment for sintering copper end electrodes - Google Patents
Method for producing multilayer ceramic capacitor and equipment for sintering copper end electrodes Download PDFInfo
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- CN102956355A CN102956355A CN2012104189687A CN201210418968A CN102956355A CN 102956355 A CN102956355 A CN 102956355A CN 2012104189687 A CN2012104189687 A CN 2012104189687A CN 201210418968 A CN201210418968 A CN 201210418968A CN 102956355 A CN102956355 A CN 102956355A
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- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 title claims abstract description 198
- 229910052802 copper Inorganic materials 0.000 title claims abstract description 198
- 239000010949 copper Substances 0.000 title claims abstract description 198
- 238000005245 sintering Methods 0.000 title claims abstract description 79
- 239000003985 ceramic capacitor Substances 0.000 title claims abstract description 68
- 238000004519 manufacturing process Methods 0.000 title claims abstract description 23
- 239000000919 ceramic Substances 0.000 claims abstract description 127
- 239000012298 atmosphere Substances 0.000 claims abstract description 96
- 230000007935 neutral effect Effects 0.000 claims abstract description 22
- 230000001590 oxidative effect Effects 0.000 claims abstract description 19
- 229910052751 metal Inorganic materials 0.000 claims abstract description 5
- 239000002184 metal Substances 0.000 claims abstract description 5
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 46
- 238000000034 method Methods 0.000 claims description 43
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 24
- 239000001301 oxygen Substances 0.000 claims description 24
- 229910052760 oxygen Inorganic materials 0.000 claims description 24
- 229910052757 nitrogen Inorganic materials 0.000 claims description 23
- 229910052799 carbon Inorganic materials 0.000 claims description 22
- 230000014759 maintenance of location Effects 0.000 claims description 18
- 238000012545 processing Methods 0.000 claims description 18
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 13
- 239000001257 hydrogen Substances 0.000 claims description 13
- 229910052739 hydrogen Inorganic materials 0.000 claims description 13
- 238000010438 heat treatment Methods 0.000 claims description 12
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 claims description 11
- 229910002091 carbon monoxide Inorganic materials 0.000 claims description 11
- 239000007789 gas Substances 0.000 claims description 8
- 239000011248 coating agent Substances 0.000 claims description 6
- 238000000576 coating method Methods 0.000 claims description 6
- 239000002003 electrode paste Substances 0.000 claims description 6
- 239000011267 electrode slurry Substances 0.000 abstract description 2
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 20
- 238000005516 engineering process Methods 0.000 description 15
- 238000012360 testing method Methods 0.000 description 12
- 229910052759 nickel Inorganic materials 0.000 description 10
- 239000000853 adhesive Substances 0.000 description 9
- 230000001070 adhesive effect Effects 0.000 description 9
- QPLDLSVMHZLSFG-UHFFFAOYSA-N Copper oxide Chemical compound [Cu]=O QPLDLSVMHZLSFG-UHFFFAOYSA-N 0.000 description 8
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 description 6
- 239000007788 liquid Substances 0.000 description 6
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical group [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 5
- 230000009286 beneficial effect Effects 0.000 description 5
- 238000009713 electroplating Methods 0.000 description 5
- 229960004643 cupric oxide Drugs 0.000 description 4
- 239000012299 nitrogen atmosphere Substances 0.000 description 4
- 238000011068 loading method Methods 0.000 description 3
- 238000004626 scanning electron microscopy Methods 0.000 description 3
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 description 2
- 238000007796 conventional method Methods 0.000 description 2
- 230000003628 erosive effect Effects 0.000 description 2
- 239000008246 gaseous mixture Substances 0.000 description 2
- 239000000047 product Substances 0.000 description 2
- 230000035939 shock Effects 0.000 description 2
- 239000002002 slurry Substances 0.000 description 2
- 238000003466 welding Methods 0.000 description 2
- 239000010953 base metal Substances 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- 239000003990 capacitor Substances 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 238000010276 construction Methods 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 238000005336 cracking Methods 0.000 description 1
- 238000007766 curtain coating Methods 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 239000007772 electrode material Substances 0.000 description 1
- 238000000227 grinding Methods 0.000 description 1
- 238000012423 maintenance Methods 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 229910000510 noble metal Inorganic materials 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 229910052763 palladium Inorganic materials 0.000 description 1
- 230000002093 peripheral effect Effects 0.000 description 1
- 239000012466 permeate Substances 0.000 description 1
- 229910052573 porcelain Inorganic materials 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 238000007639 printing Methods 0.000 description 1
- 229910052709 silver Inorganic materials 0.000 description 1
- 239000004332 silver Substances 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 239000002912 waste gas Substances 0.000 description 1
- 239000002699 waste material Substances 0.000 description 1
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- Fixed Capacitors And Capacitor Manufacturing Machines (AREA)
Abstract
The invention provides a method for producing a multilayer ceramic capacitor and equipment for sintering copper end electrodes. The method for producing the multilayer ceramic capacitor comprises the following steps that a ceramic body with inner electrodes is provided; copper electrode slurry which contains organic bond is coated on the end faces of the exposed inner electrodes of the ceramic body and is dried, so that the ceramic body with copper end electrode films is obtained; the ceramic body with the copper end electrode films is arranged in an oxidizing atmosphere to be heated so as to remove the organic bond in the copper end electrode films; the ceramic body with the copper end electrode films is arranged in a reducing atmosphere to be heated, so that the copper end electrode films of the ceramic body are subjected to reduction treatment; the ceramic body with the copper end electrode films is arranged in a neutral atmosphere to sinter the copper end electrode films, so that the ceramic body with the copper end electrodes is obtained; and a metal layer is plated on each copper end electrode of the ceramic body, so that the multilayer ceramic capacitor is formed. By the method for producing the multilayer ceramic capacitor, the density of the copper end electrode can be increased, and the reliability of the multilayer ceramic capacitor is improved.
Description
Technical field
The present invention relates to the multilayer ceramic capacitor field, particularly relate to a kind of manufacture method of multilayer ceramic capacitor and the equipment of sintered copper termination electrode.
Background technology
Multilayer ceramic capacitor comprises ceramic body, interior electrode and termination electrode.In recent years, the base metal such as nickel, copper has replaced the noble metals such as palladium, silver to become the electrode material of most multilayer ceramic capacitors.When copper was used to form terminal electrode of multi-layer ceramic capacitor, conventional copper termination sintering process generally was divided into two stages, namely gets rid of adhesive and sintering, specifically:
To be coated with the copper metal paste and be the ceramic body of copper termination film with it oven dry, load with nickel screen and be positioned on the transport tape, enter in the sintering furnace by the transport tape transmission.Be divided into the sticking section of row and sintering stage in the sintering furnace.The sticking section of a row maximum temperature generally is 450 ℃ ~ 600 ℃, and (the long-pending content of oxysome generally is 200ppm ~ 300ppm) in this gaseous mixture, and is discharged to the external world by suction opeing to pass into the gaseous mixture of nitrogen and air.Sintering stage then maximum temperature generally is 830 ℃ ~ 860 ℃, passes into nitrogen, and is discharged to the external world by suction opeing, to keep stable neutral atmosphere (the long-pending content general control of oxysome is below 10ppm).Multilayer ceramic capacitor through this PROCESS FOR TREATMENT obtains then possesses copper termination sintering and non-oxidation.
Yet, even the copper termination film is under the long-pending content of the oxysome of a hundreds of ppm, its organic bond as the electrode slurry carrier that comprises still is difficult to be decomposed and gets rid of totally, so the sticking effect of the row of common process its row of sticking stage is bad, not enough, form more carbon residue and be brought into the sintering stage, the sintering of copper is produced blanketing, cause the termination electrode density behind the sintering not enough.Loose termination electrode brings a series of integrity problems to the multilayer ceramic capacitor finished product: 1, when termination electrode is carried out electroplating processes, electroplate liquid is penetrated into its inside and corrodes ceramic main body by loose termination electrode, makes porcelain body produce micro-crack., be subject to thermal shock and further Cracking Failure occurs when the welding with the capacitor finished product of micro-crack.2, when multilayer ceramic capacitor is soldered, permeate electroplate liquid in termination electrode and be heated and be converted into gas, cause the scolding tin splash, threaten the reliability of multilayer ceramic capacitor body and peripheral element.3, because the erosion of electroplate liquid makes termination electrode reduce the adhesive force of ceramic main body.
Summary of the invention
Based on this, be necessary to provide a kind of manufacture method that improves the copper termination density and improve the multilayer ceramic capacitor of multilayer ceramic capacitor reliability.
A kind of manufacture method of multilayer ceramic capacitor may further comprise the steps:
Step 2, the end face coating of electrode comprises the copper electrode paste of organic bond in described ceramic body exposes, and dries, and obtains having the ceramic body of copper termination film;
Step 3, described ceramic body with copper termination film placed under the oxidizing atmosphere heat, to remove the organic bond in the copper termination film;
Step 4, will place under the reducing atmosphere through the described ceramic body that step 3 is processed and heat, the copper termination film of described ceramic body will be reduced processing;
Step 5, will place sintered copper termination electrode film under the neutral atmosphere through the described ceramic body that step 4 is processed, obtain having the ceramic body of copper termination; And
Step 6, on the copper termination of described ceramic body electroplated metal layer, form multilayer ceramic capacitor.
Therein among embodiment, in the described step 3, the step of removing the organic bond in the described copper termination film comprises: described oxidizing atmosphere is the mixed atmosphere of air and nitrogen, wherein, the volume content of oxygen is 1% ~ 20%, and temperature rises to T from room temperature with the heating rate of 25 ℃/min ~ 30 ℃/min
1, 400 ℃≤T
1≤ 550 ℃, in temperature T
1Temperature retention time be 20min ~ 30min.
Among embodiment, the volume content of oxygen is 12% ~ 18%, 450 ℃≤T therein
1≤ 500 ℃.
Therein among embodiment, in the described step 4, the copper termination film of described ceramic body is reduced the step of processing to be comprised: described reducing atmosphere is the mixed atmosphere of hydrogen and nitrogen, or be the mixed atmosphere of carbon monoxide and nitrogen, wherein, the volume content of hydrogen or carbon monoxide is 3% ~ 6%, and temperature is T
2, 400 ℃≤T
2≤ 550 ℃, in temperature T
2Temperature retention time be 30min ~ 40min.
Among embodiment, the volume content of hydrogen or carbon monoxide is 4% ~ 5.4%, 460 ℃≤T therein
2≤ 500 ℃.
Therein among embodiment, in the described step 5, sintered copper termination electrode film, the step that obtains having the ceramic body of copper termination comprises: described neutral atmosphere is the mixed atmosphere of air and nitrogen, and wherein, the volume content of oxygen is 10ppm ~ 20ppm, and temperature is from T
2Heating rate with 30 ℃/min ~ 35 ℃/min rises to T
3, 750 ℃≤T
3≤ 800 ℃, in temperature T
3Temperature retention time be 10min ~ 12min, afterwards from T
3Rate of temperature fall with 35 ℃/min ~ 38 ℃/min is cooled to 50 ℃ ~ 60 ℃.
A kind of equipment of sintered copper termination electrode, comprise sintering furnace and transport tape, described sintering furnace comprises the sticking section of the row who links to each other successively, reduction section and sintering stage, and described transport tape is transferred to the sticking section of described row, reduction section and sintering stage successively for the ceramic body that will have the copper termination film;
Wherein, the sticking section of described row heats for described ceramic body with copper termination film is placed under the oxidizing atmosphere, to remove the organic bond in the copper termination film;
Described reduction section is used for having the described ceramic body of removing the copper termination film behind the organic bond and places reducing atmosphere to heat, and the copper termination film of described ceramic body is reduced processing;
The described ceramic body that described sintering stage is used for having the copper termination film after reduction is processed places sintered copper termination electrode film under the neutral atmosphere, obtains described ceramic body with copper termination.
Among embodiment, on the sticking section of described row, described reduction section, described sintering stage, all be provided with for the stable suction opeing of maintenance each section atmosphere therein.
Therein among embodiment, between the sticking section of described row and the described reduction section, all be provided with between described reduction section and the described sintering stage and prevent interactional gas curtain between each section atmosphere, in the porch of described sintering furnace and the exit all be provided with and prevent that outside air from affecting the gas curtain of sintering furnace atmosphere.
The manufacture method of above-mentioned multilayer ceramic capacitor has the following advantages:
(1) ceramic body that has the copper termination film heats in the oxidizability atmosphere, can remove the organic bond in the copper termination film, reduce the carbon residual volume in the copper termination film, be beneficial to carrying out smoothly of follow-up sintering manufactured copper termination electrode, improve the density of copper termination, solve owing to the loose integrity problem that brings of copper termination, improve the reliability of multilayer ceramic capacitor.
(2) have the ceramic body of removing the copper termination film behind the organic bond and under reducing atmosphere, heat, the copper termination film is reduced processings, the electric conductivity of copper termination behind the assurance sintering.
(3) have ceramic body sintered copper termination electrode film under neutral atmosphere of the copper termination film after reduction is processed, required sintering temperature significantly reduces than the common process technology, is conducive to save energy and reduce the cost; Contain trace oxygen in the nitrogen atmosphere, trace oxygen can strengthen the adhesive force of copper termination and ceramic body substantially not in the cupric oxide termination electrode, forms and the fine and close copper termination ceramic body close attachment, that conductivity is good.
Description of drawings
Fig. 1 is the flow chart of manufacture method of the multilayer ceramic capacitor of an execution mode;
Fig. 2 is the structure chart of equipment of the sintered copper termination electrode of an execution mode;
Fig. 3 is the technological parameter figure of equipment of the sintered copper termination electrode of an execution mode;
Fig. 4 is the SEM figure of the copper termination that obtains of the manufacture method of the multilayer ceramic capacitor of embodiment 1;
Fig. 5 is another SEM figure of the copper termination that obtains of the manufacture method of the multilayer ceramic capacitor of embodiment 1;
Fig. 6 is the SEM figure of copper termination of the multilayer ceramic capacitor of control group 1;
Fig. 7 is another SEM figure of copper termination of the multilayer ceramic capacitor of control group 1.
Embodiment
For above-mentioned purpose of the present invention, feature and advantage can be become apparent more, the below is described in detail the specific embodiment of the present invention.A lot of details have been set forth in the following description so that fully understand the present invention.But the present invention can implement much to be different from alternate manner described here, and those skilled in the art can do similar improvement in the situation of intension of the present invention, so the present invention is not subjected to the restriction of following public implementation.
See also Fig. 1, the manufacture method of the multilayer ceramic capacitor of an execution mode may further comprise the steps:
Step S10, provide the ceramic body with interior electrode.
Preparation technology with ceramic body of interior electrode is: according to a conventional method ceramic powder and the mixing such as adhesive, solvent are disperseed to form slurry and it curtain coating is become the medium diaphragm.On the medium diaphragm by design configuration printing electrode size and oven dry to form interior electrode, stacked and pressurization is with the ceramic green of the sandwich construction that obtains to have dielectric layer and inner electrode layer and replace again.Ceramic green is cut into chip by preliminary dimension, carry out sintering after getting rid of its inner adhesive, form the ceramic body with interior electrode.
Step S20, the end face coating of electrode comprises the copper electrode paste of organic bond in ceramic body exposes, and dries, and obtains having the ceramic body of copper termination film.
Behind the ceramic body chamfer grinding, the end face of electrode applies and comprises the copper slurry of organic bond in ceramic body exposes, and dries, and obtains having the ceramic body of copper termination film.
Step S30, the ceramic body that will have a copper termination film place under the oxidizing atmosphere and heat, to remove the organic bond in the copper termination film.
See also Fig. 2, the equipment 100 of the sintered copper termination electrode of an execution mode comprises transport tape 120 and sintering furnace 140.
Be filled with oxidizing atmosphere in the sticking section 142 of row, this oxidizing atmosphere is the mixed atmosphere of air and nitrogen, and wherein, the volume content of oxygen is 1% ~ 20%.Preferably, the volume content of oxygen is 12% ~ 18%.
Be filled with reducing atmosphere in the reduction section 144, this reducing atmosphere is the mixed atmosphere of hydrogen and nitrogen, or is the mixed atmosphere of carbon monoxide and nitrogen, and wherein, the volume content of hydrogen or carbon monoxide is 3% ~ 6%.Preferably, the volume content of hydrogen or carbon monoxide is 4% ~ 5.4%.
Be filled with neutral atmosphere in the sintering stage 146, this neutral atmosphere is the mixed atmosphere of air and nitrogen, and wherein, the volume content of oxygen is 10ppm ~ 20ppm.
All be provided with suction opeing 148 on the sticking section 142 of row, reduction section 144, the sintering stage 146, keeping the stable of each section atmosphere, and remove waste gas waste residue that each section reaction produces etc.
Between the sticking section 142 of row and the reduction section 144, between reduction section 144 and the sintering stage 146, porch and the exit of sintering furnace 140 all be provided with gas curtain 149.Being in order to prevent influencing each other between each section atmosphere at the gas curtain between the sticking section 142 of row and the reduction section 144, between reduction section 144 and the sintering stage 146, is in order to prevent that outside air is on the impact of sintering furnace atmosphere in the porch of sintering furnace 140 and the gas curtain in exit.
Be positioned on the transport tape 120 after the ceramic body 200 usefulness nickel screens 300 that will have a copper termination film load, and by the sticking section of row 142 o'clock that transport tape 120 enters sintering furnace 140, under oxidizing atmosphere, heat, to remove the organic bond in the copper termination film.
See also Fig. 3, in the sticking section 142 of row, by the temperature gradient of each segment and the belt speed of transport tape 120 in the sticking section of the row of setting, make the ceramic body 200 with copper termination film in the sticking section of row, rise to T from room temperature with the heating rate of 25 ℃/min ~ 30 ℃/min
1, 400 ℃≤T
1≤ 550 ℃, in temperature T
1Temperature retention time be 20min ~ 30min, after enter reduction section 144 and proceed subsequent technique.Preferably, 450 ℃≤T
1≤ 500 ℃.
Ceramic body with copper termination film heats in the oxidizability atmosphere, oxygen in the oxidizing atmosphere can make the organic bond fast decoupled in the copper termination film, thereby get rid of clean organic bond, reduce the carbon residual volume in the copper termination film, be beneficial to carrying out smoothly of follow-up sintering manufactured copper termination electrode, improve the density of copper termination, solve owing to the loose integrity problem that brings of copper termination, improve the reliability of multilayer ceramic capacitor.
Step S40, will place under the reducing atmosphere through the ceramic body that step S30 processes and heat, the copper termination film of ceramic body will be reduced processing.
See also Fig. 3, will have the ceramic body of removing the copper termination film behind the organic bond and enter the reduction section 144 of sintering furnace 140 by transport tape 120, under reducing atmosphere, heat, the copper termination film is reduced processing.
In the reduction section 144, keep the belt speed of transport tape 120, having the temperature of ceramic body in reduction section of removing the copper termination film behind the organic bond is T
2, 400 ℃≤T
2≤ 550 ℃, in temperature T
2Temperature retention time be 30min ~ 40min.Preferably, 460 ℃≤T
2≤ 500 ℃.
Have the ceramic body of removing the copper termination film behind the organic bond and under reducing atmosphere, heat, the copper termination film is reduced processings, will in oxidizing atmosphere, reduce by oxidized copper the electric conductivity of copper termination behind the assurance sintering.
Step S50, will place sintered copper termination electrode film under the neutral atmosphere through the ceramic body that step S40 processes, obtain having the ceramic body of copper termination.
See also Fig. 3, the ceramic body that will have a copper termination film after reduction is processed enters the sintering stage 146 of sintering furnace 140 by transport tape 120, and sintered copper termination electrode film under neutral atmosphere obtains having the ceramic body of copper termination.
In the sintering stage 146, by setting the temperature gradient of each segment in the sintering stage, keep simultaneously the belt speed of transport tape 120, make have the copper termination film after reduction is processed ceramic body in sintering stage from T
2Heating rate with 30 ℃/min ~ 35 ℃/min rises to T
3, 750 ℃≤T
3≤ 800 ℃, in temperature T
3Temperature retention time be 10min ~ 12min, afterwards from T
3Rate of temperature fall with 35 ℃/min ~ 38 ℃/min is cooled to 50 ℃ ~ 60 ℃, and the ceramic body that will be had copper termination by transport tape 120 is sent out outside the sintering furnace 140, carries out subsequent handling after naturally cooling to room temperature.
Have ceramic body sintered copper termination electrode film under neutral atmosphere of the copper termination film after reduction is processed, required sintering temperature significantly reduces than the common process technology, is conducive to save energy and reduce the cost; Contain trace oxygen in the nitrogen atmosphere, trace oxygen can strengthen the adhesive force of copper termination and ceramic body substantially not in the cupric oxide termination electrode, forms and the fine and close copper termination ceramic body close attachment, that conductivity is good.
Step S60, on the copper termination of ceramic body electroplated metal layer, form multilayer ceramic capacitor.
According to a conventional method, electroless nickel layer and tin layer on copper termination form multilayer ceramic capacitor.
The manufacture method of above-mentioned multilayer ceramic capacitor has the following advantages:
(1) ceramic body that has the copper termination film heats in the oxidizability atmosphere, can remove the organic bond in the copper termination film, reduce the carbon residual volume in the copper termination film, be beneficial to carrying out smoothly of follow-up sintering manufactured copper termination electrode, improve the density of copper termination, solve owing to the loose integrity problem that brings of copper termination, improve the reliability of multilayer ceramic capacitor.
(2) have the ceramic body of removing the copper termination film behind the organic bond and under reducing atmosphere, heat, the copper termination film is reduced processings, the electric conductivity of copper termination behind the assurance sintering.
(3) have ceramic body sintered copper termination electrode film under neutral atmosphere of the copper termination film after reduction is processed, required sintering temperature significantly reduces than the common process technology, is conducive to save energy and reduce the cost; Contain trace oxygen in the nitrogen atmosphere, trace oxygen can strengthen the adhesive force of copper termination and ceramic body substantially not in the cupric oxide termination electrode, forms and the fine and close copper termination ceramic body close attachment, that conductivity is good.
Below in conjunction with specific embodiment, the invention will be further elaborated.
Step 2, the end face coating of electrode comprises the copper electrode paste of organic bond in ceramic body exposes, and dries, and obtains having the ceramic body of copper termination film.
Step 3, the ceramic body that will have a copper termination film are positioned on the transport tape after loading with nickel screen, and the sticking section of row by transport tape enters sintering furnace heats under oxidizing atmosphere, to remove the organic bond in the copper termination film.
Step 4, the ceramic body that will process through step 3 enter the reduction section of sintering furnace by transport tape, heat under reducing atmosphere, and the copper termination film of ceramic body is reduced processing.
Step 5, the ceramic body that will process through step 4 enter the sintering stage of sintering furnace by transport tape, and sintered copper termination electrode film under neutral atmosphere obtains having the ceramic body of copper termination.
Step 6, on the copper termination of ceramic body electroless nickel layer and tin layer, form multilayer ceramic capacitor.
Wherein, the concrete technology of the sticking section of row is: oxidizing atmosphere is the mixed atmosphere of air and nitrogen, and the volume content of oxygen is 14%, and temperature rises to T from room temperature with the heating rate of 25 ℃/min
1=480 ℃, in temperature T
1Temperature retention time be 20min.
The concrete technology of reduction section is: reducing atmosphere is the mixed atmosphere of hydrogen and nitrogen, and the volume content of hydrogen is 4.5%, and the temperature of reduction section is T
2=480 ℃, in temperature T
2Temperature retention time be 30min.
The concrete technology of sintering stage is: neutral atmosphere is the mixed atmosphere of air and nitrogen, and the volume content of oxygen is 16ppm, and temperature is from T
2Heating rate with 30 ℃/min rises to T
3=780 ℃, in temperature T
3Temperature retention time be 12min, afterwards from T
3Rate of temperature fall with 37 ℃/min is cooled to 50 ℃.
Provide 600,000 of identical ceramic bodies that provide with the step 1 of embodiment 1 to organize in contrast 1, do the processing identical with embodiment 1 by step 2, obtain copper termination according to common process sintered copper termination electrode film again.With KYKY-EM3200 type SEM(scanning electron microscopy) observe the copper termination porosity of embodiment 1 and control group 1, the result is shown in Fig. 4 ~ 7 and table 1.Afterwards, control group 1 is made the electroplating processes identical with embodiment 1 by step 6, the multilayer ceramic capacitor that the multilayer ceramic capacitor that makes and embodiment 1 make carries out the test of electric property and reliability.
See also table 1, table 1 is depicted as the copper termination porosity and the electric property of multilayer ceramic capacitor and the test result of reliability of embodiment 1 and control group 1.
Table 1
By table 1 and Fig. 4 ~ 7 as can be known, the copper termination porosity that embodiment 1 makes is significantly less than the copper termination porosity of control group 1; Simultaneously, the multilayer ceramic capacitor that the multilayer ceramic capacitor that embodiment 1 makes makes compared to control group 1, its electric property is better, and the termination electrode value of thrust is larger, and anti-sweating heat test and splash test performance are more excellent.
The multilayer ceramic capacitor of present embodiment also brings following beneficial effect when keeping the superior electrical performance:
1, make the copper termination density behind the sintering high, electroplate liquid can not be penetrated into copper termination inside when electroplating processes, so multilayer ceramic capacitor in the splash test scolding tin splash does not occur; 2, fine and close copper termination protection ceramic main body is avoided the electroplate liquid erosion, avoids the generation of ceramic body micro-crack, improves thermal shock resistance and the welding performance of multilayer ceramic capacitor; 3, copper termination is easier to sintering, can adhere to combination with ceramic body better, and the danger that not corroded by electroplate liquid, thereby the adhesive force of ceramic body is improved.
Embodiment 2
Step 2, the end face coating of electrode comprises the copper electrode paste of organic bond in ceramic body exposes, and dries, and obtains having the ceramic body of copper termination film.
Step 3, the ceramic body that will have a copper termination film are positioned on the transport tape after loading with nickel screen, and the sticking section of row by transport tape enters sintering furnace heats under oxidizing atmosphere, to remove the organic bond in the copper termination film.
Step 4, the ceramic body that will process through step 3 enter the reduction section of sintering furnace by transport tape, heat under reducing atmosphere, and the copper termination film of ceramic body is reduced processing.
Step 5, the ceramic body that will process through step 4 enter the sintering stage of sintering furnace by transport tape, and sintered copper termination electrode film under neutral atmosphere obtains having the ceramic body of copper termination.
Step 6, on the copper termination of ceramic body electroless nickel layer and tin layer, form multilayer ceramic capacitor.
Wherein, the concrete technology of the sticking section of row is: oxidizing atmosphere is the mixed atmosphere of air and nitrogen, and the volume content of oxygen is 12.5%, and temperature rises to T from room temperature with the heating rate of 30 ℃/min
1=460 ℃, in temperature T
1Temperature retention time be 30min.
The concrete technology of reduction section is: reducing atmosphere is the mixed atmosphere of carbon monoxide and nitrogen, and the volume content of carbon monoxide is 5%, and the temperature of reduction section is T
2=470 ℃, in temperature T
2Temperature retention time be 40min.
The concrete technology of sintering stage is: neutral atmosphere is the mixed atmosphere of air and nitrogen, and the volume content of oxygen is 15ppm, and temperature is from T
2Heating rate with 35 ℃/min rises to T
3=770 ℃, in temperature T
3Temperature retention time be 10min, afterwards from T
3Rate of temperature fall with 38 ℃/min is cooled to 60 ℃.
Provide 1,000,000 of identical ceramic bodies that provide with the step 1 of embodiment 2 to organize in contrast 2, do the processing identical with embodiment 2 by step 2, obtain copper termination according to common process sintered copper termination electrode film again.With KYKY-EM3200 type SEM(scanning electron microscopy) observe the copper termination porosity of embodiment 2 and control group 2, the result is as shown in table 2.Afterwards, control group 2 is made the electroplating processes identical with embodiment 2 by step 6, the multilayer ceramic capacitor that the multilayer ceramic capacitor that makes and embodiment 2 make carries out the test of electric property and reliability.
See also table 2, table 2 is depicted as the copper termination porosity and the electric property of multilayer ceramic capacitor and the test result of reliability of embodiment 2 and control group 2.
Table 2
As shown in Table 2, the copper termination porosity that makes of embodiment 2 is lower than the copper termination porosity of control group 2; Simultaneously, the multilayer ceramic capacitor that embodiment 2 makes is compared to the multilayer ceramic capacitor of control group 2, and its electric property is better, and the termination electrode value of thrust is larger, and splash test performance is more excellent.The manufacture method of this multilayer ceramic capacitor is described, can improves the copper termination density, improve simultaneously the reliability of multilayer ceramic capacitor.
Embodiment 3
Step 2, the end face coating of electrode comprises the copper electrode paste of organic bond in ceramic body exposes, and dries, and obtains having the ceramic body of copper termination film.
Step 3, the ceramic body that will have a copper termination film are positioned on the transport tape after loading with nickel screen, and the sticking section of row by transport tape enters sintering furnace heats under oxidizing atmosphere, to remove the organic bond in the copper termination film.
Step 4, the ceramic body that will process through step 3 enter the reduction section of sintering furnace by transport tape, heat under reducing atmosphere, and the copper termination film of ceramic body is reduced processing.
Step 5, the ceramic body that will process through step 4 enter the sintering stage of sintering furnace by transport tape, and sintered copper termination electrode film under neutral atmosphere obtains having the ceramic body of copper termination.
Step 6, on the copper termination of ceramic body electroless nickel layer and tin layer, form multilayer ceramic capacitor.
Wherein, the concrete technology of the sticking section of row is: oxidizing atmosphere is the mixed atmosphere of air and nitrogen, and the volume content of oxygen is 16%, and temperature rises to T from room temperature with the heating rate of 27 ℃/min
1=480 ℃, in temperature T
1Temperature retention time be 25min.
The concrete technology of reduction section is: reducing atmosphere is the mixed atmosphere of hydrogen and nitrogen, and the volume content of hydrogen is that the temperature of 4.2%I reduction section is T
2=500 ℃, in temperature T
2Temperature retention time be 35min.
The concrete technology of sintering stage is: neutral atmosphere is the mixed atmosphere of air and nitrogen, and the volume content of oxygen is 18ppm, and temperature is from T
2Heating rate with 35 ℃/min rises to T
3=780 ℃, in temperature T
3Temperature retention time be 12min, afterwards from T
3Rate of temperature fall with 37 ℃/min is cooled to 55 ℃.
Provide 1,000,000 of identical ceramic bodies that provide with the step 1 of embodiment 3 to organize in contrast 3, do the processing identical with embodiment 3 by step 2, obtain copper termination according to common process sintered copper termination electrode film again.With KYKY-EM3200 type SEM(scanning electron microscopy) observe the copper termination porosity of embodiment 3 and control group 3, the result is as shown in table 3.Afterwards, control group 3 is made the electroplating processes identical with embodiment 3 by step 6, the multilayer ceramic capacitor that the multilayer ceramic capacitor that makes and embodiment 3 make carries out the test of electric property and reliability.
See also table 3, table 3 is depicted as the copper termination porosity and the electric property of multilayer ceramic capacitor and the test result of reliability of embodiment 3 and control group 3.
Table 3
As shown in Table 3, the copper termination porosity that makes of embodiment 3 is lower than the copper termination porosity of control group 3; Simultaneously, the multilayer ceramic capacitor that embodiment 3 makes is compared to the multilayer ceramic capacitor of control group 3, and its electric property is better, and the termination electrode value of thrust is larger, and anti-sweating heat test and splash test performance are more excellent.The manufacture method of this multilayer ceramic capacitor is described, can improves the termination electrode density of multilayer ceramic capacitor, improve simultaneously the reliability of multilayer ceramic capacitor.
The manufacture method of above-mentioned multilayer ceramic capacitor has the following advantages:
(1) ceramic body that has the copper termination film heats in the oxidizability atmosphere, can remove the organic bond in the copper termination film, reduce the carbon residual volume in the copper termination film, be beneficial to carrying out smoothly of follow-up sintering manufactured copper termination electrode, improve the density of copper termination, solve owing to the loose integrity problem that brings of copper termination, improve the reliability of multilayer ceramic capacitor.
(2) have the ceramic body of removing the copper termination film behind the organic bond and under reducing atmosphere, heat, the copper termination film is reduced processings, the electric conductivity of copper termination behind the assurance sintering.
(3) have ceramic body sintered copper termination electrode film under neutral atmosphere of the copper termination film after reduction is processed, required sintering temperature significantly reduces than the common process technology, is conducive to save energy and reduce the cost; Contain trace oxygen in the nitrogen atmosphere, trace oxygen can strengthen the adhesive force of copper termination and ceramic body substantially not in the cupric oxide termination electrode, forms and the fine and close copper termination ceramic body close attachment, that conductivity is good.
The above embodiment has only expressed several execution mode of the present invention, and it describes comparatively concrete and detailed, but can not therefore be interpreted as the restriction to claim of the present invention.Should be pointed out that for the person of ordinary skill of the art without departing from the inventive concept of the premise, can also make some distortion and improvement, these all belong to protection scope of the present invention.Therefore, the protection range of patent of the present invention should be as the criterion with claims.
Claims (9)
1. the manufacture method of a multilayer ceramic capacitor is characterized in that, may further comprise the steps:
Step 1, provide the ceramic body with interior electrode;
Step 2, the end face coating of electrode comprises the copper electrode paste of organic bond in described ceramic body exposes, and dries, and obtains having the ceramic body of copper termination film;
Step 3, described ceramic body with copper termination film placed under the oxidizing atmosphere heat, to remove the organic bond in the copper termination film;
Step 4, will place under the reducing atmosphere through the described ceramic body that step 3 is processed and heat, the copper termination film of described ceramic body will be reduced processing;
Step 5, will place sintered copper termination electrode film under the neutral atmosphere through the described ceramic body that step 4 is processed, obtain having the ceramic body of copper termination; And
Step 6, on the copper termination of described ceramic body electroplated metal layer, form multilayer ceramic capacitor.
2. the manufacture method of multilayer ceramic capacitor according to claim 1, it is characterized in that, in the described step 3, the step of removing the organic bond in the described copper termination film comprises: described oxidizing atmosphere is the mixed atmosphere of air and nitrogen, wherein, the volume content of oxygen is 1% ~ 20%, and temperature rises to T from room temperature with the heating rate of 25 ℃/min ~ 30 ℃/min
1, 400 ℃≤T
1≤ 550 ℃, in temperature T
1Temperature retention time be 20min ~ 30min.
3. the manufacture method of multilayer ceramic capacitor according to claim 2 is characterized in that, the volume content of oxygen is 12% ~ 18%, 450 ℃≤T
1≤ 500 ℃.
4. the manufacture method of multilayer ceramic capacitor according to claim 1, it is characterized in that, in the described step 4, the copper termination film of described ceramic body is reduced the step of processing to be comprised: described reducing atmosphere is the mixed atmosphere of hydrogen and nitrogen, or be the mixed atmosphere of carbon monoxide and nitrogen, wherein, the volume content of hydrogen or carbon monoxide is 3% ~ 6%, and temperature is T
2, 400 ℃≤T
2≤ 550 ℃, in temperature T
2Temperature retention time be 30min ~ 40min.
5. the manufacture method of multilayer ceramic capacitor according to claim 4 is characterized in that, the volume content of hydrogen or carbon monoxide is 4% ~ 5.4%, 460 ℃≤T
2≤ 500 ℃.
6. the manufacture method of multilayer ceramic capacitor according to claim 1, it is characterized in that, in the described step 5, sintered copper termination electrode film, the step that obtains having the ceramic body of copper termination comprises: described neutral atmosphere is the mixed atmosphere of air and nitrogen, wherein, the volume content of oxygen is 10ppm ~ 20ppm, and temperature is from T
2Heating rate with 30 ℃/min ~ 35 ℃/min rises to T
3, 750 ℃≤T
3≤ 800 ℃, in temperature T
3Temperature retention time be 10min ~ 12min, afterwards from T
3Rate of temperature fall with 35 ℃/min ~ 38 ℃/min is cooled to 50 ℃ ~ 60 ℃.
7. the equipment of a sintered copper termination electrode, it is characterized in that, comprise sintering furnace and transport tape, described sintering furnace comprises the sticking section of the row who links to each other successively, reduction section and sintering stage, and described transport tape is transferred to the sticking section of described row, reduction section and sintering stage successively for the ceramic body that will have the copper termination film;
Wherein, the sticking section of described row heats for described ceramic body with copper termination film is placed under the oxidizing atmosphere, to remove the organic bond in the copper termination film;
Described reduction section is used for having the described ceramic body of removing the copper termination film behind the organic bond and places reducing atmosphere to heat, and the copper termination film of described ceramic body is reduced processing;
The described ceramic body that described sintering stage is used for having the copper termination film after reduction is processed places sintered copper termination electrode film under the neutral atmosphere, obtains described ceramic body with copper termination.
8. the equipment of sintered copper termination electrode according to claim 7 is characterized in that, all is provided with for keeping the stable suction opeing of each section atmosphere on the sticking section of described row, described reduction section, described sintering stage.
9. the equipment of sintered copper termination electrode according to claim 7, it is characterized in that, between the sticking section of described row and the described reduction section, all be provided with between described reduction section and the described sintering stage and prevent interactional gas curtain between each section atmosphere, in the porch of described sintering furnace and the exit all be provided with and prevent that outside air from affecting the gas curtain of sintering furnace atmosphere.
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