CN102956355B - The manufacture method of multilayer ceramic capacitor and the equipment of sintered copper termination electrode - Google Patents
The manufacture method of multilayer ceramic capacitor and the equipment of sintered copper termination electrode Download PDFInfo
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Abstract
The invention provides a kind of manufacture method of multilayer ceramic capacitor and the equipment of sintered copper termination electrode.A manufacture method for multilayer ceramic capacitor, comprises the following steps: provide the ceramic body with interior electrode; In ceramic body exposes, the end face coating of electrode comprises the copper electrode paste of organic bond, and dries, and obtains the ceramic body with copper termination film; Heat under the ceramic body with copper termination film is placed in oxidizing atmosphere, to remove the organic bond in copper termination film; Heat under the ceramic body with copper termination film is placed in reducing atmosphere, reduction treatment is carried out to the copper termination film of ceramic body; The ceramic body with copper termination film is placed in sintered copper termination electrode film under neutral atmosphere, obtains the ceramic body with copper termination; Electroplated metal layer on the copper termination of ceramic body, forms multilayer ceramic capacitor.The manufacture method of this multilayer ceramic capacitor, can improve the density of copper termination, improves the reliability of multilayer ceramic capacitor.
Description
Technical field
The present invention relates to 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 metal such as palladium, silver to become the electrode material of most multilayer ceramic capacitor.When copper is for the formation of terminal electrode of multi-layer ceramic capacitor, conventional copper termination sintering process is generally divided into two stages, namely gets rid of adhesive and sintering, specifically:
To copper metal paste be coated with and be the ceramic body of copper termination film by it oven dry, load with nickel screen and be positioned on transport tape, entered in sintering furnace by transport tape transmission.The sticky section of row and sintering stage is divided in sintering furnace.The sticky section maximum temperature of row is generally 450 DEG C ~ 600 DEG C, passes into the gaseous mixture (in this gaseous mixture, oxygen volume content is generally 200ppm ~ 300ppm) of nitrogen and air, and is discharged to the external world by suction opeing.Sintering stage then maximum temperature is generally 830 DEG C ~ 860 DEG C, passes into nitrogen, and is discharged to the external world by suction opeing, to keep stable neutral atmosphere (oxygen volume content general control is at below 10ppm).Through the multilayer ceramic capacitor that this PROCESS FOR TREATMENT obtains, then possess sintered and the copper termination of non-oxidation.
But, even if copper termination film is under the oxygen volume content of a hundreds of ppm, its organic bond as electrode slurry carrier comprised still is difficult to be decomposed and gets rid of totally, so it is bad, not enough that the row of common process glues the sticky effect of its row of stage, form more carbon residue and be brought into the sintering stage, blanketing is produced to the sintering of copper, causes the termination electrode density after sintering not enough.Loose termination electrode brings a series of integrity problem to multilayer ceramic capacitor finished product: 1, when end electrodes carries out electroplating processes, and electroplate liquid penetrates into its inside by loose termination electrode and corrodes ceramic main body, makes porcelain body produce micro-crack.With micro-crack capacitor finished product weld time, be subject to thermal shock and further Cracking Failure occur.2, when multilayer ceramic capacitor is soldered, the electroplate liquid permeated in termination electrode is heated and is converted into gas, causes scolding tin splash, threatens 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 improving the multilayer ceramic capacitor of copper termination density and raising multilayer ceramic capacitor reliability.
A manufacture method for multilayer ceramic capacitor, comprises the following steps:
Step one, provide the ceramic body with interior electrode;
Step 2, in described ceramic body exposes, the end face of electrode applies the copper electrode paste comprising organic bond, and dries, and obtains the ceramic body with copper termination film;
Step 3, the described ceramic body with copper termination film is placed in oxidizing atmosphere under heat, to remove the organic bond in copper termination film;
Step 4, the described ceramic body through step 3 process is placed in reducing atmosphere under heat, reduction treatment is carried out to the copper termination film of described ceramic body;
Step 5, the described ceramic body through step 4 process is placed in sintered copper termination electrode film under neutral atmosphere, obtains the ceramic body with copper termination; And
Step 6, on the copper termination of described ceramic body electroplated metal layer, formed multilayer ceramic capacitor.
Wherein in an embodiment, in described step 3, the step removing the organic bond in 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 DEG C/min ~ 30 DEG C/min
1, 400 DEG C≤T
1≤ 550 DEG C, at temperature T
1temperature retention time be 20min ~ 30min.
Wherein in an embodiment, the volume content of oxygen is 12% ~ 18%, 450 DEG C≤T
1≤ 500 DEG C.
Wherein in an embodiment, in described step 4, the step of the copper termination film of described ceramic body being carried out to reduction treatment comprises: 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 DEG C≤T
2≤ 550 DEG C, at temperature T
2temperature retention time be 30min ~ 40min.
Wherein in an embodiment, the volume content of hydrogen or carbon monoxide is 4% ~ 5.4%, 460 DEG C≤T
2≤ 500 DEG C.
Wherein in an embodiment, in described step 5, sintered copper termination electrode film, the step obtaining the ceramic body with 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
2t is risen to the heating rate of 30 DEG C/min ~ 35 DEG C/min
3, 750 DEG C≤T
3≤ 800 DEG C, at temperature T
3temperature retention time be 10min ~ 12min, after from T
350 DEG C ~ 60 DEG C are cooled to the rate of temperature fall of 35 DEG C/min ~ 38 DEG C/min.
A kind of equipment of sintered copper termination electrode, comprise sintering furnace and transport tape, described sintering furnace comprises the row's section of gluing, reduction section and the sintering stage that are connected successively, and described transport tape is used for the ceramic body with copper termination film to be transferred to described row's section of gluing, reduction section and sintering stage successively;
Wherein, described row's section of gluing heats under the described ceramic body with copper termination film is placed in oxidizing atmosphere, to remove the organic bond in copper termination film;
Described reduction section is used for that the described ceramic body with the copper termination film after removing organic bond is placed in reducing atmosphere and heats, and carries out reduction treatment to the copper termination film of described ceramic body;
Described sintering stage is used for the described ceramic body with the copper termination film after reduction treatment to be placed in sintered copper termination electrode film under neutral atmosphere, has the ceramic body of copper termination described in obtaining.
Wherein in an embodiment, described row's section of gluing, described reduction section, described sintering stage are all provided with for keeping the suction opeing that each section of atmosphere is stable.
Wherein in an embodiment, all be provided with between described row's section of gluing and described reduction section, between described reduction section and described sintering stage and prevent interactional gas curtain between each section of atmosphere, be all provided with the gas curtain preventing outside air from affecting sintering furnace atmosphere in the porch of described sintering furnace and exit.
The manufacture method of above-mentioned multilayer ceramic capacitor, has the following advantages:
(1) ceramic body with copper termination film heats in oxidation atmosphere, the organic bond in copper termination film can be removed, reduce the carbon residual volume in copper termination film, be beneficial to carrying out smoothly of follow-up sintering manufactured copper termination electrode, improve the density of copper termination, solve because copper termination loosens the integrity problem brought, improve the reliability of multilayer ceramic capacitor.
(2) ceramic body with the copper termination film after removing organic bond heats under reducing atmosphere, carries out reduction treatment to copper termination film, ensures the electric conductivity of the rear copper termination of sintering.
(3) have ceramic body sintered copper termination electrode film under neutral atmosphere of the copper termination film after reduction treatment, required sintering temperature significantly reduces than conventional processing technique, is conducive to saving energy and reduce the cost; Containing trace oxygen in nitrogen atmosphere, trace oxygen, substantially not while cupric oxide termination electrode, can strengthen the adhesive force of copper termination and ceramic body, formed and ceramic body close attachment, fine and close copper termination that conductivity is good.
Accompanying drawing explanation
Fig. 1 is the flow chart of the manufacture method of the multilayer ceramic capacitor of an execution mode;
Fig. 2 is the structure chart of the equipment of the sintered copper termination electrode of an execution mode;
Fig. 3 is the technological parameter figure of the equipment of the sintered copper termination electrode of an execution mode;
Fig. 4 is the SEM figure of the copper termination that the manufacture method of the multilayer ceramic capacitor of embodiment 1 obtains;
Fig. 5 is that another SEM of the copper termination that the manufacture method of the multilayer ceramic capacitor of embodiment 1 obtains schemes;
Fig. 6 is the SEM figure of the copper termination of the multilayer ceramic capacitor of control group 1;
Fig. 7 is that another SEM of the copper termination of the multilayer ceramic capacitor of control group 1 schemes.
Embodiment
For enabling above-mentioned purpose of the present invention, feature and advantage become apparent more, are described in detail below to the specific embodiment of the present invention.Set forth a lot of detail in the following description so that fully understand the present invention.But the present invention can be much different from alternate manner described here to implement, those skilled in the art can when without prejudice to doing similar improvement when intension of the present invention, therefore the present invention is by the restriction of following public concrete enforcement.
Refer to Fig. 1, the manufacture method of the multilayer ceramic capacitor of an execution mode, comprises the following steps:
Step S10, provide the ceramic body with interior electrode.
The preparation technology with the ceramic body of interior electrode is: ceramic powder and adhesive, solvent etc. are mixed according to a conventional method and disperse form slurry and it curtain coating is become medium diaphragm.Medium diaphragm is dried by design configuration printing electrode size to form interior electrode, more stacked and pressurization is obtaining the ceramic green with the sandwich construction that dielectric layer and inner electrode layer replace.Ceramic green is cut into chip by preliminary dimension, sinters after getting rid of its inner adhesive, form the ceramic body with interior electrode.
Step S20, in ceramic body exposes, the end face of electrode applies and comprises the copper electrode paste of organic bond, and dries, and obtains the ceramic body with copper termination film.
After ceramic body chamfer grinding, in ceramic body exposes, the end face coating of electrode comprises the copper slurry of organic bond, and dries, and obtains the ceramic body with copper termination film.
Step S30, the ceramic body with copper termination film is placed in oxidizing atmosphere under heat, to remove the organic bond in copper termination film.
Refer to Fig. 2, the equipment 100 of the sintered copper termination electrode of an execution mode, comprise transport tape 120 and sintering furnace 140.
Sintering furnace 140 comprises the row's section of gluing 142, reduction section 144 and the sintering stage 146 that are connected successively.
Be filled with oxidizing atmosphere in the sticky 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 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 sintering stage 146, this neutral atmosphere is the mixed atmosphere of air and nitrogen, and wherein, the volume content of oxygen is 10ppm ~ 20ppm.
The sticky section 142 of row, reduction section 144, sintering stage 146 are all provided with suction opeing 148, to keep the stable of each section of atmosphere, and remove the waste gas waste residue etc. of each section of reaction generation.
Porch and the exit of, sintering furnace 140 sticky between section 142 and reduction section 144, between reduction section 144 and sintering stage 146 row are all provided with gas curtain 149.The gas curtain glued between section 142 and reduction section 144, between reduction section 144 and sintering stage 146 row is to prevent influencing each other between each section of atmosphere, is to prevent outside air on the impact of sintering furnace atmosphere in the porch of sintering furnace 140 and the gas curtain in exit.
Transport tape 120 will be for having ceramic body 200 row's of being transferred to sticky section 142, reduction section 144 and sintering stage 146 successively of copper termination film.
Be positioned on transport tape 120 after ceramic body 200 nickel screen 300 with copper termination film is loaded, and when being entered row's section of gluing 142 of sintering furnace 140 by transport tape 120, heat in an oxidizing atmosphere, to remove the organic bond in copper termination film.
Refer to Fig. 3, in the sticky section 142 of row, by the temperature gradient of each segment and the belt speed of transport tape 120 in the sticky section of setting row, the ceramic body 200 making to have copper termination film rises to T from room temperature with the heating rate of 25 DEG C/min ~ 30 DEG C/min in the sticky section of row
1, 400 DEG C≤T
1≤ 550 DEG C, at temperature T
1temperature retention time be 20min ~ 30min, after enter reduction section 144 and proceed subsequent technique.Preferably, 450 DEG C≤T
1≤ 500 DEG C.
The ceramic body with copper termination film heats in oxidation atmosphere, oxygen in oxidizing atmosphere can make the organic bond fast decoupled in copper termination film, thus get rid of clean organic bond, reduce the carbon residual volume in copper termination film, be beneficial to carrying out smoothly of follow-up sintering manufactured copper termination electrode, improve the density of copper termination, solve because copper termination loosens the integrity problem brought, improve the reliability of multilayer ceramic capacitor.
Step S40, the ceramic body through step S30 process is placed in reducing atmosphere under heat, reduction treatment is carried out to the copper termination film of ceramic body.
Refer to Fig. 3, will the ceramic body removing the copper termination film after organic bond be had to be entered by transport tape 120 reduction section 144 of sintering furnace 140, and heat under reducing atmosphere, reduction treatment is carried out to copper termination film.
In reduction section 144, keep the belt speed of transport tape 120, the temperature of ceramic body in reduction section with the copper termination film after removing organic bond is T
2, 400 DEG C≤T
2≤ 550 DEG C, at temperature T
2temperature retention time be 30min ~ 40min.Preferably, 460 DEG C≤T
2≤ 500 DEG C.
The ceramic body with the copper termination film after removing organic bond heats under reducing atmosphere, carries out reduction treatment, reduced by copper oxidized in oxidizing atmosphere to copper termination film, ensures the electric conductivity of the rear copper termination of sintering.
Step S50, the ceramic body through step S40 process is placed in sintered copper termination electrode film under neutral atmosphere, obtains the ceramic body with copper termination.
Refer to Fig. 3, the ceramic body with the copper termination film after reduction treatment is entered the sintering stage 146 of sintering furnace 140 by transport tape 120, under neutral atmosphere, sintered copper termination electrode film, obtains the ceramic body with copper termination.
In sintering stage 146, by the temperature gradient of each segment in setting sintering stage, keep the belt speed of transport tape 120 simultaneously, make the ceramic body of the copper termination film after there is reduction treatment in sintering stage from T
2t is risen to the heating rate of 30 DEG C/min ~ 35 DEG C/min
3, 750 DEG C≤T
3≤ 800 DEG C, at temperature T
3temperature retention time be 10min ~ 12min, after from T
3be cooled to 50 DEG C ~ 60 DEG C with the rate of temperature fall of 35 DEG C/min ~ 38 DEG C/min, by transport tape 120, the ceramic body with copper termination sent out outside sintering furnace 140, after naturally cooling to room temperature, carry out subsequent handling.
Have ceramic body sintered copper termination electrode film under neutral atmosphere of the copper termination film after reduction treatment, required sintering temperature significantly reduces than conventional processing technique, is conducive to saving energy and reduce the cost; Containing trace oxygen in nitrogen atmosphere, trace oxygen, substantially not while cupric oxide termination electrode, can strengthen the adhesive force of copper termination and ceramic body, formed and ceramic body close attachment, fine and close copper termination that conductivity is good.
Step S60, on the copper termination of ceramic body electroplated metal layer, formed multilayer ceramic capacitor.
According to a conventional method, electroless nickel layer and tin layers on copper termination, form multilayer ceramic capacitor.
The manufacture method of above-mentioned multilayer ceramic capacitor, has the following advantages:
(1) ceramic body with copper termination film heats in oxidation atmosphere, the organic bond in copper termination film can be removed, reduce the carbon residual volume in copper termination film, be beneficial to carrying out smoothly of follow-up sintering manufactured copper termination electrode, improve the density of copper termination, solve because copper termination loosens the integrity problem brought, improve the reliability of multilayer ceramic capacitor.
(2) ceramic body with the copper termination film after removing organic bond heats under reducing atmosphere, carries out reduction treatment to copper termination film, ensures the electric conductivity of the rear copper termination of sintering.
(3) have ceramic body sintered copper termination electrode film under neutral atmosphere of the copper termination film after reduction treatment, required sintering temperature significantly reduces than conventional processing technique, is conducive to saving energy and reduce the cost; Containing trace oxygen in nitrogen atmosphere, trace oxygen, substantially not while cupric oxide termination electrode, can strengthen the adhesive force of copper termination and ceramic body, formed and ceramic body close attachment, fine and close copper termination that conductivity is good.
Below in conjunction with specific embodiment, the invention will be further elaborated.
Embodiment 1
Step one, provide the ceramic body with interior electrode 600,000 of 0805 specification X7R characteristic nominal capacity 47nF.
Step 2, in ceramic body exposes, the end face of electrode applies and comprises the copper electrode paste of organic bond, and dries, and obtains the ceramic body with copper termination film.
Step 3, by have copper termination film ceramic body nickel screen load after be positioned on transport tape, entered row's section of gluing of sintering furnace by transport tape, heat in an oxidizing atmosphere, to remove the organic bond in copper termination film.
Step 4, the ceramic body through step 3 process is entered the reduction section of sintering furnace by transport tape, heat under reducing atmosphere, reduction treatment is carried out to the copper termination film of ceramic body.
Step 5, the ceramic body through step 4 process is entered the sintering stage of sintering furnace by transport tape, under neutral atmosphere, sintered copper termination electrode film, obtains the ceramic body with copper termination.
Step 6, on the copper termination of ceramic body electroless nickel layer and tin layers, formed multilayer ceramic capacitor.
Wherein, the concrete technology of the sticky 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 DEG C/min
1=480 DEG C, at 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 DEG C, at 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
2t is risen to the heating rate of 30 DEG C/min
3=780 DEG C, at temperature T
3temperature retention time be 12min, after from T
350 DEG C are cooled to the rate of temperature fall of 37 DEG C/min.
The identical ceramic body 600,000 that theres is provided with the step one of embodiment 1 as a control group 1 is provided, do the process identical with embodiment 1 by step 2, more conveniently technique sintered copper termination electrode film obtains copper termination.By KYKY-EM3200 type SEM(scanning electron microscopy) observe the copper termination porosity of embodiment 1 and control group 1, result is as 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 obtained multilayer ceramic capacitor and embodiment 1 obtain carries out the test of electric property and reliability.
Refer to table 1, table 1 is depicted as the copper termination porosity of embodiment 1 and control group 1 and the electric property of multilayer ceramic capacitor and the test result of reliability.
Table 1
From table 1 and Fig. 4 ~ 7, the copper termination porosity that embodiment 1 obtains is significantly less than the copper termination porosity of control group 1; Meanwhile, the obtained multilayer ceramic capacitor of embodiment 1 is compared to the obtained multilayer ceramic capacitor of control group 1, and its electric property is better, and termination electrode value of thrust is larger, and resistance to soldering heat test and splash test show more excellent.
The multilayer ceramic capacitor of the present embodiment, while maintenance superior electrical performance, also brings following beneficial effect:
1, make the copper termination density after sintering high, when electroplating processes, electroplate liquid can not penetrate into copper termination inside, so multilayer ceramic capacitor, in splash test, scolding tin splash does not occur; 2, fine and close copper termination protection ceramic main body corrodes from electroplate liquid, 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 better combine with ceramic body, and not by the danger that electroplate liquid corrodes, is thus improved the adhesive force of ceramic body.
Embodiment 2
Step one, provide the ceramic body with interior electrode 1,000,000 of 0603 specification NPO characteristic nominal capacity 100pF.
Step 2, in ceramic body exposes, the end face of electrode applies and comprises the copper electrode paste of organic bond, and dries, and obtains the ceramic body with copper termination film.
Step 3, by have copper termination film ceramic body nickel screen load after be positioned on transport tape, entered row's section of gluing of sintering furnace by transport tape, heat in an oxidizing atmosphere, to remove the organic bond in copper termination film.
Step 4, the ceramic body through step 3 process is entered the reduction section of sintering furnace by transport tape, heat under reducing atmosphere, reduction treatment is carried out to the copper termination film of ceramic body.
Step 5, the ceramic body through step 4 process is entered the sintering stage of sintering furnace by transport tape, under neutral atmosphere, sintered copper termination electrode film, obtains the ceramic body with copper termination.
Step 6, on the copper termination of ceramic body electroless nickel layer and tin layers, formed multilayer ceramic capacitor.
Wherein, the concrete technology of the sticky 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 DEG C/min
1=460 DEG C, at 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 DEG C, at 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
2t is risen to the heating rate of 35 DEG C/min
3=770 DEG C, at temperature T
3temperature retention time be 10min, after from T
360 DEG C are cooled to the rate of temperature fall of 38 DEG C/min.
The identical ceramic body 1,000,000 that theres is provided with the step one of embodiment 2 as a control group 2 is provided, do the process identical with embodiment 2 by step 2, more conveniently technique sintered copper termination electrode film obtains copper termination.By KYKY-EM3200 type SEM(scanning electron microscopy) observe the copper termination porosity of embodiment 2 and control group 2, 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 obtained multilayer ceramic capacitor and embodiment 2 obtain carries out the test of electric property and reliability.
Refer to table 2, table 2 is depicted as the copper termination porosity of embodiment 2 and control group 2 and the electric property of multilayer ceramic capacitor and the test result of reliability.
Table 2
As shown in Table 2, the copper termination porosity that embodiment 2 is obtained is lower than the copper termination porosity of control group 2; Meanwhile, the multilayer ceramic capacitor that embodiment 2 obtains is compared to the multilayer ceramic capacitor of control group 2, and its electric property is better, and termination electrode value of thrust is larger, and splash test performance is more excellent.The manufacture method of this multilayer ceramic capacitor is described, copper termination density can be improved, improve the reliability of multilayer ceramic capacitor simultaneously.
Embodiment 3
Step one, provide the ceramic body with interior electrode 1,000,000 of 0603 specification Y5V characteristic nominal capacity 1.0 μ F.
Step 2, in ceramic body exposes, the end face of electrode applies and comprises the copper electrode paste of organic bond, and dries, and obtains the ceramic body with copper termination film.
Step 3, by have copper termination film ceramic body nickel screen load after be positioned on transport tape, entered row's section of gluing of sintering furnace by transport tape, heat in an oxidizing atmosphere, to remove the organic bond in copper termination film.
Step 4, the ceramic body through step 3 process is entered the reduction section of sintering furnace by transport tape, heat under reducing atmosphere, reduction treatment is carried out to the copper termination film of ceramic body.
Step 5, the ceramic body through step 4 process is entered the sintering stage of sintering furnace by transport tape, under neutral atmosphere, sintered copper termination electrode film, obtains the ceramic body with copper termination.
Step 6, on the copper termination of ceramic body electroless nickel layer and tin layers, formed multilayer ceramic capacitor.
Wherein, the concrete technology of the sticky 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 DEG C/min
1=480 DEG C, at 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 the temperature of 4.2%I reduction section is T
2=500 DEG C, at 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
2t is risen to the heating rate of 35 DEG C/min
3=780 DEG C, at temperature T
3temperature retention time be 12min, after from T
355 DEG C are cooled to the rate of temperature fall of 37 DEG C/min.
The identical ceramic body 1,000,000 that theres is provided with the step one of embodiment 3 as a control group 3 is provided, do the process identical with embodiment 3 by step 2, more conveniently technique sintered copper termination electrode film obtains copper termination.By KYKY-EM3200 type SEM(scanning electron microscopy) observe the copper termination porosity of embodiment 3 and control group 3, 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 obtained multilayer ceramic capacitor and embodiment 3 obtain carries out the test of electric property and reliability.
Refer to table 3, table 3 is depicted as the copper termination porosity of embodiment 3 and control group 3 and the electric property of multilayer ceramic capacitor and the test result of reliability.
Table 3
As shown in Table 3, the copper termination porosity that embodiment 3 is obtained is lower than the copper termination porosity of control group 3; Meanwhile, the multilayer ceramic capacitor that embodiment 3 obtains is compared to the multilayer ceramic capacitor of control group 3, and its electric property is better, and termination electrode value of thrust is larger, and resistance to soldering heat test and splash test show more excellent.The manufacture method of this multilayer ceramic capacitor is described, the termination electrode density of multilayer ceramic capacitor can be improved, improve the reliability of multilayer ceramic capacitor simultaneously.
The manufacture method of above-mentioned multilayer ceramic capacitor, has the following advantages:
(1) ceramic body with copper termination film heats in oxidation atmosphere, the organic bond in copper termination film can be removed, reduce the carbon residual volume in copper termination film, be beneficial to carrying out smoothly of follow-up sintering manufactured copper termination electrode, improve the density of copper termination, solve because copper termination loosens the integrity problem brought, improve the reliability of multilayer ceramic capacitor.
(2) ceramic body with the copper termination film after removing organic bond heats under reducing atmosphere, carries out reduction treatment to copper termination film, ensures the electric conductivity of the rear copper termination of sintering.
(3) have ceramic body sintered copper termination electrode film under neutral atmosphere of the copper termination film after reduction treatment, required sintering temperature significantly reduces than conventional processing technique, is conducive to saving energy and reduce the cost; Containing trace oxygen in nitrogen atmosphere, trace oxygen, substantially not while cupric oxide termination electrode, can strengthen the adhesive force of copper termination and ceramic body, formed and ceramic body close attachment, fine and close copper termination that conductivity is good.
The above embodiment only have expressed several execution mode of the present invention, and it describes comparatively concrete and detailed, but therefore can not be interpreted as the restriction to the scope of the claims of the present invention.It 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 (6)
1. a manufacture method for multilayer ceramic capacitor, is characterized in that, comprises the following steps:
Step one, provide the ceramic body with interior electrode;
Step 2, in described ceramic body exposes, the end face of electrode applies the copper electrode paste comprising organic bond, and dries, and obtains the ceramic body with copper termination film;
Step 3, the described ceramic body with copper termination film is placed in oxidizing atmosphere under heat, to remove the organic bond in copper termination film;
Step 4, the described ceramic body through step 3 process is placed in reducing atmosphere under heat, reduction treatment is carried out to the copper termination film of described ceramic body;
Step 5, the described ceramic body through step 4 process is placed in sintered copper termination electrode film under neutral atmosphere, obtains the ceramic body with copper termination; And
Step 6, on the copper termination of described ceramic body electroplated metal layer, formed multilayer ceramic capacitor.
2. the manufacture method of multilayer ceramic capacitor according to claim 1, it is characterized in that, in described step 3, the step removing the organic bond in 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 DEG C/min ~ 30 DEG C/min
1, 400 DEG C≤T
1≤ 550 DEG C, at 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 DEG C≤T
1≤ 500 DEG C.
4. the manufacture method of multilayer ceramic capacitor according to claim 1, it is characterized in that, in described step 4, the step of the copper termination film of described ceramic body being carried out to reduction treatment comprises: 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 DEG C≤T
2≤ 550 DEG C, at 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 DEG C≤T
2≤ 500 DEG C.
6. the manufacture method of multilayer ceramic capacitor according to claim 1, it is characterized in that, in described step 5, sintered copper termination electrode film, the step obtaining the ceramic body with 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
2t is risen to the heating rate of 30 DEG C/min ~ 35 DEG C/min
3, 750 DEG C≤T
3≤ 800 DEG C, at temperature T
3temperature retention time be 10min ~ 12min, after from T
350 DEG C ~ 60 DEG C are cooled to the rate of temperature fall of 35 DEG C/min ~ 38 DEG C/min.
Priority Applications (1)
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| CN2702256Y (en) * | 2003-12-26 | 2005-05-25 | 广东南方宏明电子科技股份有限公司 | Incineration conjuncted furnace of grain boundary layer semi-conductor ceramic chips |
| CN101127275A (en) * | 2007-09-14 | 2008-02-20 | 广东风华高新科技股份有限公司 | A making method for high voltage sheet type multi-layer porcelain capacitor |
| CN101364455A (en) * | 2008-09-26 | 2009-02-11 | 广东风华高新科技股份有限公司 | Base metal copper electrode paste and preparation of obtained capacitor |
| CN101786866A (en) * | 2009-12-22 | 2010-07-28 | 广东风华高新科技股份有限公司 | Anti-reduction dielectric ceramic material matched with copper inner electrode and sintered under high frequency and low temperature |
| CN201885572U (en) * | 2010-11-25 | 2011-06-29 | 广东风华高新科技股份有限公司 | MLCC (multilayer ceramic capacitor) atmosphere tunnel firing furnace completing rubber removal and firing once |
| CN102324290A (en) * | 2011-05-27 | 2012-01-18 | 广东风华高新科技股份有限公司 | Copper electrode zinc oxide varistor and preparation method thereof |
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| CN2702256Y (en) * | 2003-12-26 | 2005-05-25 | 广东南方宏明电子科技股份有限公司 | Incineration conjuncted furnace of grain boundary layer semi-conductor ceramic chips |
| CN101127275A (en) * | 2007-09-14 | 2008-02-20 | 广东风华高新科技股份有限公司 | A making method for high voltage sheet type multi-layer porcelain capacitor |
| CN101364455A (en) * | 2008-09-26 | 2009-02-11 | 广东风华高新科技股份有限公司 | Base metal copper electrode paste and preparation of obtained capacitor |
| CN101786866A (en) * | 2009-12-22 | 2010-07-28 | 广东风华高新科技股份有限公司 | Anti-reduction dielectric ceramic material matched with copper inner electrode and sintered under high frequency and low temperature |
| CN201885572U (en) * | 2010-11-25 | 2011-06-29 | 广东风华高新科技股份有限公司 | MLCC (multilayer ceramic capacitor) atmosphere tunnel firing furnace completing rubber removal and firing once |
| CN102324290A (en) * | 2011-05-27 | 2012-01-18 | 广东风华高新科技股份有限公司 | Copper electrode zinc oxide varistor and preparation method thereof |
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