(12) INTERNATIONAL APPLICATION PUBLISHED UNDER THE PATENT COOPERATION TREATY (PCT)
`
`(19) World Intellectual Property Organization
`International Bureau
`
`(43) International Publication Date
`8 November 2001 (08.11.2001)
`
` (10) International Publication Number
`
`WO 01/83395 A1
`
`(51) International Patent Classification7:
`H0lB 3/12
`
`C04B 35/46,
`
`(21) International Application Number:
`
`PCT/KR00/00984
`
`(22) International Filing Date: 30 August 2000 (30.08.2000)
`
`6-803. Kongneung
`[KR/KR]; Taeneung-woosung Apt.
`2—dong, Nowon~ku, Seoul 139~242 (KR). KIM, Hyo-Tae
`[KR/KR]; Kist Dormitory 36, 39-1. Hawolgok—dong,
`Sungbook-ku, Seoul 136-791 (KR).
`
`(74) Agent: PARK, Jang-Won; Jewoo Building 5th floor, 200,
`Nonhyun-dong, Kangnam-ku. Seoul 135-010 (KR).
`
`(81) Designated States (national): CN, IN, JP, US.
`
`Korean
`
`English
`
`(25) Filing Language:
`
`(26) Publication Language:
`
`(30) Priority Data:
`2000-23676
`
`3 May 2000 (03.05.2000)
`
`KR
`
`(84) Designated States (regional): European patent (AT, BE,
`CH, CY, DE, DK, ES, Fl, FR, GB, GR, IE, IT, LU, MC,
`NL, PT, SE).
`
`(71) Applicant (for all designated States except US): KOREA
`INSTITUTE OF SCIENCE AND TECHNOLOGY
`[KRIKR]; 39-1, Hawolgok-dong, Sungbook-ku, Seoul
`1364791 (KR).
`
`Published:
`
`with international search report
`
`(72) Inventors; and
`(75) Invcntors/Applicants (for US only): KIM, Yoon-Ho
`
`For two—letter codes and other abbreviations, refer to the ”Guid—
`ance Notes on Codes and Abbreviations ” appearing at the begin-
`ning ofeach regular issue ofthe PCT Gazette.
`
`(54) Title: LOW TEMPERATURE SINTERABLE AND LOW LOSS DIELECTRIC CERAMIC COMPOSITIONS AND
`METHOD THEREOF
`
`(57) Abstract: A low loss high-frequency
`dielectric ceramic composition for sintering
`at a low temperature and method of man-
`ufacturing the same which is characterized in
`that excellent dielectric properties such as a
`much lower sintering temperature and higher
`quality coefficient and dielectric constant,
`compared to a conventional high-frequency
`ceramic composition, a stabilized temperature
`coefficient, and a temperature compensating
`property varied according to a composition,
`are implemented using a low-priced material
`such as ZnO-Mo (M=Mg, Co, Ni)—TiO2.
`In addition, Ag, Cu, an alloy thereof, or
`an Ag/Pd alloy can be used as an internal
`electrode.
`Thus.
`the composition of the
`present invention can be used as a dielectric
`material
`for
`all
`sorts of high-frequency
`devices, such as a multilayer chip capacitor,
`
`chip
`filter, multilayer
`chip
`multilayer
`and
`composite
`device
`capacitor/inductor
`module,
`low temperature sintered substrate,
`resonator or filter and ceramic antenna.
`
`1100
`
`1300
`
`E
`
`I000
`
`900
`
`8 1
`
`E
`§
`3
`8
`D
`
`
`
`Temperature(C)
`
`I||||||||||||||||||||||||||||||I||||||||||||||||||||||||||||||||||||||||||||||||
`
`F1
`<
`
`In
`a
`
`30
`
`KV
`
`0
`-4
`
`Exhibit 1038
`Exhibit 1038
`IPR2016-00636
`IPR20l6-00636
`AVX Corporation
`Corporatio
`
`0.0
`
`0.1
`
`0.3
`0.2
`1* <m°'°1
`
`0.4
`
`0.5
`
`G O
`
`a
`
`000001
`
`000001
`
`

`

`W0 01/83395
`
`PCT/KR00/00984
`
`LOW TEMPERATURE SINTERABLE AND LOW LOSS DIELECTRIC
`
`CERAMIC COMPOSITIONS AND METHOD THEREOF
`
`TECHNICAL FIELD
`
`The present invention relates to a low temperature sinterable and low
`
`5
`
`loss dielectric ceramic compositions for use in fabricating various high
`
`frequency devices such as a multilayer chip capacitor, a multilayer chip filter,
`
`a multilayer chip capacitor inductor composite device and module, a low
`
`temperature sinterable substrate, a resonator or a filter and a ceramic antenna,
`
`and its method.
`
`BACKGROUND ART
`
`Recently, with the rapid development in a mobile communication and a
`
`satellite communication, a high frequency dielectric ceramics is in a high
`
`demand as a material for a high frequency integrated circuit or a dielectric
`
`l—'
`
`(I1
`
`resonator.
`
`Major characteristics of the dielectric ceramics used for a high frequency
`
`includes a high dielectric constant (5,), a quality factor (Q) and a stable and
`
`tunable temperature coefficient (1,) of a resonance frequency.
`
`Representative high frequency dielectric compositions which have been
`
`20
`
`widely known up to now are (Zr, Sn)TiO4 group, BaO-TiO2 group,
`
`(Mg,
`
`Ca)TiO3 group, and Ba-(Zn,,3Ta2,3)O3, Ba(Mg,,3Ta2,3)O3, Ba(Zn,,3Nb2,3)O3 as Ba-
`
`peropskite group etc.
`
`However, these compositions are disadvantages in that they are mostly
`
`000002
`
`000002
`
`

`

`W0 01/83395
`
`PCT/KR00/00984
`
`fired at a high temperature of 1,300~1,500°C, phase synthesis is not easy, a
`
`dielectric constant is low or a high-priced material should be used.
`
`Besides, lately, advancement of a portable information communication
`
`devices lead to development of various types of substrates and multi-chip
`
`module (MCM) by a multilayer chip high frequency devices or low temperature
`
`co-firing ceramics (LTCC), and a research and development of a low
`
`temperature firing high performance high frequency ceramics are conducted
`
`accordingly.
`
`However, there are problems that the performance of the high frequency
`
`characteristic is considerably degraded such as, for example, most of them are
`
`not sufficient in terms of density when being fired at a low temperature, a
`
`dielectric constant is decreased according to addition of a sintering aid, a
`
`quality factor is degraded and a temperature factor is changed.
`
`In addition, silver or copper conduct with a small high frequency loss and
`
`a cofiring available low temperature firing high frequency dielectric ceramic are
`
`very rare.
`
`Therefore, an object of the present invention is to provide a dielectric
`
`ceramics composition which can be fired at a very low temperature but has an
`
`excellent high frequency dielectric characteristic of various temperature
`
`compensation characteristics according to a high quality factor, a dielectric
`
`constant, a stable temperature factor and a composition, and can be
`
`implemented at a low cost.
`
`Another object of the present invention is to provide a dielectric ceramics
`
`10
`
`15
`
`20
`
`
`
`000003
`
`000003
`
`

`

`W0 01/33395
`
`PCT/KR00/00984
`
`composition which can employ Ag, Cu, their alloy or a Ag/Pd alloy as an
`
`internal electrode and thus be used for various high frequency devices, such
`
`as a multilayer chip capacitor, a multilayer chip filter, a multilayer chip
`
`capacitor/inductor composite device and a low temperature sinterable
`
`5
`
`substrate, a resonator and a filter or a ceramic antenna.
`
`DETAILED DESCRIPTION OF THE INVENTION
`
`In order to achieve the above objects, there is provided a dielectric
`
`ceramics composition which is constructed by combining 1 mole of (Zn,_
`
`10
`
`XMX)TiO3 and yTiO2(Osys0.6 as a main component, one of O~5 wt % B203, O~5
`
`wt % H3BO3, O~5 wt °/o SiO2-K20 glass, O~5 wt °/o B203 and SiO2-K20 glass, or
`
`O~5 wt % H3BO3 and SiO2-K20 glass is added as an additive thereto, and fired
`
`at a low temperature of 800~925°C,
`
`its preparation method, and a high
`
`frequency dielectric ceramics device using the same. In this respect, ‘M’ is one
`
`15
`
`of Mg, Co, Ni, ‘x’ is 0sxsO.55 in case of Mg and ‘x’ is 03x31 in case of Co, and
`
`0sxs1 in case of Ni
`
`BRIEF DESCRIPTION OF THE DRAWINGS
`
`Figure 1 is a graph showing a phase dissociation temperature of (Zn,_
`
`2 0
`
`XMX)TiO3 according to the substituted amount of Mg.
`
`MODE FOR CARRYING OUT THE PREFERRED EMBODIMENTS
`
`The present
`
`invention will now be described with reference to
`
`000004
`
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`
`

`

`WO 01/83395
`
`PCT/KR00/00984
`
`accompanying drawings.
`
`A high frequency dielectric ceramics composition of the present invention
`
`is characterized in that it has a very low firing temperature (800~925°C)
`
`compared to that of a conventional dielectric composition, has an excellent high
`
`frequency dielectric characteristic of various temperature compensation
`
`characteristics (‘cf = -52 ~ +104 ppm/°C) according to a high quality factor (Q
`
`x f = 12,000 ~ 84,000 GHz), a dielectric constant (16 3 gr < 32), a stable
`
`temperature factor and a composition, and can be implemented with a low-
`
`priced material such as ZnO, MgO, CoO, NiO, TiO2,
`
`10
`
`In addition, the high frequency dielectric ceramics composition of the
`
`present invention is also characterized in that it employs Ag, Cu, their alloy or
`
`a Ag/Pd alloy as an internal electrode and thus be used for various high
`
`frequency devices, such as a multilayer chip capacitor, a multilayer chip filter,
`
`a multilayer chip capacitor/inductor composite device and a low temperature
`
`15
`
`firing substrate, a resonator and a filter or a ceramic antenna.
`
`In the present invention, the low temperature firing composition of the
`
`present invention has an excellent quality factor (close to the existing high
`
`temperature firing composition) more than several times the existing one.
`
`In
`
`addition,
`
`in the claimed composition coverage, combination of composition
`
`20
`
`having an excellent high frequency characteristic of the almost infinite number
`
`can be obtained compared to any of the conventional ones.
`
`ZnTiO3 (crystal structure has a rhombohedral symmetry) is phase-
`
`dissociated to Zn2TiO4 (cubic symmetry) and TiO2 (rutile) at a higher
`
`
`
`000005
`
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`
`

`

`W0 01/83395
`
`PCT/KR00/00984
`
`temperature than 945°C (refer to Fig.303 of Phase Diagrams for Ceramist by
`
`the American Ceramic Society, System ZnO-TiO2 by Dulin and Rase), and thus
`
`i
`
`it is very difficult to be prepared.
`
`In order to obtain a pure ZnTiO3, phase synthesis and firing must be
`
`made at a below 945°C. A preliminary experiment of the present invention
`
`shows a result through an X-ray diffraction analysis that phase dissociation
`
`starts at near 925°C so that a thermal treatment must be performed at below
`
`925°C.
`
`10
`
`15
`
`In a preferred embodiment of the present invention, in order to remove
`
`the shortcomings, Zn“, a positive ion of A-site constituting an ABO3 type
`
`ilmenite phase ceramics, is substituted with Mg” (up to 0.55 mole), to thereby
`
`enlarge a thermal stabilization temperature of ZnTiO3 to a high temperature
`
`range (refer to Figure 1), so that the preparation process coverage is widened
`
`and the high frequency dielectric characteristic are highly improved.
`
`Figure 1 is a graph showing a phase dissociation temperature of (Zn,_,
`
`Mgx)TiO3 according to the substituted amount of Mg. In case that a region x =
`
`0, ZnTiO3 is dissociated at a temperature of 945°C, and since the dissociation
`
`temperature goes up to a high temperature by the substitution of Mg, a single
`
`phase of the (Zn,_, Mg,)TiO3 solid solution can be synthesized or fired even at
`
`20
`
`a temperature of higher than 945°C.
`
`Accordingly, a single phase can be obtained anywhere in the region ll
`
`of Figure 1, which is the phase synthesis region of the present invention.
`
`A high frequency dielectric ceramics composition in accordance with a
`
`
`
`5
`
`000006
`
`000006
`
`

`

`WO 01/83395
`
`PCT/KR00/00984
`
`preferred embodiment of the present invention will now be described.
`
`Powders (an average particle diameter is mm) of ZnO, MO (in this
`
`respect, MO is MgO, CoO or NiO) and TiO2 (>99%) was weighed according to
`
`a composition range of (Zn,_xMx)TiO3 and yTiO2 (M is one of Mg, Co and Ni, x
`
`is OsxsO.55 in case of Mg, x is OSXS1 in case of Co, x is 03x51 in case of Ni,
`
`and y is O:ys0.6), mixed in a wet ball mill method, dried at 120°C, and calcined
`
`and synthesized at a temperature of 850~950°C for four hours.
`
`The calcined powder was mixed with 0.5 wt % B203, O~5 wt % SiO2—K2O
`
`glass and a combination of O~1O wt % B203 and SiO2-K20 as a sintering aid.
`
`At this time, in case of B203, besides the oxide, a water soluble boron
`
`(H3BO3) was used to improve homogeneity in adding a little amount.
`
`Solubility (per water 100cc) of boron to cool water (30°C) and hot water
`
`(100°C) is 6.35 and 27.6 (refer to Handbook of Chemistry and Physics, 55"‘ ed.,
`
`CRC Press, 1974-75).
`
`In case of the present invention, cool water was used to make boron
`
`corresponding to the solubility to an aqueous solution,
`
`into which the main
`
`component or the main composition and the glass powder are mixed and
`
`crushed.
`
`In crushing, since the temperature of slurry goes up further (especially,
`
`up to 45°C in case of high speed centrifugal crushing), the mixture of boron can
`
`be more uniform.
`
`As for the SiO2-K20 glass, SiO2 and K2CO3 were mixed with K2CO3 by
`
`55~75 wt °/o and 25~45 wt %, melt at a temperature of 1100~1200°C, quenched
`
`1O
`
`15
`
`20
`
`F0
`
`000007
`
`
`
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`
`

`

`WO 01/83395
`
`PCT/KR00/00984
`
`at cool deionized water, ball-milled for 24 hours, thereby obtaining glass
`
`powder, and it was confirmed that an amorphous phase of glass was obtained
`
`according to an X—ray diffraction analysis result.
`
`Since the present invention is aimed at a low temperature firing at a
`
`below 925°C, in order to obtain fine powder (average particle diameter of below
`
`O.5um) less than submicron, a stabilized zirconia ball with a diameter of 2mm
`
`was used and crushed for four hours by an attrition mill, or a fine stabilized
`
`zirconia ball with a diameter of 1mm was used and subjected to a high speed
`
`centrifugal crushing for 5~1O minutes.
`
`An aqueous solution to which 2 wt % PVA binder was added is mixed
`
`with the dried powderto make a granule of about 150um and shaped to a disk
`
`test sample having a diameter of 8mm and a thickness of 3.8mm at a pressure
`
`of 98 Mpa.
`
`The shaped test sample was maintained at a temperature of 300~500°C
`
`for over 3 hours to burn out the binder, and then sintered at a temperature
`
`800~925°C at an atmosphere.
`
`At this time, a heating rate was 10°C/min. The sintered test sample was
`
`ground with an SiC polishing paper (#1500) to obtain about 0.45 ratio of
`
`diameter to thickness of the test sample.
`
`The high frequency dielectric characteristic was measured in a TEM
`
`mode by using a network analyzer (HP 8720C) by making a cylindrical dielectric
`
`ceramics resonator, and a dielectric constant was measure by a Hakki—
`
`Coleman method, a quality factor was measure by an open cavity method, a
`
`10
`
`15
`
`20
`
`
`
`7
`
`000008
`
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`

`W0 01,83,395
`
`PCT/KR00/00984
`
`temperature factor of a resonance frequency was measured by an invar cavity
`
`at a temperature range of +20~+70°C.
`
`Table 1 shows a high frequency dielectric characteristic in case that
`
`B203, boron (H3B03) and a combination component of boron and Si02-K20
`
`5
`
`glass are added as sintering aids to a main composition that x=0.01 and y=Ol2
`
`among (Zn,_XMX)Ti03 (OsxsO.55) and yTi02OsysO.6) composition.
`
`In Table 1, a 800°C—sintered body had about more than 92% relative
`
`density, and 875°C-sintered body had about more than 97% relative density.
`
`In the embodiments 2~5 and 6~10,
`
`it is noted that quality factor was
`
`10
`
`further improved in case of adding boron instead of adding B203, and as for the
`
`temperature coefficient, the variation rate according to the sintering temperature
`
`(800°C and 875°C) was smaller. This effect results from a uniformity of boron.
`
`As the sintering characteristic thanks to addition of B203, the dielectric
`
`constant and quality factor were much increased, and were increased up to
`
`15
`
`about 2 wt % and then reduced at 5 wt %.
`
`The temperature coefficient was moved to a positive as the amount of
`
`B203 is increased.
`
`Accordingly, in the embodiments of Table 1,
`
`it is anticipated that if the
`
`value ‘y’
`
`is a bit increased more than 0.2 and the amount of additive is
`
`20
`
`controlled, an excellent dielectric property of which the temperature factor is
`
`almost ‘O’ can be obtained.
`
`That is, in order to be a usable high frequency characteristic, not only
`
`Ti02, but
`
`the amount of additive needs to be controlled property, and
`
`8
`
`000009
`
`000009
`
`

`

`WO 01/83395
`
`PCT/KR00/00984
`
`accordingly, various composition groups can be obtained.
`
`Table ‘I: High frequency dielectric property of a dielectric resonator
`
`fabricated with composition of (ZnO0p99Mw)TiO3 (M=Mg) + O.2TiO2 + (B203,
`
`5
`
`H3BO3, or H3803 + SiO2-K20 glass)
`
`‘No. B203
`
`H2BO3
`
`SiO2- e|ectric Quality Temperature
`
`(wt°/o)
`
`(vvt%)
`
`K20
`
`temperat- constant
`
`factor
`
`coefficient
`
`glass
`
`ure (°C)
`
`(8,)
`
`(Qxf
`
`(rfzppm/°C)
`
`(wt%)
`
`GHz)
`
`T?-— -
`
`-
`
`2
`
`0.25
`
`-
`
`-4-
`
`3
`
`0.50
`
`-
`
`4
`
`1.00‘?
`
`5
`
`2.00
`
`-
`
`6
`
`7
`
`-
`
`-
`
`0.25
`
`0.50
`
`-
`
`-
`
`-
`
`-
`
`-
`
`800
`
`875
`
`800
`
`875
`
`800
`
`875
`
`800
`
`875
`
`800
`
`875
`
`800
`875
`
`480-0“
`
`13.8
`
`22900
`
`-22
`
`21.1
`
`22.3
`
`32400
`
`-50
`
`65700
`
`-52
`
`26.9
`
`78200
`
`-48
`
`23.0
`
`54800
`
`-43
`
`26.4
`
`84600
`
`-40
`
`19.7
`
`50100 7+4
`
`26.5
`
`80900
`
`-33
`
`19.6
`
`44800
`
`-29
`
`27.2
`
`79300
`
`-22
`
`22.1
`27.0
`
`20.2
`
`739800 ;—46
`84300 3-43
`
`50600
`
`-44
`
`875
`
`26.0
`
`85200
`
`-39
`
`
`
`000010
`
`000010
`
`

`

`W0 01,83395
`
`PCT/KR00/00984
`
`8
`
`—
`
`1.00
`
`T7
`
`2.00
`
`-
`
`-
`
`10
`
`- —"5.00
`
`3
`
`800
`
`875
`
`800
`
`875
`
`800
`875
`
`19.3
`
`47700
`
`-33
`
`25.3
`
`81200
`
`-34
`
`19.5
`
`745400 740
`
`25.7
`
`70100
`
`-20
`
`15.5
`25.1
`
`'40000
`50200
`
`-10
`+20
`
`-11’-
`
`0.50
`
`0.50
`
`800
`
`"“19.5
`
`58800
`
`-43
`
`875
`
`25.8
`
`57200
`
`+39
`
`12 K
`
`0.50
`
`1.00
`
`800
`
`.17.0
`
`42400 “-20
`
`875
`
`0.50
`
`2.00
`
`800
`
`23.5
`
`15.7
`
`58400
`
`-38
`
`l’25300‘-17
`
`875
`
`23.8
`
`45100
`
`~35
`
`$0.50
`
`7500‘ 800
`
`_‘15.4
`
`25000
`
`~21
`
`"13
`
`14
`
`-
`
`-
`
`“15—'—“—0.50
`
`5.00
`
`"W3
`
`13.7
`
`19100
`
`-19
`
`875
`
`24.1
`
`35200
`
`-29
`
`875
`
`23.4
`
`24500
`
`-43
`
`Table 2 indicates a dielectric property in case of increasing the amount
`
`of Mg and TiO2 (x = 0.55, Y = 0.6).
`
`3
`
`Table 2: High frequency dielectric property of a dielectric resonator fabricated
`
`with a composition of (Zn00A45M0‘55)TiO3 (M=Mg) + 0.6TiO_,_ + (B203, H3BO3, or
`
`H3BO3 + SiO2—K2O glass)
`
`10
`
`000011
`
`000011
`
`

`

`W0 01/83395
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`PCT/KR00/00984
`
`No. B203
`
`H2303
`
`SiO2-
`
`Sintering "Dielectric Quality Temperature
`
`(wt%)
`
`(wt%)
`
`K_,_O
`
`temperat- constant
`
`factor
`
`coefficient
`
`glass
`
`ure (°C)
`
`1 (2,)
`
`(Qxf
`
`(rf:ppm/°C)
`
`(wt%)
`
`GHz)
`
`‘1e
`
`‘
`:17
`
`-
`
`0.25
`
`—
`
`18
`
`0.50"T
`
`—
`
`—
`
`—
`
`T’T0’<)_7"’_“-
`
`900
`
`925
`900
`
`925
`
`900
`
`925
`
`E900
`
`925
`
`20.2
`
`24.3
`26.9
`
`30.1
`
`26.9
`
`29.5
`
`26.0
`
`28.4
`
`‘18300 L+6O
`
`“
`
`20700
`19700
`
`+56
`+54
`
`35300
`
`+78
`
`“20300
`
`+57
`
`44000
`
`+65
`
`22300 “+51
`
`J
`
`35300
`
`+87
`
`25.7
`
`722400
`
`+57
`
`20
`
`2.00
`
`—
`
`21
`
`‘T
`
`0.25
`
`—
`
`—
`
`900
`
`925
`
`900
`
`925
`
`0.50 —""_L900
`
`22
`
`23
`
`24
`
`25
`
`—
`
`—
`
`—
`
`—
`
`28.6
`
`30500
`
`+79
`
`27.3
`
`30.1
`
`26.5
`
`123200 "+72
`
`58900
`
`+86
`
`‘23000 "+72
`
`1.00
`
`2.00
`
`5.00
`
`—
`
`—
`
`—
`
`925
`
`900
`
`925
`
`900
`
`925
`
`900
`
`29.3
`
`46000
`
`+70
`
`“253
`
`23100 J+55
`
`28.2
`
`33400
`
`+73
`
`”‘25.5
`
`21700
`
`+68
`
`28.1
`
`23.7
`
`27300
`
`+88
`
`421200 ‘+75
`
`11
`
`000012
`
`000012
`
`

`

`WO 01/83395
`
`PCT/KR00/00984
`
`%”g?"0.:50""T0.50
`
`925
`
`900
`
`925
`
`0.50
`
`1.00
`
`900
`
`925
`
`27
`
`28
`
`—
`
`—
`
`27.5
`
`16600
`
`+104
`
`22.8
`
`26.8
`
`24.2
`
`29.0
`
`27900
`
`+54
`
`22700
`
`+79
`
`29800
`
`+46
`
`26800 +76
`
`73.50
`
`2.00
`
`900
`
`28.4
`
`‘22300
`
`+65
`
`925
`
`32.0
`
`17900
`
`+71
`
`"29 1
`
`0.50
`
`3.00
`
`900
`
`28.9
`
`27600
`
`+49
`
`925
`
`32.5
`
`19500
`
`+84
`
`30
`
`-
`
`0.50
`
`5.00
`
`900
`
`T
`
`21200
`
`+33
`
`925
`
`11900
`
`+53
`
`In the above embodiments, positive temperature coefficients were
`
`obtained. In this case, a temperature coefficient of ‘O’ can be naturally obtained
`
`by adequately reducing the amount of TiO_,_.
`
`5
`
`Meanwhile, in case that x > 0.55, the dielectric constant and the quality
`
`factor were much degraded than those ofthe present invention, and most of
`
`all, the sintering characteristic is degraded as the amount of Mg is increased.
`
`Table 3 indicates a composition exhibiting an excellent dielectric property
`
`with a temperature coefflcient of ‘O’ on the basis of Table ‘I and Table 2.
`
`10
`
`Table 3: High frequency dielectric property of a dielectric resonator fabricated
`
`with a composition of (ZnOo_,0M0_30)TiO3 (M=Mg) + O.2TiO2 + (B203, + SiO2-K20
`
`glass)
`
`000013
`
`000013
`
`

`

`wo 01/83395
`
`PCT/KR00/00984
`
`No. B203
`
`SiO2-K20 Sintering Dielectric Quality
`
`Temperature
`
`(wt%) glass
`
`temperat— constant
`
`factor
`
`coefficient
`
`(wt°/o)
`
`ure (°C)
`
`(9,)
`
`(Qxf GHZ)
`
`(rf:ppm/°C)
`
`31
`T
`32
`
`-
`
`0.50
`
`925
`
`16.6
`
`26900
`
`0.25
`
`24.5
`
`65300
`
`716
`L
`-11
`
`33
`
`0.50
`
`.44..
`34
`1.00
`
`35
`
`36
`
`1.50
`
`2.00
`
`”24.9
`
`69700
`
`-6
`
`24.7
`
`74700
`
`-10
`
`_.
`
`24.4
`
`24.2
`
`1 69000
`
`467300
`
`-1
`
`-5
`
`37
`
`-
`
`1.00
`
`925
`
`17.1
`
`" 27200
`
`"-27
`
`24.8
`
`56500
`
`-14
`
`38
`
`0.25
`
`39
`
`0.50
`
`40
`
`1.00
`
`41
`
`1.59
`
`42
`
`2.00
`
`0.25
`44
`__.:__t:j_...
`
`0.50
`45
`.e.___:.:
`
`46
`1.00
`
`47
`1.50
`
`
`48
`
`2.00
`
`“25.0
`
`59200
`
`25.0
`
`59300
`
`-7
`
`-2
`
`24.7
`
`55400
`
`"0
`
`24.5
`
`” 55800
`
`+1
`
`-14
`
`-9
`
`_l
`
`-4
`L__
`
`+5
`
`‘+2
`
`43
`
`-
`
`‘” 2.00
`
`925
`
`18.3
`
`20300
`
`25.1
`
`"" 52200
`
`25.2
`
`52700
`
`25.0
`
`55700
`
`j 25.3
`
`‘ 48100
`
`24.9
`
`1
`
`50800
`
`+14
`
`13
`
`000014
`
`000014
`
`

`

`W0 01,83395
`
`PCT/KR00/00984
`
`SiO2—K2O Sintering Dielectric Quality
`% No. B203
`.
`(wt%) glass
`temperat— constant
`factor
`
`_'_Temperature
`coefficient
`
`(vvt%)
`
`ure (°C)
`
`(2,)
`
`(Qxf GHz)
`
`(rfzppm/°C)
`
`49
`
`-
`
`3.00
`
`900
`
`E)" 0.25
`
`51
`
`0.50
`
`52
`
`1.00
`
`53
`
`1.50
`
`5? 2.00
`
`17.6
`
`21.9
`
`25400
`
`‘_33500
`
`23.8
`
`39100
`
`-24
`
`-20
`
`-10
`
`25.6
`
`25.6
`
`25.5
`
`38400
`
`"+17
`
`74800
`
`+20
`
`42100 _‘ +25
`
`55
`
`-
`
`5.00
`
`900
`
`‘ 19.5
`
`19500
`
`56
`
`0.25
`
`57 0.50
`
`58
`
`1.00
`
`59
`
`1.50
`
`60
`
`2.00
`
`218
`
`27100
`
`228
`
`30700
`
`23.9
`
`31600
`
`-17
`
`-20
`
`-32
`
`-11
`
`250
`
`36800
`
`+24
`
`25.1
`
`37700
`
`+31
`
`In the embodiments 32~60, an excellent dielectric property with a
`
`dielectric constant of more than 24, a quality factor of more than 50000 and a
`
`temperature factor of i 30ppm/°C was obtained from the combination of less
`
`than 2 wt % B203 (or H3BO3) and S102-K20 glass.
`
`Table 4 shows an influence of B203 and H3BO3 additive for the
`
`composition of (Zn0_,0Mg0_30)TiO3 and 0,2TiO2.
`
`
`
`14
`
`000015
`
`000015
`
`

`

`WO 01/33395
`
`PCT/KR00/00984
`
`Table 4: High frequency dielectric property of a dielectric resonator fabricated
`
`with a composition of (ZnO0_,0M0 30)TiO3 (M=Mg) + O.2TiO2 + (B203, or H3BO3)
`
`No. B203
`
`H2BO3
`
`Sintering
`
`Dielectric Quality
`
`Temperature
`
`(vvt%)
`
`(vvt%)
`
`temperat— constant
`
`factor
`
`coefficient
`
`ure (°C)
`
`(8,)
`
`(Qxf GHz)
`
`(rf:ppm/°C)
`
`_6_1——?’*——j9OO
`
`19.3
`
`_‘51200 ‘-31
`
`925
`225
`
`
`84400
`
`62‘"”c)‘.25'—-—_ 900
`
`925
`
`23.6
`
`25.7
`
` 00 22.8
`
`925
`
`'64
`
`1.00
`
`- —'9'00
`
`65
`
`2.00
`
`-
`
`925
`
`900
`
`925
`
`66‘-0 0.25
`
`900
`
`925
`
`?‘‘'-'_"T5?0_” 900
`
`925
`
`50000
`
`86100
`
`44000
`
`77400
`
`46300
`
`78000
`
`25.5
`
`224
`
`25.2
`
`23.1
`
`"“56600
`
`25.8
`
`87600
`
`23.5
`
`25.3
`
`23.6
`
`25.3
`
`52000
`
`84300
`
`46200
`
`81700
`
`-29
`
`-23
`
`-16
`
`-23
`
`-13
`
`-15
`
`+1
`
`0
`
`-1
`
`-16
`
`-15
`
`-6
`
`-7
`
`68
`
`-
`
`0
`
`‘T00 1900
`i 925
`
`"'”2§6—_*53700
`25.2
`79300
`
`"510
`-5
`
`15
`
`000016
`
`000016
`
`

`

`W0 01,83,395
`
`PCT/KR00/00984
`
`69
`
`-
`
`2.00
`
`900
`
`24.5
`
`56600
`
`-12
`
`925
`
`26.1
`
`77200
`
`70
`
`-
`
`5.00
`
`900
`
`16.5
`
`40000
`
`925
`
`25.1
`
`60200
`
`-7
`
`-4
`
`-4
`
`In the embodiments 62~65 and 66~69,
`
`it is noted that the dielectric
`
`constant and the quality factor were higher when H3BO3 were added than
`
`B203, and especially, the stability of the temperature factor according to the
`
`sintering temperature was excellent, which testifies the effect of the present
`
`invention.
`
`In
`
`the present
`
`invention,
`
`a high frequency dielectric ceramics
`
`composition may be constituted by combining a combination of (Zn,_aMg,_bCo,_
`
`CNi,_d)TiO3 and yTiO2 as a main component and one of O~5 wt % B203, O~5
`
`wt % HBBO3, O~5 wt % SiO2—K2O glass, O~5 wt % B203 and SiO2-K20 glass, or
`
`O~5 wt % H3BO3 and SiO2-K20 glass as an additive, which satisfies conditions
`
`of Osas1, Osbs1, Oscsl, Osdsl and OsysO.6.
`
`INDUSTRIAL APPLICABILITY
`
`As so far described, a high frequency dielectric characteristic having an
`
`excellent various temperature compensation varied according to the high
`
`quality factor, the dielectric constant and the stable temperature coefficient and
`
`composition but having a very low sintering temperature compared with the
`
`conventional dielectric composition can be implemented at a low-priced
`
`10
`
`15
`
`
`
`16
`
`000017
`
`000017
`
`

`

`WO 01/83395
`
`PCT/KR00/00984
`
`material such as ZnO, MgO, C00, NiO or TiO2.
`
`In addition, since Ag, Cu or their alloy or Ag/Pd alloy can be used as an
`
`internal electrode, and thus, can be used as various high frequency devices,
`
`i.e., a multilayer chip capacitor, a multilayer chip filter, a multilayer chip
`
`capacitor/inductor composite device and a low-temperature sinterable
`
`substrate, a resonator and a filter or a ceramic antenna.
`
`Especially,
`
`the low-temperature sintered composition obtains a
`
`remarkably high quality factor more than several times that of the conventional
`
`one.
`
`10
`
`In addition, combination of the almost infinite number of compositions
`
`exhibiting the excellent high frequency characteristic can be obtained in the
`
`composition range of the present invention.
`
`
`
`17
`
`000018
`
`000018
`
`

`

`wo 01/33395
`
`PCT/KR00/00984
`
`CLAIMS
`
`1.
`
`A high frequency dielectric ceramics composition constituted by
`
`combining a combination of (Zn,_xMx)TiO3 and yTiO2 as a main component, into
`
`which one of O~5 wt % B203, O~5 wt % H3BO3, O~5 wt °/o SiO2-K20 glass, O~5
`
`wt % B203 and SiO2-K20 glass, or O~5 wt °/o H3BO3 and SiO2—K2O glass is
`
`added as an additive, satisfies conditions of
`
`M is Mg, Co or Ni,
`
`‘x’
`
`is Osxs0.55 in case of Mg and ‘x’
`
`is Osxs1.0 in case of Co, and
`
`10
`
`05x51 .0 in case of Ni, and
`
`OsysO.6.
`
`2.
`
`A high frequency dielectric ceramics composition preparation
`
`method in which material powder of ZnO, MO (in this respect, MO is MgO, CoO
`
`or NiO) and TiO2 is weighed according to a composition range of (Zn,_xMx)TiO3
`
`and yTiO2 (M is one of Mg, Co and Ni, x is OsxsO.55 in case of Mg, x is Osxst
`
`in case of Co, x is 03x31 in case of Ni, and y is OsysO.6), mixed and dried,
`
`the dried powder is calcined at a temperature of 850~950°C,
`
`the calcined powder is mixed with one of O~5 wt % B203, O~5 wt °/o
`
`H3BO3, O~5 wt % SiO2-K20 glass, O~5 wt % B203 and SIOZ-K20 glass, or O~5
`
`15
`
`20
`
`wt % H3BO3 and SiO2-K20 glass as an additive,
`
`the mixed powder is crushed,
`
`the crushed power is shaped,
`
`18
`
`000019
`
`
`
`000019
`
`

`

`WO 01/83395
`
`PCT/KR00/00984
`
`the shaped body is fired at a temperature of 800~925°C, and
`
`(Zn,_,M,)TiO3 is calcined at a temperature corresponding to a region
`
`(region ll) of below a phase dissociation temperature as shown in Figure 1 to
`
`obtain
`
`(Zn,_xMx)TiO3
`
`(M is Mg, Co
`
`or Ni)
`
`of
`
`a
`
`single phase of
`
`rhombohedral/hexagonal crystal.
`
`3.
`
`The method of claim 2, wherein the shaped body is made in a
`
`manner that an aqueous solution adding a PVA binder is sprayed onto the
`
`crushed powder to make a granule, to which a pressure is applied.
`
`4.
`
`The method of claim 3, further comprises a step for maintaining
`
`the shaped body at a temperature of 300~500°C for a predetermined time and
`
`removing the binder.
`
`5.
`
`The method of claim 2, wherein (Zn,_,M,)TiO3 is first calcined, and
`
`the calcined (Zn,_XMx)TiO3 is mixed with one of O~5 wt % B203, O~5 wt % H3BO3,
`
`O~5 wt % SiO2-K20 glass, O~5 \/vt °/o B203 and SiO2-K20 glass, or O~5 wt °/o
`
`H3BO3 and SiO2-K20 glass as an additive, and then fired.
`
`6.
`
`A high frequency dielectric ceramics composition constituted by
`
`combining a combination (Zn,_aMg,_bCo,_cNi,_d)TiO3 and yTiO2 as a main
`
`component, into which one of O~5 wt % B203, O~5 wt °/o H3BO3, O~5 wt °/o SiO2—
`
`KZO glass, O~5 wt % B203 and SiO2—K2O glass, or O~5 wt °/o H3BO3 and SiO2-
`
`10
`
`15
`
`20
`
`
`
`19
`
`000020
`
`000020
`
`

`

`WO 01/83395
`
`PCT/KR00/00984
`
`K20 glass is added as an additive, satisfies conditions of
`
`Osasl, Osbs1, 0:031, Osdsl and
`
`OsysO.6.
`
`7.
`
`Various high frequency devices such as a multilayer chip
`
`capacitor, a multilayer chip filter, a multilayer chip capacitor/inductor composite
`
`device and a module, a low-temperature sintered substrate, a resonator and
`
`a filter or a ceramic antenna, are fabricated by using the dielectric composition
`
`of claim 1.
`
`Ln
`
`10
`
`
`
`20
`
`000021
`
`000021
`
`

`

`W001/83395
`
`PCT/KR00/00984
`
`1/1
`
`O
`5
`9
`2
`
`Z 8D
`
`500 350 900 9501000
`
`Ton-np.(°C)
`
`0.0
`
`0.1
`
`0.2
`
`0.3
`
`0.4
`
`0.5
`
`1 (mole)
`
`000022
`
`13oo
`
`1100
`
`1000
`
`5:00
`
`,. mo
`,
`
`01
`
`0I
`
`- 3 E
`
`8.
`E
`°
`*'
`
`000022
`
`

`

`INTERNATIONAL SEARCH REPORT
`
`international application No.
`PCT/KR00/00984
`
`A.
`
`CLASSIFICATION OF SUBJECT MATTER
`
`IPC7 C04B 35/46, H0lB 3/12
`
`According to International Patent Classification (IPC) or to both national classification and IPC
`FIELDS SEARCHED
`
`Minimun documentation searched (classification system followed by classification symbols)
`IPC7 C04B
`
`Documentation searched other than minimun documentation to the extent that such documents are included in the fileds searched
`
`korean patents and applications for inventions since l975
`korean utility models and applications for utility models since 1975
`
`Electronic data base consulted during the intertnational search (name of data base and, where practicable, search trerms used)
`
`NPS
`
`C. DOCUMENTS CONSIDERED TO BE RELEVANT
`
`Citation ofdocument, with indication, where appropriate, ofthe relevant passages
`
`Relevant to claim No.
`
`A
`
`A
`
`A
`
`A
`
`JP 06612449 A(MARUWA CERAMIC) 21 NOVEMBER 1994
`see the whole document
`
`KR 93—0020437 A( KIM KYENG YONG) 04 OCTOBER 1993
`see the whole document
`
`KR 95-0045810 A(KITECH ) 30 NOVEMBER 1995
`see the whole document
`
`KR 96-0050579 A( KAIST) 31 OCTOBER 1996
`see the whole document
`
`"E"
`
`"L"
`
`E Further documents are listed in the continuation ofBox C.
`Special categories of cited documents:
`*
`"A" document defining the general state ofthe art which is not considered
`to be of particular relevence
`earlier application or patent but published on or after the international
`filing dale
`document which may throw doubts on priority claim(s) or which is
`Cited 10 establish the Publication dale Of Ci1fl1i0I1 0!’ 01116!’
`Special T935011 (3-5 SP9-Clf1"-d)
`"0" document referring to an oral disclosure, use, exhibition or other
`meélfls
`document published prior to the international filing date but later
`than the priority date claimed
`
`"P"
`
`B 309 Patent famll)’ annex-
`"T" later document published afler the international filing date or priority
`date and not in conflict with the application but cited to understand
`the principle or theory underlying the invention
`"X" document of panicular relevence‘, the claimed invention cannot be
`considered novel or cannot be considered to involvean inventive
`step when the document is taken alone
`"Y" document of particular relevence; the claimed invention cannot be
`considered to involve an inventive step when the document is
`combined with one or more other such documents,such combination
`being obvious to a person skilled in the art
`"&" document member ofthe same patent family
`
`Date of the actual completion of the international search
`
`Date of mailing of the international search report
`
`23 JANUARY 2001 (23-01-3001)
`
`29 JANUARY 2001 (29.01.2001)
`
`
`
`Name and mailing address ofthe ISA/KR
`Korean Industrial Property Olfice
`Government Complex—Taejon, Dunsan-dong, So-ku, Taejon
`Metropolitan City 302-701, Republic of Korea
`
`Authorized Officer
`
`HONG, Soon Chil
`
`Facsimile No. g2.42-472.7140
`
`Telephone No,
`
`82-42-481-5560
`
`Form PCT/ISA/210 (second sheet) (July 1998)
`
`000023
`
`000023
`
`