JPH0660718A - Resistor paste and ceramics board - Google Patents
Resistor paste and ceramics boardInfo
- Publication number
- JPH0660718A JPH0660718A JP4266688A JP26668892A JPH0660718A JP H0660718 A JPH0660718 A JP H0660718A JP 4266688 A JP4266688 A JP 4266688A JP 26668892 A JP26668892 A JP 26668892A JP H0660718 A JPH0660718 A JP H0660718A
- Authority
- JP
- Japan
- Prior art keywords
- resistance
- resistor paste
- glass powder
- value
- tcr
- 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.)
- Withdrawn
Links
Classifications
-
- C—CHEMISTRY; METALLURGY
- C03—GLASS; MINERAL OR SLAG WOOL
- C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
- C03C8/00—Enamels; Glazes; Fusion seal compositions being frit compositions having non-frit additions
- C03C8/14—Glass frit mixtures having non-frit additions, e.g. opacifiers, colorants, mill-additions
- C03C8/18—Glass frit mixtures having non-frit additions, e.g. opacifiers, colorants, mill-additions containing free metals
-
- C—CHEMISTRY; METALLURGY
- C03—GLASS; MINERAL OR SLAG WOOL
- C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
- C03C3/00—Glass compositions
- C03C3/04—Glass compositions containing silica
- C03C3/062—Glass compositions containing silica with less than 40% silica by weight
- C03C3/064—Glass compositions containing silica with less than 40% silica by weight containing boron
-
- C—CHEMISTRY; METALLURGY
- C03—GLASS; MINERAL OR SLAG WOOL
- C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
- C03C3/00—Glass compositions
- C03C3/04—Glass compositions containing silica
- C03C3/062—Glass compositions containing silica with less than 40% silica by weight
- C03C3/064—Glass compositions containing silica with less than 40% silica by weight containing boron
- C03C3/066—Glass compositions containing silica with less than 40% silica by weight containing boron containing zinc
-
- C—CHEMISTRY; METALLURGY
- C03—GLASS; MINERAL OR SLAG WOOL
- C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
- C03C3/00—Glass compositions
- C03C3/04—Glass compositions containing silica
- C03C3/076—Glass compositions containing silica with 40% to 90% silica, by weight
- C03C3/097—Glass compositions containing silica with 40% to 90% silica, by weight containing phosphorus, niobium or tantalum
-
- C—CHEMISTRY; METALLURGY
- C03—GLASS; MINERAL OR SLAG WOOL
- C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
- C03C8/00—Enamels; Glazes; Fusion seal compositions being frit compositions having non-frit additions
- C03C8/02—Frit compositions, i.e. in a powdered or comminuted form
- C03C8/04—Frit compositions, i.e. in a powdered or comminuted form containing zinc
-
- C—CHEMISTRY; METALLURGY
- C03—GLASS; MINERAL OR SLAG WOOL
- C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
- C03C8/00—Enamels; Glazes; Fusion seal compositions being frit compositions having non-frit additions
- C03C8/14—Glass frit mixtures having non-frit additions, e.g. opacifiers, colorants, mill-additions
Abstract
Description
【０００１】[0001]
【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。BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a resistor paste suitable for a ceramic substrate and a ceramic substrate using the same.
【０００２】[0002]
【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Ag又はAg−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。その際
に使用されていた抵抗体ペーストは主としてRuO2とガラ
スからなっていた。2. Description of the Related Art The resistance in a conventional hybrid integrated circuit is such that an Ag or Ag-Pd conductor is formed on or inside a ceramic substrate, a resistor paste is printed between them, and the temperature is about 850 to 900 ° C. in an oxidizing atmosphere such as air. It was formed by firing at. The resistor paste used at that time consisted mainly of RuO 2 and glass.
【０００３】最近ではマイグレーション等の信頼性の面
からAg又はAg−Pd導体に代わり、Cu導体が使用されるよ
うになってきている。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RuO2は使用できな
い。Recently, Cu conductors have come to be used in place of Ag or Ag-Pd conductors in terms of reliability such as migration. However, since the Cu conductor is oxidized unless it is fired in a non-oxidizing atmosphere such as nitrogen, it is not possible to use RuO 2 that is reduced in a non-oxidizing atmosphere and does not form resistance.
【０００４】そこで最近、LaB6粉末とガラス粉末、SnO2
ドープ品とガラス粉末、珪化物とガラス粉末等が提案さ
れている。しかし上記組み合わせは抵抗値や抵抗値温度
係数（ＴＣＲ）がまだ充分に安定して得られないという
欠点がある。Therefore, recently, LaB 6 powder and glass powder, SnO 2
Doped products and glass powders, silicides and glass powders, etc. have been proposed. However, the above combination has a drawback that the resistance value and the temperature coefficient of resistance (TCR) are not yet sufficiently stable.
【０００５】[0005]
【発明が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、ＴＣＲ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。DISCLOSURE OF THE INVENTION The present invention provides a resistor paste and a ceramic substrate which have not hitherto been known and which can be fired in a non-oxidizing atmosphere such as nitrogen and stably obtain a resistance value and TCR. It is intended to be newly provided.
【０００６】[0006]
【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30〜99.5と金属二硼化物粉末
0.5 〜70からなり、該ガラス粉末の組成中にTa2O5, Nb2
O5のうち少なくとも一種を含有し、更にFe2O3,CuO, Ni
O, CoO, MnO, MoO3, WO3, Cr2O3, Bi2O3, CeO2, Sb2O3,
In2O3, SnO2,V2O5 のうち少なくとも一種を含有してな
ることを特徴とする抵抗体ペースト等を提供する。SUMMARY OF THE INVENTION The present invention has been made to solve the above-mentioned problems, in which the inorganic component is substantially expressed in weight% and glass powder 30 to 99.5 and metal diboride powder are contained.
0.5 to 70, and the composition of the glass powder contains Ta 2 O 5 and Nb 2
Contains at least one of O 5 , and further contains Fe 2 O 3 , CuO, Ni
O, CoO, MnO, MoO 3 , WO 3 , Cr 2 O 3 , Bi 2 O 3 , CeO 2 , Sb 2 O 3 ,
Provided is a resistor paste containing at least one of In 2 O 3 , SnO 2 , and V 2 O 5 .
【０００７】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。なお％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 a single-layer or multi-layer ceramic substrate, such as printing on a ceramic substrate such as a solidified alumina substrate after firing, or a green sheet for a ceramic substrate. After being formed by the method (1), it is fired in a non-oxidizing atmosphere such as a nitrogen atmosphere. Note that% means% by weight unless otherwise specified.
【０００８】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 30 〜99.5％ 金属二硼化物粉末 0.5 〜70 ％ からなり、以下順次これらについて説明する。In the resistor paste of the present invention, the inorganic component is substantially composed of 30 to 99.5% of glass powder and 0.5 to 70% of metal diboride powder, which will be sequentially described below.
【０００９】ガラス粉末は、低温度（例えば 900℃以
下）で充分に流動性を有し、焼成時に上記金属二硼化物
粉末を覆って充分に濡らし、かつ焼結するSiO2−B2O3系
ガラスのものが好ましい。The glass powder has a sufficient fluidity at a low temperature (for example, 900 ° C. or lower), is covered with the metal diboride powder at the time of firing, is sufficiently wet, and is sintered. SiO 2 -B 2 O 3 Glass based glass is preferable.
【００１０】かかるガラス粉末の含有量が30％より少な
いと金属二硼化物粉末を充分に濡らすことができないた
め、焼結層に空孔が多くなり、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、また抵抗値の安定性が低下するので好ましくなく、
99.5％を超えると、金属二硼化物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。本発明
にかかるガラス粉末は上記範囲中40〜98％の範囲が望ま
しい。When the content of the glass powder is less than 30%, the metal diboride powder cannot be sufficiently wetted, so that the sintered layer has many pores, and by firing the resistor paste of the present invention, The strength of the resulting resistor becomes weaker, and the stability of the resistance value decreases, which is not preferable,
If it exceeds 99.5%, the adhesion between metal diboride powders decreases, and the above resistance value becomes too large, which is not suitable. The glass powder according to the present invention is preferably in the range of 40 to 98% in the above range.
【００１１】金属二硼化物は導電性機能を有し、金属二
硼化物のうちで特に望ましいのはTi、Zr、Al及びNbの金
属二硼化物で、最も望ましくはZrB2である。The metal diboride has a conductive function, and among the metal diborides, particularly preferable are metal diborides of Ti, Zr, Al and Nb, and most preferably ZrB 2 .
【００１２】本発明にかかるガラス粉末の粒度は、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
きすぎると金属二硼化物粉末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。平均粒径は
0.5〜6 μｍが望ましい範囲であり、特に望ましい範囲
は 1〜5 μｍである。If the particle size of the glass powder according to the present invention is too small, the above resistance value becomes too large, which is not preferable. If it is too large, the metal diboride powder cannot be sufficiently wetted and the sintered layer has many pores. It is not preferable. The average particle size is
A preferable range is 0.5 to 6 μm, and a particularly preferable range is 1 to 5 μm.
【００１３】一方、本発明にかかる金属二硼化物粉末の
粒度は、小さすぎると抵抗値が大きくなりすぎ好ましく
なく、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大きくなるので好ましくない。平均
粒径は0.01〜5 μｍの範囲が望ましい範囲であり、特に
望ましい範囲は0.05〜3 μｍである。On the other hand, if the particle size of the metal diboride powder according to the present invention is too small, the resistance value becomes too large, which is not preferable, and if it is too large, it becomes non-uniform on the ceramic substrate and the dispersion of the resistance value becomes large, which is preferable. Absent. The average particle size is preferably in the range of 0.01 to 5 μm, and particularly preferably in the range of 0.05 to 3 μm.
【００１４】本発明にかかるガラス粉末の役割として金
属二硼化物粉末を良好に濡らしかつ基板（アルミナ等）
との密着に優れている必要がある。また窒素雰囲気中の
焼成による還元等の変化が起こりにくい等の理由によ
り、硼珪酸系のものが望ましく、以下のものが特に望ま
しい。The role of the glass powder according to the present invention is to wet the metal diboride powder well and to form the substrate (alumina or the like).
It must have good adhesion with. Further, borosilicates are preferable, and the followings are particularly preferable, because changes such as reduction due to firing in a nitrogen atmosphere are unlikely to occur.
【００１５】本発明にかかるガラス粉末は、無機成分が
実質的に SiO2 7〜60％ Al2O3 0〜30％ MgO+CaO+SrO+BaO 10〜60％ (MgO 0〜40％，CaO 0 〜40％，SrO 0 〜60％, BaO 0 〜
60％) Li2O+Na2O+K2O+Cs2O 0〜10％ PbO 0〜10％ ZnO 0〜20％ ZrO2+TiO2 0〜10％ B2O3 5〜40％ Ta2O5+Nb2O5 0.1〜60％ (Ta2O5 0〜60％, Nb2O5 0 〜50％) 金属酸化物（Fe2O3+CuO+NiO+CoO+MnO+MoO3+WO3+Cr2O3+B
i2O3+CeO2+Sb2O3+In2O3+SnO2+V2O5 ） 0.1〜20％ (Fe2O3 0〜20％, CuO 0 〜20％, NiO 0 〜20％, CoO 0
〜20％, MnO 0 〜20％, MoO3 0〜20％, WO3 0 〜20％,
Cr2O3 0 〜20％, Bi2O3 0 〜20％, CeO2 0〜20％, Sb2O
3 0 〜20％, In2O3 0 〜20％, SnO2 0〜20％, V2O5 0〜
20％) からなり、順次これらについて説明する。In the glass powder according to the present invention, the inorganic component is substantially SiO 2 7-60% Al 2 O 3 0-30% MgO + CaO + SrO + BaO 10-60% (MgO 0-40%, CaO 0-40%, SrO 0-60%, BaO 0-
60%) Li 2 O + Na 2 O + K 2 O + Cs 2 O 0-10% PbO 0-10% ZnO 0-20% ZrO 2 + TiO 20 0-10% B 2 O 3 5-40% Ta 2 O 5 + Nb 2 O 5 0.1~60% (Ta 2 O 5 0~60%, Nb 2 O 5 0 ~50%) metal oxide (Fe 2 O 3 + CuO + NiO + CoO + MnO + MoO 3 + WO 3 + Cr 2 O 3 + B
i 2 O 3 + CeO 2 + Sb 2 O 3 + In 2 O 3 + SnO 2 + V 2 O 5 ) 0.1 to 20% (Fe 2 O 3 0 to 20%, CuO 0 to 20%, NiO 0 to 20 %, CoO 0
~ 20%, MnO 0 ~ 20%, MoO 30 ~ 20%, WO 30 ~ 20%,
Cr 2 O 3 0 ~20%, Bi 2 O 3 0 ~20%, CeO 2 0~20%, Sb 2 O
3 0 ~20%, In 2 O 3 0 ~20%, SnO 2 0~20%, V 2 O 5 0~
20%) and will be explained in order.
【００１６】かかる組成において、SiO2はガラスのネッ
トワークフォーマーであり、7 ％未満であると軟化点が
低くなりすぎ耐熱性が低下し、再焼成時に変形を生じや
すくなるので好ましくない。一方、SiO2が60％を超える
と、軟化点が高くなりすぎ、焼成時にガラスの流動が悪
くなり、金属二硼化物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。In such a composition, SiO 2 is a glass network former, and if it is less than 7%, the softening point becomes too low, the heat resistance is lowered, and deformation is likely to occur during re-baking, which is not preferable. On the other hand, when the SiO 2 content exceeds 60%, the softening point becomes too high, the flow of the glass deteriorates during firing, the metal diboride powder cannot be covered and wetted, and the voids in the sintered layer increase. It is not suitable because the stability of resistance becomes worse. Desirably, it is in the range of 10 to 45%.
【００１７】Al2O3 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。30％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。Al 2 O 3 is not essential, but the inclusion of Al 2 O 3 is effective in improving the moisture resistance. If it exceeds 30%, the softening temperature of the glass becomes high and the sinterability deteriorates, which is not suitable. It is preferably 18% or less.
【００１８】MgO+CaO+SrO+BaO はMgO 等の各物質の重量
和を表し、各物質が単独併用で使用できることを意味す
る。この作用は、ガラス粉末製造時の溶解性を向上させ
るため及び熱膨張係数を調整する働きがある。10％未満
である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く、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 + BaO represents the weight sum of each substance such as MgO and means that each substance can be used alone or in combination. This action has the function of improving the solubility in the production of glass powder and adjusting the coefficient of thermal expansion. When it is less than 10%, the above-mentioned solubility is not sufficiently improved and devitrification is likely to occur during glass production, and when it exceeds 60%, the coefficient of thermal expansion becomes too large, and neither is suitable. Desirably,
It is in the range of 15-55%.
【００１９】また、上記 MgO+CaO+SrO+BaOのうちの Mg
O, CaO はそれぞれ40％を超え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+BaOの内のSrO は60％を超えると
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 〜55％である。Of the above MgO + CaO + SrO + BaO, Mg
O and CaO are not suitable because the coefficient of thermal expansion becomes too large when they exceed 40%. The preferred range is 0-35%. Of the above MgO + CaO + SrO + BaO, if the SrO content exceeds 60%, the coefficient of thermal expansion becomes too large and is inappropriate. The preferred range is 0-55%.
【００２０】Li2O+Na2O+K2O+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、また抵抗値を高
くする作用がある。10％を超えると熱膨張係数が大きく
なりすぎ、基板とのマッチングが悪くなり、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。Li 2 O + Na 2 O + K 2 O + Cs 2 O is not essential, but it has the effect of improving the solubility of the glass and increasing the resistance value. If it exceeds 10%, the coefficient of thermal expansion becomes too large, the matching with the substrate becomes poor, and the possibility of cracking in the thick film after firing is not appropriate. Desirably 8% or less.
【００２１】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、また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 has an effect as a glass flux component and also has an effect of increasing the resistance value. If it exceeds 10%, the resistance value becomes unstable, which is not suitable. It is preferably 5% or less.
【００２２】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。ZnO is not essential, but can be contained up to 20% to improve the solubility of the glass.
% Or less is a desirable range.
【００２３】ZrO2+TiO2 は必須ではないが、添加によ
り、抵抗体の耐湿信頼性を向上させることができる。添
加量は10％が可能であるが、望ましくは 7％以下であ
る。ZrO 2 + TiO 2 is not essential, but the addition can improve the humidity resistance reliability of the resistor. The addition amount can be 10%, but is preferably 7% or less.
【００２４】B2O3はフラックス成分として用いるが、5
％未満である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。B 2 O 3 is used as a flux component, but 5
If it is less than%, the softening point becomes high, the sintering becomes insufficient, and the sintered layer has too many pores. On the other hand, if it exceeds 40%, the water resistance of the glass decreases, which is not suitable. It is preferably in the range of 7 to 38%.
【００２５】Ta2O5 及びNb2O5 の少なくとも一種は必須
成分であり、抵抗値とＴＣＲの調整のために使用する。
Ta2O5,Nb2O5 を導入することにより、より抵抗値の低い
ものが可能となり、また高抵抗値でのＴＣＲを正の方向
に動かし、さらに高抵抗値での抵抗値バラツキを小さく
する効果がある。その量は、目標抵抗値に合致するよう
に決める。At least one of Ta 2 O 5 and Nb 2 O 5 is an essential component and is used for adjusting the resistance value and TCR.
By introducing Ta 2 O 5 and Nb 2 O 5 , it becomes possible to have a lower resistance value, and the TCR at high resistance values can be moved in the positive direction to further reduce the variation in resistance values at high resistance values. Has the effect of The amount is determined so as to match the target resistance value.
【００２６】但し、Ta2O5 は60％、Nb2O5 は50％、Ta2O
5+Nb2O5 は60％を超えるとガラス化が困難となり、Ta2O
5+Nb2O5 は 0.1％未満であると効果が少ない。Ta2O5 の
望ましい範囲は 0〜50％、Nb2O5 の望ましい範囲は 0〜
45％、Ta2O5+Nb2O5 の望ましい範囲は 1〜50％である。However, Ta 2 O 5 is 60%, Nb 2 O 5 is 50%, Ta 2 O
If 5 + Nb 2 O 5 exceeds 60%, vitrification becomes difficult, and Ta 2 O 5
5 + Nb 2 O 5 is less effective if less than 0.1%. The desirable range of Ta 2 O 5 is 0 to 50%, and the desirable range of Nb 2 O 5 is 0 to 50%.
The desirable range of 45% and Ta 2 O 5 + Nb 2 O 5 is 1 to 50%.
【００２７】添加する金属酸化物については、Fe2O3, C
uO, NiO, CoO, MnO, MoO3, WO3, Cr2O3, Bi2O3, CeO2,
Sb2O3, In2O3, SnO2, V2O5等が単独又は併用して使用で
きる。従って、少なくとも一種は必須成分である。抵抗
値の調整、ＴＣＲの調整、及びレーザートリミング性の
改良の機能を有する。Regarding the metal oxide to be added, Fe 2 O 3 , C
uO, NiO, CoO, MnO, MoO 3, WO 3, Cr 2 O 3, Bi 2 O 3, CeO 2,
Sb 2 O 3 , In 2 O 3 , SnO 2 , V 2 O 5 and the like can be used alone or in combination. Therefore, at least one is an essential component. It has functions of adjusting resistance, adjusting TCR, and improving laser trimming property.
【００２８】これらの金属酸化物中の中で望ましいもの
はCuO, NiO, MoO3, MnO であり、特に望ましいものはCu
O, NiOである。以下にそれぞれの機能を列挙する。Fe2O
3 は抵抗値を上げ、ＴＣＲを負の方向へ動かす。CuO は
抵抗値を下げ、ＴＣＲを正の方向へ動かす。NiO は抵抗
値を下げ、ＴＣＲを正の方向へ動かす。CoO は抵抗値を
下げ、ＴＣＲを正の方向へ動かす。MnO は抵抗値を下
げ、ＴＣＲを正の方向へ動かす。MoO3は抵抗値を下げ、
ＴＣＲを正の方向へ動かす。WO3 は抵抗値を上げ、ＴＣ
Ｒを負の方向へ動かす。Among these metal oxides, CuO, NiO, MoO 3 and MnO are preferable, and Cu is particularly preferable.
O and NiO. Each function is listed below. Fe 2 O
3 increases resistance and moves TCR in the negative direction. CuO lowers the resistance and moves the TCR in the positive direction. NiO lowers the resistance and moves the TCR in the positive direction. CoO lowers the resistance and moves the TCR in the positive direction. MnO lowers resistance and moves TCR in the positive direction. MoO 3 lowers resistance,
Move the TCR in the positive direction. WO 3 increases resistance, TC
Move R in the negative direction.
【００２９】Cr2O3 は抵抗値を上げ、ＴＣＲを負の方向
へ動かす。Bi2O3 は抵抗値を下げ、ＴＣＲを負の方向へ
動かす。CeO2は抵抗値を下げ、ＴＣＲを負の方向へ動か
す。Sb2O3 は抵抗値を下げ、ＴＣＲを正の方向へ動か
す。In2O3 は抵抗値を下げ、ＴＣＲを負の方向へ動か
す。SnO2は抵抗値を下げ、ＴＣＲを負の方向へ動かす。
V2O5は抵抗値を上げ、ＴＣＲを正の方向へ動かす。以上
の効果がある。更に、抵抗値の調整のためにレーザート
リミングを行う際のカット性を向上させることができ
る。Cr 2 O 3 raises the resistance value and moves the TCR in the negative direction. Bi 2 O 3 lowers the resistance and moves the TCR in the negative direction. CeO 2 lowers the resistance and moves the TCR in the negative direction. Sb 2 O 3 lowers the resistance and moves the TCR in the positive direction. In 2 O 3 lowers the resistance and moves the TCR in the negative direction. SnO 2 lowers the resistance and moves the TCR in the negative direction.
V 2 O 5 raises the resistance and moves the TCR in the positive direction. There are the above effects. Further, it is possible to improve the cutting property when performing laser trimming for adjusting the resistance value.
【００３０】ガラス組成率の量は、目標抵抗、ＴＣＲ、
レーザートリミング性に合致させる量を含有するが、上
記金属酸化物の総量は０．１％未満であると効果がな
く、２０％を超えると高温放置試験による抵抗値ドリフ
トが大きくなり好ましくない。望ましくは１〜１５％の
範囲である。The amount of the glass composition ratio depends on the target resistance, TCR,
Although the amount of the metal oxide contained is in conformity with the laser trimming property, if the total amount of the above metal oxides is less than 0.1%, there is no effect, and if it exceeds 20%, the resistance value drift due to the high temperature storage test becomes large, which is not preferable. It is preferably in the range of 1 to 15%.
【００３１】また、上記金属酸化物のなかで、抵抗値、
ＴＣＲを調整し、抵抗値のドリフトを安定させる効果に
優れているのはCuO, NiO, MoO3, MnO であり、このうち
CuO,NiO が特に優れている。Among the above metal oxides, the resistance value,
CuO, NiO, MoO 3 and MnO have the excellent effect of adjusting the TCR and stabilizing the drift of the resistance value.
CuO and NiO are particularly excellent.
【００３２】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。 SiO2 10〜45％ Al2O3 0〜18％ MgO+CaO+SrO+BaO 15〜55％ (MgO 0 〜35％，CaO 0 〜35％，SrO 0 〜55％，BaO 0
〜55％） Li2O+Na2O+K2O+Cs2O 0〜 8％ PbO 0〜 5％ ZnO 0〜15％ ZrO2+TiO2 0〜 7％ B2O3 7〜38％ Ta2O5+Nb2O5 1〜50％ (Ta2O5 0〜50％，Nb2O5 0 〜45％) 金属酸化物（Fe2O3+CuO+NiO+CoO+MnO+MoO3+WO3+Cr2O3+B
i2O3+CeO2+Sb2O3+In2O3+SnO2+V2O5 ） 1〜15％ (Fe2O3 0〜15％, CuO 0 〜15％, NiO 0 〜15％, CoO 0
〜15％, MnO 0 〜15％, MoO3 0〜15％, WO3 0 〜15％,
Cr2O3 0 〜15％, Bi2O3 0 〜15％, CeO2 0〜15％, Sb2O
3 0 〜15％, In2O3 0 〜15％, SnO2 0〜15％, V2O5 0〜
15％)The desirable ranges of the composition of the glass powder described above are summarized as follows. SiO 2 10-45% Al 2 O 3 0-18% MgO + CaO + SrO + BaO 15-55% (MgO 0-35%, CaO 0-35%, SrO 0-55%, BaO 0
~55%) Li 2 O + Na 2 O + K 2 O + Cs 2 O 0~ 8% PbO 0~ 0~15% 5% ZnO ZrO 2 + TiO 2 0~ 7% B 2 O 3 7~38% Ta 2 O 5 + Nb 2 O 5 1~50% (Ta 2 O 5 0~50%, Nb 2 O 5 0 ~45%) metal oxide (Fe 2 O 3 + CuO + NiO + CoO + MnO + MoO 3 + WO 3 + Cr 2 O 3 + B
i 2 O 3 + CeO 2 + Sb 2 O 3 + In 2 O 3 + SnO 2 + V 2 O 5 ) 1 to 15% (Fe 2 O 3 0 to 15%, CuO 0 to 15%, NiO 0 to 15 %, CoO 0
~ 15%, MnO 0 ~ 15%, MoO 3 ~ 15%, WO 30 ~ 15%,
Cr 2 O 3 0 ~ 15%, Bi 2 O 3 0 ~ 15%, CeO 2 0 ~ 15%, Sb 2 O
3 0 ~15%, In 2 O 3 0 ~15%, SnO 2 0~15%, V 2 O 5 0~
(15%)
【００３３】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。The composition of the resistor paste of the present invention is one in which the powders are mixed in the above proportions. The following 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. Will be described.
【００３４】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
練し、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；ブチルカルビトールア
セテート；ブチルカルビトール；2,2,4-トリメチルペン
タンジオール-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 composed of an organic binder and a solvent is added to the composition of the resistor paste of the present invention, and the mixture is kneaded to form a paste. As the organic binder, ethyl cellulose, acrylic resin, ethylene-vinyl acetate copolymer resin, poly α-methylstyrene resin, and as the solvent, α-terpineol; butyl carbitol acetate; butyl carbitol; 2,2,4-trimethyl Pentanediol-1,3-monoisobutyrate; diethylene glycol di-n-butyl ether and the like can usually be used. Further, a surfactant may be added as a dispersant.
【００３５】次いで焼成後の固化したアルミナ基板、ま
た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ペーストを所定の回路に印
刷，乾燥後、酸素濃度 20ppm以下の窒素雰囲気中で 800
〜1000℃、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 ℃、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 〜1000
℃、5 〜30分で焼成する。この焼成条件の望ましい範囲
は 880〜920 ℃、7 〜15分である。Then, in order to prepare a conductor on a solidified alumina substrate after firing or a ceramic substrate such as a glass ceramic substrate, a Cu paste is printed on a predetermined circuit and dried, and then in a nitrogen atmosphere having an oxygen concentration of 20 ppm or less. 800
Bake at ~ 1000 ° C for about 5 to 30 minutes. The preferable range of the firing conditions is 880 to 920 ° C and 7 to 15 minutes. Next, after printing the resistor paste of the present invention at a predetermined location where a resistor is to be provided, the resistor paste is dried and then 800 to 1000 in the nitrogen atmosphere.
Bake at 5 ℃ for 30 minutes. The preferable range of the firing conditions is 880 to 920 ° C and 7 to 15 minutes.
【００３６】多層セラミックス基板一括焼成の場合は、
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リーンシートを
熱圧着後積層し、上記窒素雰囲気中で 800〜1000℃、数
分〜数時間で一括焼成し、多層基板を作成する。In the case of simultaneous firing of multilayer ceramic substrates,
The Cu paste and the green paste of the ceramics for the ceramics substrate on which the resistor paste of the present invention is printed are thermocompression-bonded and laminated, and then collectively baked in the nitrogen atmosphere at 800 to 1000 ° C. for several minutes to several hours to form a multilayer. Create the board.
【００３７】なお、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。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 ％添加することができる。In the resistor paste of the present invention, a coloring pigment such as a metal oxide or a heat resistant inorganic pigment is used for coloring.
~ 5% can be added. Further, during the production of glass, 0-5% of nitrates, arsenous acid, sulfates, fluorides, chlorides and the like can be added as fining agents and melting accelerators.
【００３８】[0038]
【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、1350〜1500℃で 2〜3 時間撹拌しつつ加熱した。次
いでこれを水砕またはフレーク状とし、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。次いで金属二硼化物として表１に示す
ZrB2, TiB2, AlB2，NbB2を平均粒径0.01〜５μｍ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金属
二硼化物粉末を表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。EXAMPLES Each raw material of the glass powder according to the present invention was prepared in a ratio shown in Table 1 in terms of oxide, put in a platinum crucible, and heated at 1350 to 1500 ° C. for 2 to 3 hours while stirring. Next, this was crushed into water or flakes, and further crushed by a crushing device so as to have an average particle size of 0.5 to 6 μm, to produce a glass powder. Then shown in Table 1 as metal diboride
ZrB 2 , TiB 2 , AlB 2 and NbB 2 were adjusted to have an average particle size of 0.01 to 5 μm. Next, these glass powders and the above metal diboride powders were mixed in the proportions shown in Table 1 to obtain a composition for the resistor paste of the present invention.
【００３９】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30×104 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。Then, an organic vehicle consisting of ethyl cellulose as an organic binder and α-terpineol as a solvent was added to these and kneaded to prepare a paste having a viscosity of 30 × 10 4 cps. Then, on the solidified alumina substrate, a Cu paste was screen-printed on a predetermined circuit as an electrode of the resistor according to the present invention, dried, and baked at 900 ° C. for 10 minutes in a nitrogen atmosphere having an oxygen concentration of 20 ppm or less.
【００４０】次いで抵抗所定箇所に上記抵抗体ペースト
を200 メッシュスクリーンでスクリーン印刷、乾燥し、
酸素濃度 20ppm以下の窒素雰囲気中で900 ℃、10分で焼
成した。焼成膜厚は約15μｍであった。Next, the resistor paste is screen-printed on a predetermined portion of the resistor with a 200-mesh screen and dried,
Baking was performed at 900 ° C. for 10 minutes in a nitrogen atmosphere having an oxygen concentration of 20 ppm or less. The baked film thickness was about 15 μm.
【００４１】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、ＴＣＲ、高温放
置による抵抗値ドリフトを測定した。これらの結果を表
１〜表４（サンプル番号１〜１３）に記載した。表１、
表３には、ガラス粉末の組成（金属酸化物を除く）等を
示し、表２、表４には、ガラス粉末中の金属酸化物及び
焼成後の抵抗体の特性等を示す。なお、表２、表４中の
ＸＸは、Fe2O3+CoO+WO3+Cr2O3+Bi2O3+CeO2+Sb2O3+In2O3
+SnO2+V2O5である。これらの表から明らかなように本発
明にか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充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 formed on the ceramic substrate. With respect to this circuit, resistance value, TCR, and resistance value drift due to high temperature storage were measured. The results are shown in Tables 1 to 4 (sample numbers 1 to 13). Table 1,
Table 3 shows the composition of the glass powder (excluding the metal oxide) and the like, and Tables 2 and 4 show the characteristics of the metal oxide in the glass powder and the resistor after firing. XX in Tables 2 and 4 is Fe 2 O 3 + CoO + WO 3 + Cr 2 O 3 + Bi 2 O 3 + CeO 2 + Sb 2 O 3 + In 2 O 3
+ SnO 2 + V 2 O 5 . As is apparent from these tables, it is recognized that the resistor paste according to the present invention has excellent resistance characteristics and can be sufficiently used as a resistor paste for thick film circuits.
【００４２】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３〜
表４（サンプル番号14、15）に記載した。As comparative examples, the same evaluations were made for those other than the resistor paste according to the present invention.
The results are shown in Table 4 (sample numbers 14 and 15).
【００４３】[0043]
【表１】 [Table 1]
【００４４】[0044]
【表２】 [Table 2]
【００４５】[0045]
【表３】 [Table 3]
【００４６】[0046]
【表４】 [Table 4]
【００４７】なお各特性の測定方法は次の通りである。 1) 抵抗値 １mm□抵抗パターンにてデジタルマルチメーターで測定 2) ＣＶ（抵抗値バラツキ） 抵抗値測定結果のσ／平均値The measuring method of each characteristic is as follows. 1) Resistance value 1mm □ Measured with a digital multimeter using a resistance pattern 2) CV (resistance value variation) σ / average value of resistance value measurement results
【００４８】3) 抵抗値温度係数（ＴＣＲ） 25℃ ,−55℃ ,＋125 ℃の抵抗値（Ｒ25 ,Ｒ-55 , Ｒ
125 ）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。 Cold TCR＝［（R25 − R-55 ）／｛ R25×(25-(-5
5))｝］×106(ppm/℃） Hot TCR＝［（R125− R25）／｛ R25×(125-25)｝］×
106(ppm/℃）3) Resistance temperature coefficient (TCR) 25 ° C., −55 ° C., + 125 ° C. resistance value (R 25 , R −55 , R
125 ) was measured by a resistance meter in a constant temperature bath and calculated by the following formula. Cold TCR = [(R 25 − R −55 ) / {R 25 × (25-(-5
5))}] × 10 6 (ppm / ° C) Hot TCR = [(R 125 −R 25 ) / {R 25 × (125-25)}] ×
10 6 (ppm / ℃)
【００４９】4）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。 変化率＝（Ｒ100h−Ｒ0 ）／Ｒ0 ×100 （％） 上式において Ｒ100h＝ 100時間後の抵抗値 Ｒ0 ＝抵抗の初期値4) Resistance drift due to high temperature storage It was left for 100 hours in a constant temperature bath of 150 ° C., and calculated by the following formula. Rate of change = (R 100h −R 0 ) / R 0 × 100 (%) In the above formula, R 100h = resistance value after 100 hours R 0 = initial value of resistance
【００５０】[0050]
【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。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. The effect that the value drift characteristic is excellent is also recognized.
───────────────────────────────────────────────────── フロントページの続き (51)Int.Cl.5 識別記号 庁内整理番号 ＦＩ 技術表示箇所 Ｃ０４Ｂ 35/58 １０５ Ｄ Ｈ０５Ｋ 1/09 Ｂ 6921−4Ｅ ─────────────────────────────────────────────────── ─── Continuation of the front page (51) Int.Cl. 5 Identification code Office reference number FI technical display location C04B 35/58 105 D H05K 1/09 B 6921-4E
Claims (3)
粉末30〜99.5と金属二硼化物粉末0.5 〜70からなり、該
ガラス粉末の組成中にTa2O5, Nb2O5のうち少なくとも一
種を含有し、更にFe2O3, CuO, NiO, CoO, MnO, MoO3, W
O3, Cr2O3, Bi2O3, CeO2, Sb2O3, In2O3, SnO2, V2O5の
うち少なくとも一種を含有してなることを特徴とする抵
抗体ペースト。1. An inorganic component is substantially composed of glass powder 30 to 99.5 and metal diboride powder 0.5 to 70 in terms of% by weight, and Ta 2 O 5 and Nb 2 O 5 are contained in the composition of the glass powder. At least one of them is contained, and further Fe 2 O 3 , CuO, NiO, CoO, MnO, MoO 3 , W
O 3, Cr 2 O 3, Bi 2 O 3, CeO 2, Sb 2 O 3, In 2 O 3, SnO 2, V 2 O 5 resistor paste which is characterized by containing at least one of .
体ペースト。 2. The resistor paste according to claim 1, wherein the metal diboride is ZrB 2 .
されたセラミックス基板。3. A ceramic substrate baked using the resistor paste according to claim 1.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP4266688A JPH0660718A (en) | 1992-06-10 | 1992-09-09 | Resistor paste and ceramics board |
Applications Claiming Priority (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP4-176186 | 1992-06-10 | ||
| JP17618692 | 1992-06-10 | ||
| JP4266688A JPH0660718A (en) | 1992-06-10 | 1992-09-09 | Resistor paste and ceramics board |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPH0660718A true JPH0660718A (en) | 1994-03-04 |
Family
ID=26497211
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP4266688A Withdrawn JPH0660718A (en) | 1992-06-10 | 1992-09-09 | Resistor paste and ceramics board |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH0660718A (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2005060117A (en) * | 2003-08-08 | 2005-03-10 | Kitakyushu Foundation For The Advancement Of Industry Science & Technology | Electroconductive glass for antistatic glass lining |
| JP2009530845A (en) * | 2006-03-20 | 2009-08-27 | フエロ コーポレーション | Aluminum-boron solar cell contact |
-
1992
- 1992-09-09 JP JP4266688A patent/JPH0660718A/en not_active Withdrawn
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2005060117A (en) * | 2003-08-08 | 2005-03-10 | Kitakyushu Foundation For The Advancement Of Industry Science & Technology | Electroconductive glass for antistatic glass lining |
| JP2009530845A (en) * | 2006-03-20 | 2009-08-27 | フエロ コーポレーション | Aluminum-boron solar cell contact |
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Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| A300 | Withdrawal of application because of no request for examination |
Free format text: JAPANESE INTERMEDIATE CODE: A300 Effective date: 19991130 |