US20020064669A1

US20020064669A1 - Joining material for electronic components, electronic components and a method for manufacturing the same

Info

Publication number: US20020064669A1
Application number: US10/001,677
Authority: US
Inventors: Takeshi Oobuchi; Yasunori Koda
Original assignee: NGK Insulators Ltd
Current assignee: NGK Insulators Ltd
Priority date: 1998-02-25
Filing date: 2001-10-31
Publication date: 2002-05-30
Also published as: JPH11243034A; EP0939061A1; DE69908445T2; DE69908445D1; EP0939061B1; JP4257711B2; US6376085B1

Abstract

A joining material for an electronic component was disclosed. The component has a plurality of functional layers, each selected from a magnetic layer and dielectric layer and joined with each other. The joining material comprising a glass and a composition of a mol % of ZnO, b mol % of BaO and c mol % of TiO₂(a=12-45, b=4-45, c=18-81, a+b+c=100), wherein 0.1 to 10 weight parts of the glass is added to 100 weight parts of the composition.

Description

BACKGROUND OF THE INVENTION

1. Technical Field

The invention relates to a joining material for an electronic component, such as capacitor, inductors, resistors, stacked type and coaxial type dielectric filters, Stacked type LC filters, composite LC components and composite LCR modules, an electronic component and a method for manufacturing the same.

2. Related Arts

When manufacturing a stacked type dielectric filter, a paste for an internal layer electrode is printed on each of a predetermined number of greensheets, which are then laminated to produce laminated greensheets. This laminated greensheets are then sintered at a temperature of 700° C. to 1100° C. to produce a base body with the internal layer electrodes. After the base body is polished, a metal paste for an outer electrode is printed on predetermined regions on the surface of the body and fired to form the outer electrodes. A composite LC filter with an inductor and capacitor is also known.

When producing such composite electronic components, a predetermined number of greensheets for, for example, a dielectric layer and magnetic layer are laminated to provide laminated greensheets, which are then co-fired to join the magnetic and dielectric layers. It is also known to provide a greensheet of a joining layer between the greensheets of the magnetic and dielectric layers to provide laminated greensheets which are then co-fired. In Japanese publication Tokkohei 120605/1995, a ceramic material, obtained by firing a mixture of ZnO, TiO ₂and CuO, is used for the joining layer for preventing the peeling between the dielectric layers and magnetic layers and diffusion of the ingredients of both layers with each other. In Japanese patent application publication Tokkaihei 36913/1997, a ceramic material is provided between the dielectric and magnetic layers for improving the adhesive strength of the layers and for preventing diffusion of the ingredients of both layers with each other, the ceramic material being obtained by mixing a glass contained in the dielectric layer with a ceramic of 15 to 40 mol % of BaO and 60 to 85 mol % of TiO₂and firing.

SUMMARY OF THE INVENTION

However, according to the inventor's research, warp may occur in the magnetic or dielectric layer depending on the compositions of both layers and their firing schedule. When the amount of warp is out of the specification for manufacturing a filter, such filter with impermissible warp is discarded as a defective, thus decreasing its manufacturing yield. The inventors further found that warp was also induced in the layers during sintering process.

The object of the invention is, in an electronic component having a plurality of functional layers each selected from a magnetic layer and dielectric layer and joined with each other, to prevent warp in the magnetic layers or the dielectric layer.

The invention provides a joining material for an electronic component having a plurality of functional layers each selected from a magnetic layer and dielectric layer, the functional layers being joined with the joining material with each other, the joining material comprising a glass and a composition of a mol % of ZnO, b mol % of BaO and c mol % of TiO ₂(a=12-45, b=4-45, c=18-81, a+b+c=100), wherein 0.1 to 10 weight parts of the glass is added to 100 weight parts of the composition.

The invention also provides a joining material for the electric component, the joining material comprising a glass and a composition of a mol % of ZnO, b mol % of BaO, c mol % of TiO ₂and d mol % of MnO (a=12-45, b=4-45, c=18-81, d≦10, a+b+c+d=100), wherein 0.1 to 10 weight parts of the glass is added to 100 weight parts of the composition.

The invention also provides a joining material for the electric component, the joining material comprising a glass and a composition of a mol % of ZnO, b mol % of BaO, c mol % of TiO ₂and e mol % of Al₂O₃(a=12-45, b=4-45, c=18-81, e≦10, a+b+c+e=100), wherein 0.1 to 10 weight parts of the glass is added to 100 weight parts of the composition.

The invention also provides a joining material for the electric component, the joining material comprising a glass and a composition of a mol % of ZnO, b mol % of BaO, c mol % of TiO ₂, d mol % of MnO and e mol % of Al₂O₃(a=12-45, b=4-45, c=18-81, d≦10, e≦10, a+b+c+d+e=100), wherein 0.1 to 10 weight parts of the glass is added to 100 weight parts of the composition.

The invention also provides an electronic component having the functional layers and a joining layer for joining the adjacent functional layers, wherein the joining layer is composed of sintered product of each of the joining materials. That is, a layer composed of each of the joining materials is fired to form the joining layer. The joining layer is made of the sintered product obtained by firing the joining material.

The invention also provides an electronic component having the functional layers and a joining layer, wherein the joining layer is composed of sintered product showing at least one of a peak corresponding to BaNd ₂Ti₅O₁₄and a peak corresponding to BaNd₂Ti₄O₁₂when measured by means of powdery X-ray diffraction method.

The invention also provides a method for manufacturing an electronic component having the functional layers and a joining layer, the method comprising the steps of:

laminating the functional layers already sintered to provide a laminated body, wherein a layer made of each of the joining materials is provided, and

firing the joining material to form the joining layer.

laminating greensheets, for the functional layers, to provide laminated greensheets, wherein a layer made of each of the joining materials is provided, and

firing the laminated greensheets with the layer made of the joining material to form the functional layers and the joining layer.

The inventors researched the above described warp of a dielectric layer or magnetic layer and finally made the following discovery. According to state-of-the-art knowledge, it is possible to improve the adhesive strength and therefore to prevent the peeling of the magnetic and dielectric layers, by adjusting the thermal expansion coefficient of joining ceramics between the magnetic and dielectric layers to those of both layers.

However, in actual manufacturing process, depending on the selection of materials for the magnetic and dielectric layers and sintering schedule, even when the thermal coefficient of the joining ceramics is adjusted to those of the magnetic and dielectric layers, warp may be observed during the sintering process. This phenomenon probably means that the magnetic, dielectric and joining layers shrink at different firing shrinkage rates at certain or even almost any time point during the sintering.

The inventors, based on the above discovery, successfully provide a solution. That is, the above warp may be considerably decreased or even prevented, on a wide variety of materials for magnetic and dielectric layers, by providing a joining material of each of the above specific compositions.

In the above compositions, for further reducing the warp of the magnetic or dielectric layer, a content of ZnO (a mol %) may preferably be 25 to 40 mol %, a content of BaO (b mol %) may preferably be 5 to 15 mol %, and a content of TiO ₂(c mol %) may preferably be 45 to 65 mol %.

A glass contained in the inventive joining material may preferably be selected from a group consisting of ZnO—SiO ₂—B₂O₃glass, PbO—B₂O₃—SiO₂glass, Al₂O₃—CaO—B₂O₃—SiO₂glass, B₂O₃—SiO₂glass, MgO—Al₂O₃—SiO₂cordierite glass, and ZnO—MgO—Al₂O₃—SiO₂cordierite glass, and most preferably be ZnO—SiO₂—B₂O₃glass. These glasses may further contain TiO₂, ZrO₂or Y₂O₃.

The greensheets for the inventive joining layer may be made brown, by adding not more than 10 mol % of MnO to the inventive joining material, to distinguish the brown-colored greensheet from greensheets for magnetic and dielectric layers. The joining layer may also be colored by adding at least one metal oxide selected from a group consisting of Cr ₂O₃, Fe₂O₃and NiO.

Not more than 10 mol % of Al ₂O₃may be added to the inventive joining material to further improve the adhesive strength of functional layers. Not more than 10 mol % of at least one metal oxide selected form a group consisting of Y₂O₃and ZrO₂may be also added to the inventive joining material to further improve the adhesive strength of adjacent functional layers.

More than 10 mol % of MnO added to the joining material might reduce the adhesive strength between the functional layers. More than 10 mol % of Al ₂O₃added to the joining material might increase the warp of functional layers.

In the invention, at least one of the functional layers functions as an element in an equivalent circuit, and therefore functions as an electronic device layer. Such electronic device layer includes inductor, capacitor and resistor layers. The inductor layer may preferably comprises a magnetic layer and an inductor, such as a coil, as a conductor embedded within the magnetic layer. The capacitor layer may preferably comprises a dielectric layer and a capacitor as a conductor embedded within the dielectric layer. The magnetic layer means a layer made of a magnetic material, in the invention.

The invention is particularly suitable for a composite electronic component, preferably being an LC filter, stacked type dielectric filter or an LCR integrated substrate.

The dielectric layer may be preferably made of a TiO ₂, TiO₂CaO, BaO—TiO₂, BaO—TiO₂—Nd₂O₃, BaO—TiO₂—Nd₂O₃—Bi₂O₃, BaO TiO₂—ZnO, BaO—Al₂O₃—SiO₂, MgO—CaO—TiO₂, BaO—MgO—Ta₂O₅or Al₂O₃series oxide. Such oxide may include a glass, which is preferably selected from B₂O₃—SiO₂, CaO—B₂O₃—SiO₂, CaO—Al₂O₃—B₂O₃—SiO₂and CaO—Al₂O₃—TiO₂—SiO₂series glasses.

The magnetic layer may preferably be made of a Fe ₂O₃—NiO—CuO—ZnO, Fe₂O₃—NiO—CuO—ZnO—SiO₂, NiO—ZnO, or CuO—ZnO or feroux planar series oxide. These magnetic material may contain not more than 5 weight percent of CoO or MnO, and about 1 weight percent of SiO, CaO, PbO, or Bi₂O₃constituting a glass. When applying these materials, warp may be induced more often, thus increasing the need for the invention.

When the joining layer has a thickness of not smaller than 10 μm, an amount of warp may be considerably reduced and the tensile strength thereof may be improved. The upper limit of the thickness is not particularly mentioned, however, the layer with a thickness of not larger than 500 μm is practical.

BRIEF DESCRIPTION OF THE DRAWINGS

FIG. 1 is a view schematically showing an LC filter suitable for applying the invention, [0033]
FIG. 2 is a perspective view showing greensheets needed for manufacturing the filter of FIG. 1, [0034]
FIG. 3 is a view schematically showing a stacked type dielectric filter suitable for applying the invention, [0035]
FIG. 4 is a perspective view showing greensheets needed for manufacturing the filter of FIG. 3, [0036]
FIG. 5 is a view schematically showing a stacked type LCR filter suitable for applying the invention, [0037]
FIG. 6 is a perspective view showing greensheets needed for manufacturing the filter of FIG. 5, [0038]
FIG. 7 is a photograph showing a polished surface of the filter sintered according to experimental number 16 within the invention, and [0039]
FIG. 8 is a photograph showing a polished surface of the filter sintered according to control experimental number 19 outside of the invention. [0040]
FIG. 1 is a view schematically showing an LC filter, and FIG. 2 is a perspective view needed for manufacturing an LC filter of FIG. 1. [0041]
As shown in FIG. 2, [0042] greensheets 7A, 7B, 7C, 7D, 7E, 7F, 7G, 7H and 7I for an inductor layer, greensheet 8 for a joining layer, and greensheets 9A, 9B, 9C, 9D, 9E, 9F, 9G, 9H, 9I and 9J for a capacitor layer are laminated. 13A for conductor paste are printed on the greensheets 7B to 7H for inductor layers, according to a coil pattern designed by a lumped parameter circuit. 14A for conductor paste are printed on the greensheets for a capacitor layer, according to a capacitor pattern designed by a lumped parameter circuit.
These greensheets are laminated and heat-pressed to provide laminated greensheets, which are then cut into a predetermined shape to provide a cut body. The cut body is sintered at a temperature of 800 to 950° C. and further subjected to barrel polishing. Paste for an outer electrode is printed on the surface of the sintered body according to a predetermined pattern, dried and then fired at a temperature of 500 to 850° C. to provide an LC filter shown in FIG. 1. The thus obtained LC filter comprises an [0043] inductor layer 2A, a joining layer 4A and a capacitor layer 5A. 3A is a coil pattern and 6A is a capacitor pattern.
FIG. 3 is a view schematically showing a stacked type dielectric filter, and FIG. 4 is a perspective view showing greensheets needed for manufacturing the filter of FIG. 3. [0044]
As shown in FIG. 4, greensheets [0045] 15A and 15B for register layers, a greensheet 8 for a joining layer and greensheets 9A to 9R for a capacitor layer are laminated. 16A for conductor paste are printed on the greensheet 15A, according to an electrode pattern designed for connection with an outer mounting part or inner conductors. 16A for resistor paste are printed on the greensheet 15B, according to a connecting-electrode pattern designed by a distributed constant circuit, or lamped parameter circuit, or the combination thereof. Capacitor patterns 14B, designed by a distributed constant circuit, or lamped parameter circuit, or the combination thereof, are printed on the greensheets 9B, 9C, 9D, 9E and 9F for a capacitor layer.
These greensheets are laminated and heat-pressed to provide laminated greensheets, which are then cut into a predetermined shape to provide a cut body. The cut body is sintered at a temperature of 700 to 1100° C. and further subjected to barrel polishing. Paste for an outer electrode is printed on the surface of the sintered body according to a desired pattern, dried and then fired at a temperature of 500 to 900° C. to provide a [0046] filter 10 shown in FIG. 5. The thus obtained filter comprises a resistor layer 11A, a joining layer 4B and a capacitor layer 5B. 12 is a connecting electrode pattern and 6B is a capacitor pattern.
FIG. 5 is a view schematically showing a stacked type LCR filter, and FIG. 6 is a perspective view showing greensheets needed for manufacturing the filter of FIG. 5. [0047]
As shown in FIG. 6, greensheets [0048] 15C and 15D for register layers, a greensheet 8 for a joining layer, greensheets 7J, 7K, 7L, 7M, 7N, 7O, 7P, 7Q, 7R and 7S for an inductor layer, another greensheet 8, and greensheets 9S, 9T, 9U, 9V, 9X and 9Y for a capacitor layer are laminated. 16B for conductor paste are printed on the outer greensheet 15C, according to an electrode pattern designed for connection with a surface mount part or inner conductors. Paste regions for electrodes are printed on the greensheet 15D, according to a coil pattern designed by a distributed constant circuit, or lamped parameter circuit, or the combination thereof. Paste regions for electrodes are printed on the greensheets 7L to 7Q for an inductor layer, according to an inductor pattern designed by a distributed constant circuit, or lamped parameter circuit, or the combination thereof. Paste regions for electrodes are printed on the greensheets 9U, 9V, 9W and 9X for a capacitor layer, according to a capacitor pattern designed by a distributed constant circuit, or lumped parameter circuit, or the combination thereof.
These greensheets are laminated and heat-pressed to provide a laminated greensheets, which are then cut into a predetermined shape to provide a cut body. The cut body is sintered at a temperature of 700 to 1100° C. and further subjected to barrel polishing. Paste for an outer electrode is printed on the surface of the sintered body according to a desired pattern, dried and then fired at a temperature of 700 to 1100° C. to provide an [0049] LCR filter 20 shown in FIG. 5. The thus obtained filter comprises a resistor layer 11B, joining layers 4A and 4B, an inductor layer 2B and a capacitor layer 5C. 12 is a connecting-electrode pattern and 3B is a coil pattern.

EXPERIMENT A

Greensheets shown in FIG. 2 were prepared. For greensheets for an inductor layer, nickel oxide, zinc oxide, copper oxide and ferrous oxide were weighed to a predetermined composition, mixed and calcined to provide a calcined body, which was then granulated to ceramic powder. To the ceramic powder, an organic binder, a plasticizer, a dispersing material and solvents, such as xylene and butanol, were added, blended and shaped by means of doctor blade method to provide greensheets with a thicknesses of 30 to 200 μm. Paste mainly consisting of silver was printed on some of the greensheets. [0050]
Zinc oxide, barium oxide and titanium oxide were weighed to a predetermined composition as shown in tables 1 and 2, mixed and calcined to provide a calcined body, which was then granulated to ceramic powder. To the ceramic powder, ZnO—SiO[0051] ₂—B₂O₃series glass powder already granulated was added (the content was varied as shown in tables 1 and 2), and an organic binder, a plasticizer, a dispersing material and solvents, such as xylene and butanol, were further added, blended and shaped by means of doctor blade method to provide a greensheet 8 with a thickness of 10 to 1000 μm.
Titanium oxide and calcium oxide were weighed to a predetermined composition, mixed and calcined to provide a calcined body, which was then granulated to ceramic powder. To the ceramic powder, ZnO—SiO[0052] ₂—B₂O₃series glass powder already granulated was added, and an organic binder, a plasticizer, a dispersing material and solvents, such as xylene and butanol, were further added blended and shaped by means of doctor blade method to provide greensheets for a capacitor layer with thicknesses of 10 to 1000 μm. Paste mainly consisting of silver was printed on some of the greensheets.
These greensheets were laminated, heat-pressed and cut into a predetermined shape to provide a cut body, which was then sintered at a temperature of not higher than 1100° C. Paste mainly consisting of silver was printed on the thus obtained sintered body according to an outer electrode pattern and fired to provide an LC filter. [0053]
The color of each greensheet for a joining [0054] layer 8 was observed with eyes. Further, the thus obtained LC filter was embedded within a resin body and polished with the surrounding resin. The amount of warp of each filter was measured with an automated dimension measuring apparatus. The specification for the amount of warp of each sintered filter was not larger than 30 μm.

The thickness of the joining

layer

4A was also measured on each filter. Aluminum rods, for measuring an adhesive strength, were adhered and fixed on the surfaces of the magnetic and dielectric layers, respectively, to provide a sample. The aluminum rods of each sample were fixed in a tensile strength measuring apparatus to measure its tensile strength. The adhesive strength was defined as a value at the moment of fracture. These experimental results were shown in tables 1 and 2.

TABLE 1


				ZnO—SiO₂—B₂O₃	color of	amount of warp	amount of warp	thickness of
	ZnO	BaO	TiO₂	glass content	greensheet for	after the sintering	during the	intermediate	adhesive strength
No.	mol %	mol %	mol %	weight parts	intermediate layer	(μm)	sintering (μm)	layer (μm)	(kgf)

1	10	22	68	2	gray	150	520	80	1
2	13	22	65	0.5	gray	not larger than 30	50	80	15
3	33	12	55	3	gray	not larger than 30	70	80	26
4	45	6	49	5	gray	not larger than 30	60	80	9
5	50	5	45	2	gray	140	410	80	1
6	37	3	60	2	gray	180	730	80	2
7	36	5	59	4	gray	not larger than 30	40	80	11
8	31	12	57	7	gray	not larger than 30	60	80	19
9	20	45	35	10	gray	not larger than 30	80	80	22
10	15	50	35	2	gray	130	350	80	1

TABLE 2


				ZnO—SiO₂—B₂O₃	color of	amount of warp	amount of warp	thickness of
	ZnO	BaO	TiO₂	glass content	greensheet for	after the sintering	during the	intermediate	adhesive strength
No.	mol %	mol %	mol %	weight parts	intermediate layer	(μm)	sintering (μm)	layer (μm)	(kgf)

11	45	40	15	2	gray	140	490	80	0.6
12	44	38	18	1	gray	not larger than 30	50	80	17
13	32	12	56	8	gray	not larger than 30	70	80	13
14	14	5	81	2	gray	not larger than 30	40	80	24
15	12	4	84	2	gray	110	350	80	1
16	33	12	55	2	gray	not larger than 30	60	80	21
17	33	12	55	2	gray	not larger than 30	50	80	not larger than 0.5
18	33	12	55	2	gray	not larger than 30	40	80	21
19	33	12	55	0	gray	230	not less than 1000	80	not larger than 0.5

As can be seen from the results, when adjusting a content of zinc oxide to 12 to 45 mol %, a content of barium oxide to 4 to 45 mol %, a content of TiO[0057] ₂to 18 to 81 mol % and a content of ZnO—SiO₂—B₂O₃series glass to 0.5 to 10 weight parts, the amount of warp was considerably decreased to not high than 30 μm.
X-ray diffraction curve was measured on each sample of experimental numbers of 2, 3, 4, 7, 8, 9, 12, 13, 14, 16, 17 and 18 show in tables 1 and 2. Consequently, either of or both peaks corresponding to BaNd[0058] ₂Ti₅O₁₄and BaNd₂Ti₄O₁₂was found.
Then, when the above cut bodies of experimental numbers 16 and 19 before the sintering were subjected to the sintering, each body's appearance was observed by means of a heating microscope to take a photograph showing the dielectric layer, magnetic layer and joining layer. In the filter of the number 16 fallen within the invention, the amount of warp of each functional layer was up to 30 μm. On the contrary, in the filter of the control experimental number 19, the amount of warp of the whole filter was more than 1000 μm. [0059]

EXPERIMENT B

LC filters were produced as described in the experiment A, however, manganese oxide or alumina was added to a greensheet for a joining layer. The composition of the greensheet was changed as shown in FIG. 3, which also shows the experimental results.

TABLE 3


							color of
	ZnO	BaO	TiO₂			ZnO—SiO₂—B₂O₃	greensheet for	amount of warp	amount of warp	thickness of	adhesive
	mol	mol	mol	MnO	Al₂O₃	glass content	intermediate	after the sintering	during the	intermediate	strength
No.	%	%	%	mol %	mol %	weight parts	layer	(μm)	sintering (μm)	layer (μm)	(kgf)

21	33	12	55	0	0.5	2	gray	not larger than 30	50	80	26
22	31	12	52	0	5	2	gray	not larger than 30	40	80	22
23	30	11	49	0	10	2	gray	not larger than 30	30	80	18
24	29	11	48	0	12	2	gray	70	290	80	2
25	33	12	55	0.1	0	2	brown	not larger than 30	50	80	29
26	31	12	52	5	0	2	brown	not larger than 30	60	80	20
27	30	11	49	10	0	2	brown	not larger than 30	50	80	19
28	29	11	48	12	0	2	brown	not larger than 30	80	80	not larger
											than 0.5

Consequently, same as the experiment A, when adjusting a content of zinc oxide to 12 to 45 mol %, a content of barium oxide to 4 to 45 mol %, a content of TiO[0061] ₂to 18 to 81 mol % and a content of ZnO—SiO₂—B₂O₃series glass to 0.1 to 10 weight parts, the amount of warp of each filter was decreased to not higher than 80 μm during the sintering, and to not higher than 30 μm after the sintering. Further, the greensheet was colored brown by adding MnO. However, when MnO was added in an amount of more than 10 mol %, the adhesive strength was lowered.
Although the addition of alumina increased considerably the adhesive strength, when alumina was added in an amount of more than 10 mol %, the amount of warp of the filter after the sintering was more than 70 μm. [0062]

EXPERIMENT C

LC filters were manufactured as described in the experiment A, however, the compositions of the greensheets for joining layers were changed as shown in table 4, showing the experimental results.

TABLE 4


							color of
	ZnO	BaO	TiO₂			ZnO—SiO₂—B₂O₃	greensheet for	amount of warp	amount of warp	thickness of	adhesive
	mol	mol	mol	MnO	Al₂O₃	glass content	intermediate	after the sintering	during the	intermediate	strength
No.	%	%	%	mol %	mol %	weight parts	layer	(μm)	sintering (μm)	layer (μm)	(kgf)

31	33	12	54	0.1	0.5	2	brown	not larger than 30	50	80	35
32	33	12	54	0.1	0.5	14	brown	100	420	80	not larger
											than 0.5
33	30	11	49	5	5	2	brown	not larger than 30	60	80	20
34	30	11	49	5	5	0	brown	260	920	80	not larger
											than 0.5
35	26	10	44	10	10	2	brown	not larger than 30	60	80	19
36	26	10	44	10	10	12	brown	90	310	80	not larger
											than 0.5
37	25	9	42	12	12	2	brown	70	260	80	1
38	25	9	42	12	12	0	brown	180	660	80	not larger
											than 0.5

Consequently, same as the experiment A, when adjusting contents of zinc oxide, barium oxide, titanium oxide, manganese oxide and alumina according to the invention and a content of ZnO—SiO[0064] ₂—B₂O₃series glass to 0.1 to 10 weight parts, the amount of warp of each filter was considerably decreased during the sintering. When the amount of the glass was out of a range of 0.1 to 10 weight parts, the amount of warp was more than 70 μm.

EXPERIMENT D

LC filters were manufactured as described in the experiment A, however, the compositions of the greensheets for joining layers were adjusted in the preferred range of the invention and thicknesses of the joining layers were changed. The results were shown in table 5.

TABLE 5


							color of
	ZnO	BaO	TiO₂			ZnO—SiO₂—B₂O₃	greensheet for	amount of warp	amount of warp	thickness of	adhesive
	mol	mol	mol	MnO	Al₂O₃	glass content	intermediate	after the sintering	during the	intermediate	strength
No.	%	%	%	mol %	mol%	weight parts	layer	(μm)	sintering (μm)	layer (μm)	(kgf)

39	33	12	55	1	1	2	brown	70	270	5	1
40	33	12	55	1	1	2	brown	60	240	10	5
41	33	12	55	1	1	2	brown	50	190	100	9
42	33	12	55	1	1	2	brown	not larger than 30	50	200	12
43	33	12	55	1	1	2	brown	not larger than 30	40	300	23
44	33	12	55	1	1	2	brown	not larger than 30	50	400	35
45	33	12	55	1	1	2	brown	not larger than 30	30	500	46

Consequently, same as the experiment A, the amount of warp of each filter was considerably decreased according to the invention. Further, when the thickness of the joining layer was adjusted to not smaller than 30 μm, the amount of warp was considerably lowered and the adhesive strength was considerably improved. [0066]

EXPERIMENT E

Greensheets shown in FIG. 4 were prepared. In greensheets for a resistor layer, alumina powder and almino-calcium borosilicate glass were mixed with an organic binder, a plasticizer, a dispersing material and solvents such as xylene and butanol, blended and then shaped by means of doctor blade method to provide greensheets with thicknesses of 0.01 to 1.0 μm. Paste mainly consisting of silver was printed on some of the greensheets. [0067]
33 mol % of Zinc oxide, 12 mol % of barium oxide and 55 mol % of titanium oxide were weighed, mixed and calcined to provide a calcined body, which was then granulated to ceramic powder. To the ceramic powder, 2 weight parts of ZnO—SiO[0068] ₂—B₂O₃series glass powder already granulated was added, and an organic binder, a plasticizer, a dispersing material and solvents, such as xylene and butanol, were further added, blended and shaped by means of doctor blade method to provide a greensheet 8 with a thickness of 10 to 1000 μm.
Barium oxide, titanium oxide, neodymium oxide and bismuth oxide were weighed, mixed and calcined to provide a calcined body, which was then granulated to ceramic powder. To the ceramic powder, an organic binder, a plasticizer, a dispersing material and solvents, such as xylene and butanol, were further added, blended and shaped by means of doctor blade method to provide greensheets for a capacitor layer with thicknesses of 10 to 500 μm. Paste mainly consisting of silver was printed on some of the greensheets. [0069]
These greensheets were laminated and heat-pressed to provide a laminated body, which was then cut into a cut body with a predetermined shape. The cut body was sintered at a temperature of not higher than 1100° C. to obtain a stacked trace dielectric filter, whose amount of warp was found to be not larger than 30 μm. [0070]

EXPERIMENT F

Greensheets as shown in FIG. 6 were prepared. Greensheets for resistor, joining and capacitor layers were manufactured as described in the experiment E. Greensheets for an inductor layer were also manufactured, as described in the experiment A. [0071]
These greensheets were laminated and heat-pressed to provide a laminated body, which was then cut into a cut body with a predetermined shape. The cut body was then sintered at a temperature not higher than 1100° C. to obtain an LCR filter, whose amount of warp was found to be not large than 30 μm. [0072]

Claims

1. A joining material for an electronic component having a plurality of functional layers each selected from a magnetic layer and dielectric layer, the functional layers being joined with each other by means of the joining material, the joining material comprising a glass and a composition of a mol % of ZnO, b mol % of BaO and c mol % of TiO₂(a=12-45, b=4-45, c=18-81, a+b+c=100), wherein 0.1 to 10 weight parts of the glass is added to 100 weight parts of the composition.

2. A joining material for an electronic component having a plurality of functional layers each selected from a magnetic layer and dielectric layer, the functional layers being joined with each other by means of the joining material, the joining material comprising a glass and a composition of a mol % of ZnO, b mol % of BaO, c mol % of TiO₂and d mol % of MnO (a=12-45, b=4-45, c=18-81, d≦10, a+b+c+d=100), wherein 0.1 to 10 weight parts of the glass is added to 100 weight parts of the composition.

3. A joining material for an electronic component having a plurality of functional layers each selected from a magnetic layer and dielectric layer, the functional layers being joined with each other by means of the joining material, the joining material comprising a glass and a composition of a mol % of ZnO, b mol % of BaO, c mol % of TiO₂and e mol % of Al₂O₃(a=12-45, b=4-45, c=18-81, e≦10, a+b+c+e=100), wherein 0.1 to 10 weight parts of the glass is added to 100 weight parts of the composition.

4. A joining material for an electronic component having a plurality of functional layers each selected from a magnetic layer and dielectric layer, the functional layers being joined with each other by means of the joining material, the joining material comprising a glass and a composition of a mol % of ZnO, b mol % of BaO, c mol % of TiO₂, d mol % of MnO and e mol % of Al₂O₃(a=12-45, b=4-45, c=18-81, d≦10, e≦10, a+b+c+d+e=100), wherein 0.1 to 10 weight parts of the glass is added to 100 weight parts of the composition.

5. The joining material as claimed in each of claims 1 to 4, wherein a content of ZnO is 25 to 40 mol %, a content of BaO is 5 to 15 mol % and a content of TiO₂is 45 to 65 mol %.

6. The joining material as claimed in each of claims 1 to 5, further comprising not more than 10 mol % of at least one metal oxide selected from a group consisting of Cr₂O₃, Fe₂O₃and NiO.

7. The joining material as claimed in each of claims 1 to 5, further comprising not more than 10 mol % of at least one metal oxide selected from a group consisting of Y₂O₃and ZrO₂.

8. The joining material for an electronic component as claimed in each of claims 1 to 7, wherein the glass is selected from a group consisting of ZnO—SiO₂—B₂O₃glass, PbO—B₂O₃—SiO₂glass, Al₂O₃—CaO—B₂O₃—SiO₂glass, B₂O₃—SiO₂glass, MgO—Al₂O₃—SiO₂cordierite glass, and ZnO—MgO—Al₂O₃—SiO₂cordierite glass.

9. An electronic component having a plurality of functional layers each selected from a magnetic layer and dielectric layer and a joining layer, wherein the joining layer is composed of sintered product of the joining material as claimed in each of claims 1 to 8.

10. An electronic component having a plurality of functional layers each selected from a magnetic layer and dielectric layer and a joining layer, wherein the joining layer is composed of sintered product showing at least one of a peak corresponding to BaNd₂Ti₅O₁₄and a peak corresponding to BaNd₂Ti₄O₁₂, when measured by means of powdery X-ray diffraction method.

11. The electronic component as claimed in claim 9 or 10, wherein the joining layer has a thickness of not smaller than 10 μm and not larger than 500 μm.

12. A method for manufacturing an electronic component having a plurality of functional layers each selected from a magnetic layer and dielectric layer and joining layer, the method comprising the steps of:

laminating the functional layers already sintered to provide a laminated body, wherein a layer made of the joining material as claimed in each of claims 1 to 8 is provided, and

firing the joining material to form the joining layer.

13. A method for manufacturing an electronic component having a plurality of functional layers each selected from a magnetic layer and dielectric layer and a joining layer, the method comprising the steps of:

laminating greensheets, for the functional layers, to provide laminated greensheets, wherein a layer made of the joining material as claimed in each of claims 1 to 8 is provided, and

14. The method as claimed in claim 12 or 13, wherein the layer made of the joining material is provided as a form of a greensheet, paste slurry, or thin film.