JPH03131545A - Resistor paste and ceramics substrate - Google Patents
Resistor paste and ceramics substrateInfo
- Publication number
- JPH03131545A JPH03131545A JP2170196A JP17019690A JPH03131545A JP H03131545 A JPH03131545 A JP H03131545A JP 2170196 A JP2170196 A JP 2170196A JP 17019690 A JP17019690 A JP 17019690A JP H03131545 A JPH03131545 A JP H03131545A
- Authority
- JP
- Japan
- Prior art keywords
- resistor paste
- resistance value
- powder
- glass powder
- glass
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
- 239000000758 substrate Substances 0.000 title claims description 20
- 239000000919 ceramic Substances 0.000 title claims description 16
- 239000000843 powder Substances 0.000 claims abstract description 34
- 239000011521 glass Substances 0.000 claims abstract description 33
- ZKATWMILCYLAPD-UHFFFAOYSA-N niobium pentoxide Chemical compound O=[Nb](=O)O[Nb](=O)=O ZKATWMILCYLAPD-UHFFFAOYSA-N 0.000 abstract description 18
- 239000012298 atmosphere Substances 0.000 abstract description 9
- 239000000203 mixture Substances 0.000 abstract description 8
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 abstract description 6
- PBCFLUZVCVVTBY-UHFFFAOYSA-N tantalum pentoxide Inorganic materials O=[Ta](=O)O[Ta](=O)=O PBCFLUZVCVVTBY-UHFFFAOYSA-N 0.000 abstract description 6
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 abstract description 4
- FUJCRWPEOMXPAD-UHFFFAOYSA-N Li2O Inorganic materials [Li+].[Li+].[O-2] FUJCRWPEOMXPAD-UHFFFAOYSA-N 0.000 abstract description 3
- 229910052757 nitrogen Inorganic materials 0.000 abstract description 3
- KKCBUQHMOMHUOY-UHFFFAOYSA-N Na2O Inorganic materials [O-2].[Na+].[Na+] KKCBUQHMOMHUOY-UHFFFAOYSA-N 0.000 abstract description 2
- XUCJHNOBJLKZNU-UHFFFAOYSA-M dilithium;hydroxide Chemical compound [Li+].[Li+].[OH-] XUCJHNOBJLKZNU-UHFFFAOYSA-M 0.000 abstract description 2
- XOLBLPGZBRYERU-UHFFFAOYSA-N tin dioxide Chemical compound O=[Sn]=O XOLBLPGZBRYERU-UHFFFAOYSA-N 0.000 abstract 4
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 abstract 2
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 abstract 2
- MCMNRKCIXSYSNV-UHFFFAOYSA-N Zirconium dioxide Chemical compound O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 abstract 2
- 229910052681 coesite Inorganic materials 0.000 abstract 1
- 229910052593 corundum Inorganic materials 0.000 abstract 1
- 229910052906 cristobalite Inorganic materials 0.000 abstract 1
- 238000002156 mixing Methods 0.000 abstract 1
- 239000000377 silicon dioxide Substances 0.000 abstract 1
- 235000012239 silicon dioxide Nutrition 0.000 abstract 1
- 229910052682 stishovite Inorganic materials 0.000 abstract 1
- 229910052905 tridymite Inorganic materials 0.000 abstract 1
- 229910001845 yogo sapphire Inorganic materials 0.000 abstract 1
- 239000004020 conductor Substances 0.000 description 16
- 238000010304 firing Methods 0.000 description 10
- 230000001590 oxidative effect Effects 0.000 description 8
- 239000010949 copper Substances 0.000 description 7
- 239000012299 nitrogen atmosphere Substances 0.000 description 7
- 238000010586 diagram Methods 0.000 description 6
- 230000000694 effects Effects 0.000 description 6
- 239000002245 particle Substances 0.000 description 6
- 238000004519 manufacturing process Methods 0.000 description 5
- 239000010410 layer Substances 0.000 description 4
- 101100348017 Drosophila melanogaster Nazo gene Proteins 0.000 description 3
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 3
- 239000011230 binding agent Substances 0.000 description 3
- 230000007423 decrease Effects 0.000 description 3
- 238000000034 method Methods 0.000 description 3
- 239000001301 oxygen Substances 0.000 description 3
- 229910052760 oxygen Inorganic materials 0.000 description 3
- KDLHZDBZIXYQEI-UHFFFAOYSA-N palladium Substances [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 description 3
- 239000011148 porous material Substances 0.000 description 3
- 239000002904 solvent Substances 0.000 description 3
- WUOACPNHFRMFPN-SECBINFHSA-N (S)-(-)-alpha-terpineol Chemical compound CC1=CC[C@@H](C(C)(C)O)CC1 WUOACPNHFRMFPN-SECBINFHSA-N 0.000 description 2
- 239000001856 Ethyl cellulose Substances 0.000 description 2
- ZZSNKZQZMQGXPY-UHFFFAOYSA-N Ethyl cellulose Chemical compound CCOCC1OC(OC)C(OCC)C(OCC)C1OC1C(O)C(O)C(OC)C(CO)O1 ZZSNKZQZMQGXPY-UHFFFAOYSA-N 0.000 description 2
- OVKDFILSBMEKLT-UHFFFAOYSA-N alpha-Terpineol Natural products CC(=C)C1(O)CCC(C)=CC1 OVKDFILSBMEKLT-UHFFFAOYSA-N 0.000 description 2
- 229940088601 alpha-terpineol Drugs 0.000 description 2
- 238000004040 coloring Methods 0.000 description 2
- 229920001249 ethyl cellulose Polymers 0.000 description 2
- 235000019325 ethyl cellulose Nutrition 0.000 description 2
- 230000004907 flux Effects 0.000 description 2
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 2
- 229920005989 resin Polymers 0.000 description 2
- 239000011347 resin Substances 0.000 description 2
- 238000003860 storage Methods 0.000 description 2
- 229910052715 tantalum Inorganic materials 0.000 description 2
- 230000029305 taxis Effects 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- KZVBBTZJMSWGTK-UHFFFAOYSA-N 1-[2-(2-butoxyethoxy)ethoxy]butane Chemical compound CCCCOCCOCCOCCCC KZVBBTZJMSWGTK-UHFFFAOYSA-N 0.000 description 1
- QTBSBXVTEAMEQO-UHFFFAOYSA-M Acetate Chemical compound CC([O-])=O QTBSBXVTEAMEQO-UHFFFAOYSA-M 0.000 description 1
- 229920000178 Acrylic resin Polymers 0.000 description 1
- 239000004925 Acrylic resin Substances 0.000 description 1
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- KOPBYBDAPCDYFK-UHFFFAOYSA-N Cs2O Inorganic materials [O-2].[Cs+].[Cs+] KOPBYBDAPCDYFK-UHFFFAOYSA-N 0.000 description 1
- 229910019704 Nb2O Inorganic materials 0.000 description 1
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 description 1
- GCPXMJHSNVMWNM-UHFFFAOYSA-N arsenous acid Chemical compound O[As](O)O GCPXMJHSNVMWNM-UHFFFAOYSA-N 0.000 description 1
- 150000001805 chlorine compounds Chemical class 0.000 description 1
- 239000008395 clarifying agent Substances 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 238000004031 devitrification Methods 0.000 description 1
- AKUNKIJLSDQFLS-UHFFFAOYSA-M dicesium;hydroxide Chemical compound [OH-].[Cs+].[Cs+] AKUNKIJLSDQFLS-UHFFFAOYSA-M 0.000 description 1
- 239000002270 dispersing agent Substances 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 239000005038 ethylene vinyl acetate Substances 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
- 150000002222 fluorine compounds Chemical class 0.000 description 1
- 239000002241 glass-ceramic Substances 0.000 description 1
- 239000001023 inorganic pigment Substances 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- 229910044991 metal oxide Inorganic materials 0.000 description 1
- 150000004706 metal oxides Chemical class 0.000 description 1
- 230000005012 migration Effects 0.000 description 1
- 238000013508 migration Methods 0.000 description 1
- 150000002823 nitrates Chemical class 0.000 description 1
- 229910052763 palladium Inorganic materials 0.000 description 1
- 239000000049 pigment Substances 0.000 description 1
- 229910052697 platinum Inorganic materials 0.000 description 1
- 229920001200 poly(ethylene-vinyl acetate) Polymers 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 229910021332 silicide Inorganic materials 0.000 description 1
- FVBUAEGBCNSCDD-UHFFFAOYSA-N silicide(4-) Chemical compound [Si-4] FVBUAEGBCNSCDD-UHFFFAOYSA-N 0.000 description 1
- 229910052709 silver Inorganic materials 0.000 description 1
- 239000004332 silver Substances 0.000 description 1
- 239000002356 single layer Substances 0.000 description 1
- 238000005245 sintering Methods 0.000 description 1
- 150000003467 sulfuric acid derivatives Chemical class 0.000 description 1
- 239000004094 surface-active agent Substances 0.000 description 1
- 238000004017 vitrification Methods 0.000 description 1
Landscapes
- Glass Compositions (AREA)
- Non-Adjustable Resistors (AREA)
Abstract
Description
【発明の詳細な説明】
［産業上の利用分野］
本発明はセラミックス基板に適した抵抗体ペースト及び
それを用いたセラミックス基板に関するものである。DETAILED DESCRIPTION OF THE INVENTION [Field of Industrial Application] The present invention relates to a resistor paste suitable for ceramic substrates and a ceramic substrate using the same.
［従来の技術］
従来混成集積回路における抵抗はセラミックス基板上又
は内部に銀（Ａｇ）又はＡｇ−パラジウム（Ｐｄ）導体
を形成し、その間に抵抗体ペーストを印刷し、空気等の
酸化性雰囲気中で約８５０〜９００℃で焼成し、形成さ
れていた。[Prior Art] Conventionally, a resistor in a hybrid integrated circuit is made by forming a silver (Ag) or Ag-palladium (Pd) conductor on or inside a ceramic substrate, printing a resistor paste between them, and placing the conductor in an oxidizing atmosphere such as air. It was formed by firing at about 850 to 900°C.
その際に使用されていた抵抗体ペーストは主としてＲｕ
Ｏ２とガラスからなっていた。The resistor paste used at that time was mainly Ru.
It consisted of O2 and glass.
しかし最近ではマイグレーション等の信頼性の面からＡ
ｇ又はＡｇ−Ｐｄ導体に代わり、銅（Ｃｕ）導体が使用
されるようになってきている。However, recently, due to reliability issues such as migration,
Copper (Cu) conductors are increasingly being used to replace g or Ag--Pd conductors.
しかしＣｕ導体は窒素等の非酸化性雰囲気中で焼成しな
いと酸化されてしまうため、非酸化性雰囲気で還元され
抵抗を形成しないＲＩＩ０２は使用できない。However, since the Cu conductor will be oxidized unless it is fired in a non-oxidizing atmosphere such as nitrogen, RII02, which is reduced in a non-oxidizing atmosphere and does not form a resistance, cannot be used.
そこで最近、Ｌ ａ Ｂ ｅ粉末とガラス粉末、 ５ｎ
０２ド一プ品とガラス粉末、珪化物とガラス粉末等が提
案されている。Therefore, recently, L a B e powder and glass powder, 5n
02 doped products, glass powder, silicide and glass powder, etc. have been proposed.
しかし上記組み合わせは抵抗値や抵抗値温度係数（ＴＣ
Ｒ）がまだ十分に安定して得られないという欠点がある
。However, the above combinations are limited by resistance value and temperature coefficient of resistance (TC).
There is a drawback that R) cannot yet be obtained in a sufficiently stable manner.
［発明の解決しようとする課題］
本発明は、窒素等の非酸化性雰囲気中で焼成が可能で、
抵抗値、抵抗値温度係数（ＴＣＰ）が安定的に得られる
従来知られていなかった抵抗体ペースト及びセラミック
ス基板を新規に提供することを目的とするものである。[Problems to be solved by the invention] The present invention can be fired in a non-oxidizing atmosphere such as nitrogen,
The object of the present invention is to provide a new resistor paste and ceramic substrate that are hitherto unknown and can stably obtain resistance values and temperature coefficients of resistance (TCP).
［課題を解決するための手段］
本発明は、前述の問題点を解決すべくなされたものであ
り、無機成分が重量％表示で実質的に、ガラス粉末２０
〜７０とＳｎＯ□及び／又はｓｂをドープした５ｎｕ２
粉末３０〜８０からなり、当該ガラス粉末は重量％表示
で実質的に５１０２７〜５０゜Ａ１□０３０〜２０、Ｍ
ｇＯ＋ＣａＯ＋ＳｒＯ１０〜６０． ＭｇＯＯ〜４０、
ＣａＯＯ〜４０． ＳｒＯＯ〜６０． Ｌｉ２Ｏ＋
ＮａｚＯ＋ＫｚＯ＋Ｃｓ、００〜１０． ＰｂＯＯ〜１
０． Ｚｎ００〜２０． Ｚｒ０ｚ＋Ｔｉ０ｚ Ｏ〜１
０． Ｂ２Ｏ３５〜４０． Ｔａ２ｅｓ Ｏ〜６０゜Ｎ
ｂ２０５０〜５０． Ｔａ２０５＋ＮｂｚＯｓ ｏ、ｉ
〜６ｏからなる抵抗体ペースト等を提供するものであ
る。[Means for Solving the Problem] The present invention has been made to solve the above-mentioned problems, and the inorganic component is substantially 20% by weight of glass powder.
~70 and 5nu2 doped with SnO□ and/or sb
Powder 30-80, the glass powder is substantially 51027-50°A1□030-20, M
gO+CaO+SrO10-60. MgOO~40,
CaOO~40. SrOO~60. Li2O+
NazO+KzO+Cs, 00-10. PbOO~1
0. Zn00~20. Zr0z+Ti0z O~1
0. B2O35-40. Ta2es O~60°N
b2050-50. Ta205+NbzOs o,i
6o is provided.
以下、本発明の詳細な説明する。The present invention will be explained in detail below.
本発明の抵抗体ペーストは単層又は多層セラミックス基
板に使用するのに適したものであり、焼成後の固化した
アルミナ基板等のセラミックス基板、あるいはセラミッ
クス基板用のグリーンシート上に印刷等の方法により形
成した後、窒素雰囲気中等の非酸化性雰囲気中で焼成さ
れるものである。尚％は特に記載しない限り、重量％を
意味する。The resistor paste of the present invention is suitable for use in single-layer or multi-layer ceramic substrates, and can be applied to ceramic substrates such as solidified alumina substrates after firing, or by printing or other methods on green sheets for ceramic substrates. After forming, it is fired in a non-oxidizing atmosphere such as a nitrogen atmosphere. Note that % means weight % unless otherwise specified.
本発明の抵抗体ペーストは無機成分が実質的に ガラス粉末 ２０〜７０％ 導電物質粉末 ３０〜８０％ からなり、以下順次これらについて説明する。The resistor paste of the present invention contains substantially no inorganic components. Glass powder 20-70% Conductive material powder 30-80% These are explained below in order.
ガラス粉末は、低温度（例えば９００’Ｃ以下）で充分
に流動性を有し、焼成時に上記導電物質粉末を覆って充
分に濡らし、かつ焼結するＳｉＯ□−Ｂ２０３系ガラス
のものが好ましい。The glass powder is preferably SiO□-B203 glass, which has sufficient fluidity at low temperatures (for example, 900'C or lower) and covers and sufficiently wets the conductive material powder during firing and sinters.
かかるガラス粉末の含有量が２０％より少ないど導電物
質粉末を充分に濡らすことができないため、焼結層に空
孔が多（なり、本発明の抵抗体ペーストを焼成すること
によって得られる抵抗体の強度が弱くなり、又抵抗値の
安定性が低下するので好ましくな（，７０％を越えると
、導電物質粉末間の接着が少なくなり、上記抵抗値が大
きくなりすぎ適当でない。If the content of such glass powder is less than 20%, the conductive material powder cannot be sufficiently wetted, and the sintered layer will have many pores. If it exceeds 70%, the adhesion between the conductive material powders will decrease, and the resistance value will become too large, which is not suitable.
本発明にかかるガラス粉末は上記範囲中２５〜６５％の
範囲が望ましい。The glass powder according to the present invention preferably has a content of 25 to 65% of the above range.
一方導電物質粉末としては、通常市販されているＳｎＯ
□、Ｓｂを通常５ｂｚ０３の酸化物としてドープしたＳ
ｎＯ□が単独又は併用して使用できるが、その理由は、
かかる物質は、導電率が高い、すなわち抵抗率が低い特
性を有するため、導電物質とガラスとの複合体である本
発明にがかる抵抗体の抵抗値を目標に合致させることが
可能であるためである。On the other hand, the conductive material powder is SnO, which is usually commercially available.
□, Sb doped as oxide, usually 5bz03
nO□ can be used alone or in combination, and the reason is that
This is because such a material has a property of high electrical conductivity, that is, low resistivity, and therefore it is possible to match the resistance value of the resistor according to the present invention, which is a composite of a conductive material and glass, to the target. be.
ｓｂをＳｎＯ□にドープしたものは、ドープしないＳｎ
Ｏ□に比較して抵抗値が低（なり、ドープ量が多くなる
と抵抗値が高くなる。本発明にかかる抵抗が１０ ＭΩ
以下のものなら、上記ドープ量は５ｂｚＯａの酸化物換
算で０〜２０％が適正な範囲であり、望ましい範囲は０
．１〜１５％、特に望ましい範囲は１〜１０％である、
また本発明にかがる抵抗がＩＯＭΩ以上ならば、上記ド
ープ量は５ｂ２０ａの酸化物換算で２０％以上のものも
使用できる。sb doped into SnO□, undoped Sn
The resistance value is low (compared to O□), and the resistance value increases as the amount of doping increases.
For the following, the appropriate doping amount is 0 to 20% in terms of 5bzOa oxide, and the desirable range is 0.
．． 1 to 15%, a particularly desirable range is 1 to 10%,
Further, if the resistance according to the present invention is IOMΩ or more, the above-mentioned doping amount can be 20% or more in terms of 5b20a oxide.
本発明にかかるガラスの粒度は、小さすぎると上記抵抗
値が大きくなりすぎ好ましくなく、大きすぎると、ガラ
スを充分に濡らすことができず、焼結層に空孔が多くな
り好ましくない。If the particle size of the glass according to the present invention is too small, the above-mentioned resistance value becomes too large, which is undesirable. If it is too large, the glass cannot be sufficiently wetted, and the sintered layer has many pores, which is not preferable.
平均粒径は０．５〜６μｍが必要な範囲であり、望まし
い範囲は１〜５μｍである。The required average particle diameter is 0.5 to 6 μm, and the desirable range is 1 to 5 μm.
一方、本発明にかかる導電物質粉末の粒度は小さすぎる
と抵抗値が太き（なり過ぎ好ましくな（、大きすぎると
セラミックス基板上で不均一になり、抵抗値のバラツキ
が太き（なるので好ましくない。平均粒径は０．０１〜
５μｍの範囲が必要な範囲であり、望ましい範囲は０．
０５〜３μｍである。On the other hand, if the particle size of the conductive material powder according to the present invention is too small, the resistance value will become large (unpreferably), and if it is too large, it will become uneven on the ceramic substrate and the variation in resistance value will become large (unpreferably). No. Average particle size is 0.01~
The necessary range is 5 μm, and the desirable range is 0.5 μm.
05-3 μm.
本発明にかかるガラス粉末は、無機成分が実質的に
５ｉＯｚ ７〜５０％Ａ１□０３０〜
２０％
ＭｇＯ＋ＣａＯ＋Ｓｒ０ １０〜６０％（Ｍｇ０
０〜４０％、 ＣａＯＯ〜４０％、 ＳｒＯＯ〜６０％
）Ｌｉ２０＋Ｎａ２Ｏ＋に２０＋Ｃ５ｚＯｏ〜ｔｏ％ｐ
ｂｏ ｏ〜１０％Ｚｎ０
０〜２０％
Ｚｒ０ｚ＋Ｔｉ０ｚ ０〜１０％８２０３
５〜４０％
ＴａｚＯｓ＋ＮｂｚＯｓ ０．１〜６０％Ｔａ
ｚＯｓ ０〜６０％Ｎｂ２Ｏ５０〜５
０％
からなり、順次これらについて説明する。The glass powder according to the present invention has an inorganic component of substantially 5iOz 7-50%A1□030-
20% MgO+CaO+Sr0 10-60% (Mg0
0~40%, CaOO~40%, SrOO~60%
) Li20+Na2O+ to 20+C5zOo~to%p
bo o~10%Zn0
0~20% Zr0z+Ti0z 0~10%8203
5~40% TazOs+NbzOs 0.1~60%Ta
zOs 0~60%Nb2O50~5
0%, and these will be explained in turn.
かかる組成において、ＳｉＯ□はガラスのネットワーク
フォーマ−であり、７％より少ないと、軟化点が低くな
りすぎ耐熱性が低下し、再焼成時に変形を生じ易（なる
ので好ましくない。In such a composition, SiO□ is a glass network former, and if it is less than 7%, the softening point becomes too low, the heat resistance decreases, and deformation is likely to occur during re-firing, which is not preferable.
一方、ＳｉＯ□が５０％より多いと、軟化点が高くなり
過ぎ、焼成時にガラスの流動が悪くなり、導電物質粉末
を覆って濡らすことができず、焼結層の空孔が多くなり
すぎ、抵抗の安定性が悪くなるので適当でない。望まし
くは、１０〜４５％の範囲である。On the other hand, when SiO This is not appropriate because the stability of the resistance will deteriorate. Desirably, it is in the range of 10 to 45%.
Ａ１□０３は必須ではないが、含有することにより、耐
湿性の向上に効果がある。２０％を超えるとガラスの軟
化温度が高くなり、焼結性が悪くなり適当でない。望ま
しくは１８％以下である。Although A1□03 is not essential, its inclusion is effective in improving moisture resistance. If it exceeds 20%, the softening temperature of the glass will become high and the sinterability will deteriorate, making it unsuitable. It is preferably 18% or less.
ＭｇＯ＋ＣａＯ＋ＳｒＯはガラス粉末製造時の溶解性を
向上さすため及び熱膨張係数を調整する働きがある。１
０％より少ないと上記の溶解性が充分に向上しないと共
にガラス製造時に失透を生じやす（，６０％を超えると
熱膨張係数が大きくなりすぎ、いずれも適当でない。望
ましくは、１５〜５５％の範囲である。MgO+CaO+SrO functions to improve the solubility during glass powder production and to adjust the coefficient of thermal expansion. 1
If it is less than 0%, the above-mentioned solubility will not be sufficiently improved, and devitrification will easily occur during glass production. is within the range of
また、上記ＭｇＯ＋ＣａＯ＋ＳｒＯの内のＭｇＯ，Ｃａ
Ｏはそれぞれ４０％以上であると、熱膨張係数が大きく
なりすぎ、不適当である。望ましい範囲は０〜３５％で
ある。上記ＭｇＯ＋ＣａＯ＋ＳｒＯの内のＳｒＯは６０
％以上であると熱膨張係数が太き（なりすぎ、不適当で
ある。望ましい範囲は０〜５５％である。Also, MgO, Ca in the above MgO+CaO+SrO
If O is 40% or more, the coefficient of thermal expansion becomes too large, which is inappropriate. A desirable range is 0-35%. SrO in the above MgO+CaO+SrO is 60
% or more, the coefficient of thermal expansion becomes too thick (too large, which is inappropriate).The desirable range is 0 to 55%.
ＬｉｚＯ＋ＮａｚＯ＋に２０＋Ｃｓ２Ｏは必須ではない
が、ガラスの溶解性の向上を図ることができ、又抵抗値
を高くする作用がある。１０％を超えると、熱膨張係数
が太き（なりすぎ、基板とのマツチングが悪くなり、焼
成後厚膜にクラックが入る可能性が大となり、適当でな
い。望ましくは８％以下である。Although 20+Cs2O is not essential to LizO+NazO+, it can improve the solubility of glass and has the effect of increasing the resistance value. If it exceeds 10%, the coefficient of thermal expansion becomes too large (too much), the matching with the substrate becomes poor, and the possibility of cracks appearing in the thick film after firing becomes large, which is not appropriate.The coefficient of thermal expansion is preferably 8% or less.
ＰｂＯは必須ではないが、ガラスのフラックス成分とし
ての効果があり、又抵抗値を高くする作用がある。１０
％を超えると抵抗値が不安定になるため適当でない。望
ましくは５％以下である。Although PbO is not essential, it is effective as a flux component of the glass and also has the effect of increasing the resistance value. 10
% is not suitable because the resistance value becomes unstable. It is preferably 5% or less.
ＺｎＯは必須ではないが、ガラスの溶解性の改善のため
に２０％まで含有させることが可能であり、１５％以下
が望ましい範囲である。Although ZnO is not essential, it can be contained up to 20% to improve the solubility of the glass, with a desirable range of 15% or less.
ＺｒＯ□＋ＴｉＯ□は必須ではないが、添加することに
より、抵抗体の耐湿信頼性を向上さすことができる。添
加量は１０％が可能であるが、望ましくは７％以下であ
る。Although ZrO□+TiO□ is not essential, adding it can improve the moisture resistance reliability of the resistor. The amount added can be 10%, but is preferably 7% or less.
Ｂ２０．はフラックス成分として用いるが、５％より少
ないと軟化点が高くなり、焼結不足となり、焼結層に空
孔が多くなりすぎる。また４０％を超えるとガラスの耐
水性が低下し適当でない。望ましくは７〜３８％の範囲
である。B20. is used as a flux component, but if it is less than 5%, the softening point will be high, resulting in insufficient sintering, and the sintered layer will have too many pores. Moreover, if it exceeds 40%, the water resistance of the glass decreases and is not suitable. It is preferably in the range of 7 to 38%.
ＴａｚＯｓ、 Ｎｂ２Ｏ５は、抵抗値と抵抗値温度係数
（ＴＣＲ）の調整のために使用する。TazOs and Nb2O5 are used to adjust the resistance value and temperature coefficient of resistance (TCR).
Ｔａｘｅｓ、 ＮｂｚＯｓを導入することにより、抵抗
値を高い方向へ動かすことができ、更にＴＣＲを正の方
向へ動かす効果がある。その鼠は、目標抵抗値に合致す
るように決める。By introducing Taxes and NbzOs, it is possible to move the resistance value in a higher direction, and there is also the effect of moving the TCR in a positive direction. The mouse decides to match the target resistance value.
但し、Ｔａｘｅｓは６０％、Ｎｂ２Ｏ，は５０％、Ｔａ
２０５＋ＮｂｚＯｓは６０％を超えるとガラス化が困難
となり、ＴａｚＯｓ＋Ｎｂ２０ｇは０．１以下であると
効果が少ない。Ｔａ２０５の望ましい範囲は０〜５０％
、Ｎｂ２Ｏ５の望ましい範囲は０〜４５％、Ｔａ２０５
＋Ｎｂ２Ｏ５の望ましい範囲は１〜５０％である。However, Taxes is 60%, Nb2O is 50%, Ta
When the content of 205+NbzOs exceeds 60%, vitrification becomes difficult, and when the content of 20g of TazOs+Nb is 0.1 or less, the effect is small. The desirable range of Ta205 is 0-50%
, the desirable range of Nb2O5 is 0-45%, Ta205
The desirable range of +Nb2O5 is 1 to 50%.
Ｔａ２０５． Ｎｂ２Ｏ５，ＴａｚＯｓ＋ＮｂｚＯｓの
必要な範囲、望ましい範囲については、それぞれ第１図
、第２図、第３図に示す。Ta205. The necessary and desirable ranges of Nb2O5 and TazOs+NbzOs are shown in FIGS. 1, 2, and 3, respectively.
第１図はＴａ２ｅｓを単独（ＮｂｚＯｓ：Ｏ）で使用す
る場合のＴａＪｓの量の抵抗値に対する必要な範囲と望
ましい範囲を示す説明図、
第２図はＮｂ、Ｏ５を単独（ＴａｚＯｓ・Ｏ）で使用す
る場合のＮｂ２Ｏ５の量の抵抗値に対する必要な小百四
と望ましい範囲を示す説明図、
第３図はＴａｚＯｓ ＋ ＮｂｚＯｓの量の抵抗値（こ
対する必要な範囲と望ましい範囲を示す説明図、更に第
１〜３図の主な点を以下にまとめる。Figure 1 is an explanatory diagram showing the necessary and desirable ranges for the resistance value of the amount of TaJs when Ta2es is used alone (NbzOs:O), and Figure 2 is an explanatory diagram showing the necessary and desirable ranges for the resistance value of TaJs when Ta2es is used alone (NbzOs:O). Fig. 3 is an explanatory diagram showing the necessary range and desirable range of the resistance value of the amount of TazOs + NbzOs when used. Furthermore, the main points of Figures 1 to 3 are summarized below.
ＴａａＯｓ、Ｎｂ２Ｏ５
をそれぞれ単独で使用する場合の
各抵抗値に対するＴａｚ０５＋
ＮｂＪｓの使用範囲
ＴａｚＯｓとＮｂ２Ｏ５を併用して使用する場合の各抵
抗値に対するＴａ２ｅｓ 、ＮｂｚＯｓの使用範囲以上
記載したガラス粉末の組成の望ましい範囲についてまと
めると以下の通りとなる。Usage range of Taz05+NbJs for each resistance value when TaaOs and Nb2O5 are used alone Usage range of Ta2es and NbzOs for each resistance value when TazOs and Nb2O5 are used together Desirable composition of the glass powder described above The scope can be summarized as follows.
Ｓｉ０□ １０〜４５％Ａｌ２Ｏ３０〜
１８％
ＭｇＯ＋ＣａＯ＋ＳｒＯ１５〜５５％
（Ｍｇ００〜３５％、 Ｃａ００〜３５％、 Ｓｒ００
〜５５％）ＬｉｚＯ＋ＮａｚＯ＋ＫｚＯ＋Ｃ５ｚＯＯ〜
８％ｐｂｏ ｏ〜５％
ＺｎＯ０〜１５％
Ｚｒ０ｚ＋Ｔｉ０ｚ Ｑ〜 ７％
８２０３ ７〜３８％Ｔａｚ
Ｏｓ＋ＮｂｚＯｓ １〜５０％Ｔａ２
０５ ０〜５０％Ｎｂ２Ｏ５Ｏ
〜４５％
本発明の抵抗体ペーストの組成物は、各粉末が上記割合
に混合されているものであり、以下本発明の抵抗体ペー
ストの作製方法とそれを使用した厚膜回路の製造の一例
について説明する。Si0□ 10~45% Al2O30~
18% MgO+CaO+SrO15-55% (Mg00-35%, Ca00-35%, Sr00
~55%) LizO+NazO+KzO+C5zOO~
8%pbo o~5% ZnO0~15% Zr0z+Ti0z Q~7%
8203 7-38%Taz
Os+NbzOs 1~50%Ta2
05 0-50%Nb2O5O
~45% The composition of the resistor paste of the present invention is one in which each powder is mixed in the above ratio, and below is an example of the method for producing the resistor paste of the present invention and the production of a thick film circuit using the same. I will explain about it.
上記本発明の抵抗体ペーストの組成物に有機バインダー
、溶剤からなる有機ビヒクルを添加し、混合し、ペース
ト状とする。この有機バインダーとしては、エチルセル
ロース、アクリル樹脂、エチレン−酢酸ビニル共重合樹
脂、ポリα−メチルスチレン樹脂、溶剤としては、α−
テルピネオール；ブチルカルピトールアセテート；ブチ
ルカルピトール、 ２，２．４−１−リメチルベンクン
ジオール−１，３，−モノイソブチレート；ジエチレン
グリコールジ−ｎ−ブチルエーテル等が通常使用できる
。さらに分散剤として界面活性剤を添加してもよい。An organic vehicle consisting of an organic binder and a solvent is added to the composition of the resistor paste of the present invention and mixed to form a paste. The organic binder includes ethyl cellulose, acrylic resin, ethylene-vinyl acetate copolymer resin, polyα-methylstyrene resin, and the solvent includes α-
Terpineol; butylcarpitol acetate; butylcarpitol, 2,2,4-1-limethylbencunediol-1,3,-monoisobutyrate; diethylene glycol di-n-butyl ether, etc. can be commonly used. Furthermore, a surfactant may be added as a dispersant.
次いで焼成後の固化したアルミナ基板、又はガラスセラ
ミックス基板等のセラミックス基板上に導体を作成する
ために、Ｃｕを主成分とするＣｕペースト等の導体ペー
ストを所定の回路パターンに印刷等の方法で形成、乾燥
後、酸素濃度約２０ｐｐｍ以下の窒素雰囲気等の非酸化
性雰囲気中で８００〜１０００℃程度、５〜３０分程度
で焼成する。この焼成条件の望ましい範囲は８８０〜９
２０℃、７〜１５分である。次いで抵抗を設けるべき所
定の箇所に上記本発明の抵抗体ペーストを印刷した後乾
燥させ、上記窒素雰囲気中、８００〜ｌＯ圓℃程度、５
〜３０分程度で焼成する。この焼成条件の望ましい範囲
は８８０〜９２０°Ｃ，７〜１５分である。Next, in order to create a conductor on the solidified alumina substrate after firing or a ceramic substrate such as a glass-ceramic substrate, a conductor paste such as Cu paste containing Cu as a main component is formed into a predetermined circuit pattern by a method such as printing. After drying, it is fired at about 800 to 1000° C. for about 5 to 30 minutes in a non-oxidizing atmosphere such as a nitrogen atmosphere with an oxygen concentration of about 20 ppm or less. The desirable range of this firing condition is 880 to 9
20°C, 7 to 15 minutes. Next, the resistor paste of the present invention is printed on a predetermined location where a resistor is to be provided, dried, and heated at about 800 to 10 °C in the nitrogen atmosphere at 5°C.
Bake in about 30 minutes. The preferred range of firing conditions is 880-920°C and 7-15 minutes.
多層セラミックス基板−括焼成の場合は、上記Ｃｕペー
ストと本発明の抵抗体ペーストを印刷したセラミックス
基板用等のセラミックスのグノーンシートを熱圧着後積
層し、上記窒素雰囲気等の非酸化性雰囲気中で８００〜
１０００℃程度。In the case of bulk firing of multilayer ceramic substrates, ceramic gnome sheets for ceramic substrates printed with the above-mentioned Cu paste and the resistor paste of the present invention are laminated after thermocompression bonding, and then heated for 800 min in a non-oxidizing atmosphere such as the above-mentioned nitrogen atmosphere. ~
About 1000℃.
数分〜数時間で一括焼成し、多層基板を作成する。Batch firing is performed in a few minutes to several hours to create a multilayer board.
尚本発明の抵抗体ペーストには、着色のために金属酸化
物、耐熱性無機顔料等の着色顔料を０〜５％添加するこ
とができる。Note that 0 to 5% of a coloring pigment such as a metal oxide or a heat-resistant inorganic pigment can be added to the resistor paste of the present invention for coloring.
また、ガラス製造時、清澄剤、溶融促進剤として硝酸塩
、亜ヒ酸、硫酸塩、フッ化物、塩化物等を０〜５％添加
してすることができる。Further, during glass production, 0 to 5% of nitrates, arsenous acid, sulfates, fluorides, chlorides, etc. can be added as clarifying agents and melting accelerators.
［実施例］
本発明にかかるガラス粉末の各原料を酸化物換算で表−
１に示す割合で調合し、これを白金ルツボに入れ、１３
５０〜１５００℃で２〜３時間撹拌しつつ加熱撹拌した
。次いでこれを水砕又はフレーク状とし、更に粉砕装置
により平均粒径０．５〜６μｍになるように粉砕し、ガ
ラス粉末を製造した。次いで導電物質としてＳｎＯ□及
び／又はｓｂを５ｂ２ｏ、の酸化物換算で５％ドープし
たＳｎＯ□の粉末を平均粒径０．０１〜５１ｔｍになる
ように調整した。次いでこれらのガラス粉末と上記導電
物質粉末を表−１に記載の割合で混合し、本発明の抵抗
体ペーストにかかる組成物を得た。[Example] Each raw material of the glass powder according to the present invention is shown in terms of oxides.
Mix the proportions shown in 1, put this in a platinum crucible, and 13
The mixture was heated and stirred at 50 to 1500°C for 2 to 3 hours. Next, this was pulverized into water or flakes, and further pulverized using a pulverizer to an average particle size of 0.5 to 6 μm to produce glass powder. Next, SnO□ powder doped with 5% of SnO□ and/or sb as a conductive material in terms of 5b2o oxide was adjusted to have an average particle size of 0.01 to 51 tm. Next, these glass powders and the above-mentioned conductive material powder were mixed in the proportions shown in Table 1 to obtain a composition for the resistor paste of the present invention.
次いでこれらに有機バインダーとしてエチルセルロース
、溶剤としてα−テルピネオールからなる有機ビヒクル
を添加し、混練し、粘度が３０Ｘ １０’ ｃｐｓのペ
ーストを作成した。次いで固化したアルミナ基板上に本
発明にかかる抵抗の電極としてＣｕペーストを所定の回
路にスクリーン印刷、乾燥し、酸素濃度２０ｐｐｍ以下
の窒素雰囲気中９００℃、１０分で焼成した。Next, an organic vehicle consisting of ethyl cellulose as an organic binder and α-terpineol as a solvent was added and kneaded to prepare a paste having a viscosity of 30×10′ cps. Next, on the solidified alumina substrate, a Cu paste was screen printed as a resistor electrode according to the present invention in a predetermined circuit, dried, and fired at 900° C. for 10 minutes in a nitrogen atmosphere with an oxygen concentration of 20 ppm or less.
次いで抵抗所定箇所に上記抵抗体ペーストを２００メツ
シユスクリーンでスクリーン印刷、乾燥し、酸素濃度２
０ｐｐｍ以下の窒素雰囲気中で９００℃ｌＯ分で焼成し
た。焼成膜厚は約１５μｍであった。Next, the above resistor paste was screen printed on a predetermined location of the resistor using a 200 mesh screen, dried, and the oxygen concentration was reduced to 2.
It was fired at 900° C. for 10 minutes in a nitrogen atmosphere of 0 ppm or less. The fired film thickness was about 15 μm.
このようにしてセラミック基板上に回路を作成した。こ
の回路について、抵抗値、抵抗温度係数（ＴＣＰ）、高
温放置による抵抗値ドリフトを測子した。これらの結果
を表−１に言Ｐ井した。表−１から明らかなように本発
明にがかる抵抗体ペーストは抵抗特性に優れ、厚膜回路
用抵抗体ペーストとして十分使用できる特性を有するこ
とが認められる。In this way, a circuit was created on the ceramic substrate. Regarding this circuit, the resistance value, temperature coefficient of resistance (TCP), and resistance value drift due to high temperature storage were measured. These results are shown in Table 1. As is clear from Table 1, the resistor paste according to the present invention has excellent resistance characteristics and is recognized to have characteristics that can be used sufficiently as a resistor paste for thick film circuits.
比較例として本発明にかかる抵抗体ペースト以外のもの
についても同様の評価を行ったので表−１に記載した。As a comparative example, similar evaluations were conducted on resistor pastes other than the resistor paste according to the present invention, which are listed in Table 1.
なお各特性の測定方法は次の通りである。The method for measuring each characteristic is as follows.
ｉ）抵抗値及び抵抗値温度係数（ＴＣＲ）２５℃、−５
５℃、 ＋１２５℃の抵抗値（Ｒ２５゜Ｒ−ｓｓ ＋
Ｒ＋ｚｓ ）を恒温槽中で抵抗計により測定し、次の式
により算出した。i) Resistance value and temperature coefficient of resistance (TCR) 25°C, -5
Resistance value at 5℃, +125℃ (R25゜R-ss +
R+zs) was measured using a resistance meter in a constant temperature bath, and calculated using the following formula.
ｉｉ）高温放置による抵抗値ドリフト
１５０℃の恒温槽中で１００時間放置し、次の式により
算出した。ii) Resistance value drift due to high temperature storage The resistance value was calculated by the following formula after being left in a constant temperature bath at 150° C. for 100 hours.
上式において Ｒ１００Ｉ’ｌ” １００時間後の抵抗値 Ｒ。In the above formula R100I’l” Resistance value after 100 hours R.
＝抵抗の初期値
［発明の効果］
本発明の抵抗体ペーストは、窒素雰囲気等の非酸化性雰
囲気中で焼成が可能で、安定した信頼性の高い抵抗をセ
ラミックス基板上に形成可能であり、特に高温放置によ
る抵抗値ドリフト特性に優れているという効果も認めら
れる。=Initial value of resistance [Effects of the invention] The resistor paste of the present invention can be fired in a non-oxidizing atmosphere such as a nitrogen atmosphere, and a stable and highly reliable resistor can be formed on a ceramic substrate. In particular, the effect of excellent resistance value drift characteristics when left at high temperatures is also recognized.
第１図： Ｔａ＊Ｏｓを単独（Ｎｂ２０ｇ＝０）で使用
する場合のＴａ１ｌｓの量の抵抗値に対する必要な範囲
と望ましい範囲を示す説明図。
第２図： Ｎｂ２Ｏ５を単独（Ｔａ２０ｓ”０）で使用
する場合のＮｂＪｓの量の抵抗値に対する必要な範囲と
望ましい範囲を示す説明図。
第３図： ＴａＪｓ ＋ ＮｂａＯｓの量の抵抗値に対
する必要な範囲と望ましい範囲を示す説明図。FIG. 1: An explanatory diagram showing the necessary range and desirable range of the amount of Ta1ls with respect to the resistance value when Ta*Os is used alone (Nb20g=0). Figure 2: Explanatory diagram showing the necessary range and desirable range of the resistance value of the amount of NbJs when Nb2O5 is used alone (Ta20s"0). Figure 3: The necessary range of the resistance value of the amount of TaJs + NbaOs Explanatory diagram showing ranges and desirable ranges.
Claims (2)
０〜７０とＳｎＯ＿２及び／又はＳｂをドープしたＳｎ
Ｏ＿２粉末３０〜８０からなり、当該ガラス粉末は重量
％表示で実質的にＳｉＯ＿２７〜５０，Ａｌ＿２Ｏ＿３
０〜２０，ＭｇＯ＋ＣａＯ＋ＳｒＯ１０〜６０，ＭｇＯ
０〜４０，ＣａＯ０〜４０，ＳｒＯ０〜６０，Ｌｉ＿２
Ｏ＋Ｎａ＿２Ｏ＋Ｋ＿２Ｏ＋Ｃｓ＿２Ｏ０〜１０，Ｐｂ
Ｏ０〜１０，ＺｎＯ０〜２０，ＺｒＯ＿２＋ＴｉＯ＿２
０〜１０，Ｂ＿２Ｏ＿３５〜４０，Ｔａ＿２Ｏ＿５０〜
６０，Ｎｂ＿２Ｏ＿５０〜５０，Ｔａ＿２Ｏ＿５＋Ｎｂ
＿２Ｏ＿５０．１〜６０からなる抵抗体ペースト。(1) The inorganic component is substantially 2% by weight of glass powder.
Sn doped with 0-70 and SnO_2 and/or Sb
It consists of O_2 powder 30-80, and the glass powder is substantially SiO_27-50, Al_2O_3 in weight%.
0~20, MgO+CaO+SrO10~60, MgO
0~40, CaO0~40, SrO0~60, Li_2
O+Na_2O+K_2O+Cs_2O0~10,Pb
O0~10, ZnO0~20, ZrO_2+TiO_2
0~10, B_2O_35~40, Ta_2O_50~
60, Nb_2O_50~50, Ta_2O_5+Nb
A resistor paste consisting of _2O_50.1 to 60.
たセラミックス基板。(2) A ceramic substrate fired using the resistor paste described in item 1.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP1-183701 | 1989-07-18 | ||
| JP18370189 | 1989-07-18 |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPH03131545A true JPH03131545A (en) | 1991-06-05 |
Family
ID=16140438
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP2170196A Pending JPH03131545A (en) | 1989-07-18 | 1990-06-29 | Resistor paste and ceramics substrate |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH03131545A (en) |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2006248859A (en) * | 2005-03-11 | 2006-09-21 | Tdk Corp | Conductive paste, electronic component and electronic apparatus |
| JP2008030994A (en) * | 2006-07-28 | 2008-02-14 | Nihon Yamamura Glass Co Ltd | Bismuth-based lead-free powdered glass |
| US7544314B2 (en) | 2004-09-01 | 2009-06-09 | Tdk Corporation | Glass composition for thick film resistor paste, thick film resistor paste, thick-film resistor, and electronic device |
-
1990
- 1990-06-29 JP JP2170196A patent/JPH03131545A/en active Pending
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US7544314B2 (en) | 2004-09-01 | 2009-06-09 | Tdk Corporation | Glass composition for thick film resistor paste, thick film resistor paste, thick-film resistor, and electronic device |
| JP2006248859A (en) * | 2005-03-11 | 2006-09-21 | Tdk Corp | Conductive paste, electronic component and electronic apparatus |
| JP2008030994A (en) * | 2006-07-28 | 2008-02-14 | Nihon Yamamura Glass Co Ltd | Bismuth-based lead-free powdered glass |
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