JPH0380591A - Resistor paste and ceramic substrate - Google Patents
Resistor paste and ceramic substrateInfo
- Publication number
- JPH0380591A JPH0380591A JP1215038A JP21503889A JPH0380591A JP H0380591 A JPH0380591 A JP H0380591A JP 1215038 A JP1215038 A JP 1215038A JP 21503889 A JP21503889 A JP 21503889A JP H0380591 A JPH0380591 A JP H0380591A
- Authority
- JP
- Japan
- Prior art keywords
- powder
- resistor paste
- resistance
- ceramic substrate
- 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 abstract description 24
- 239000000919 ceramic Substances 0.000 title claims abstract description 17
- 239000000843 powder Substances 0.000 claims abstract description 46
- 239000011521 glass Substances 0.000 claims abstract description 30
- 239000004020 conductor Substances 0.000 claims description 18
- 239000012299 nitrogen atmosphere Substances 0.000 abstract description 8
- 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
- 239000011230 binding agent Substances 0.000 abstract description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 abstract description 4
- 238000005245 sintering Methods 0.000 abstract description 2
- XOLBLPGZBRYERU-UHFFFAOYSA-N tin dioxide Chemical compound O=[Sn]=O XOLBLPGZBRYERU-UHFFFAOYSA-N 0.000 abstract 4
- 239000000126 substance Substances 0.000 abstract 2
- PJXISJQVUVHSOJ-UHFFFAOYSA-N indium(III) oxide Inorganic materials [O-2].[O-2].[O-2].[In+3].[In+3] PJXISJQVUVHSOJ-UHFFFAOYSA-N 0.000 abstract 1
- 238000010304 firing Methods 0.000 description 12
- 239000000203 mixture Substances 0.000 description 8
- 239000002245 particle Substances 0.000 description 7
- 239000012298 atmosphere Substances 0.000 description 6
- 239000010949 copper Substances 0.000 description 6
- 230000001590 oxidative effect Effects 0.000 description 6
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 4
- 230000007423 decrease Effects 0.000 description 4
- 239000010410 layer Substances 0.000 description 4
- 238000004519 manufacturing process Methods 0.000 description 4
- 239000011148 porous material Substances 0.000 description 4
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 3
- 230000000694 effects Effects 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
- 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
- 101100348017 Drosophila melanogaster Nazo gene Proteins 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
- MCMNRKCIXSYSNV-UHFFFAOYSA-N Zirconium dioxide Chemical compound O=[Zr]=O MCMNRKCIXSYSNV-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
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 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
- 239000000463 material Substances 0.000 description 2
- 238000002844 melting Methods 0.000 description 2
- 230000008018 melting Effects 0.000 description 2
- 238000000034 method Methods 0.000 description 2
- 229910052757 nitrogen Inorganic materials 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
- 229910052725 zinc Inorganic materials 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
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 description 1
- XYLMUPLGERFSHI-UHFFFAOYSA-N alpha-Methylstyrene Chemical compound CC(=C)C1=CC=CC=C1 XYLMUPLGERFSHI-UHFFFAOYSA-N 0.000 description 1
- 229910000410 antimony oxide Inorganic materials 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
- 229910052802 copper Inorganic materials 0.000 description 1
- 238000005336 cracking Methods 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
- 229910044991 metal oxide Inorganic materials 0.000 description 1
- 150000004706 metal oxides Chemical class 0.000 description 1
- 238000013508 migration Methods 0.000 description 1
- 230000005012 migration Effects 0.000 description 1
- 239000011812 mixed powder Substances 0.000 description 1
- 150000002823 nitrates Chemical class 0.000 description 1
- VTRUBDSFZJNXHI-UHFFFAOYSA-N oxoantimony Chemical compound [Sb]=O VTRUBDSFZJNXHI-UHFFFAOYSA-N 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
- 150000003467 sulfuric acid derivatives Chemical class 0.000 description 1
- 239000004094 surface-active agent Substances 0.000 description 1
Landscapes
- Non-Adjustable Resistors (AREA)
- Conductive Materials (AREA)
- Parts Printed On Printed Circuit Boards (AREA)
- Compositions Of Oxide Ceramics (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用に適した抵抗体ペーストに
関するものである。DETAILED DESCRIPTION OF THE INVENTION [Industrial Application Field] The present invention relates to a resistor paste suitable for ceramic substrates.
［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Ｒｕ０−は使用できない。However, since Cu conductors are oxidized unless fired in a non-oxidizing atmosphere such as nitrogen, Ru0-, which is reduced in a non-oxidizing atmosphere and does not form a resistance, cannot be used.
そこで最近、ＬａＢ５粉末とガラス粉末、 ＳｎＯ□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。Therefore, recently, LaB5 powder and glass powder, SnO□ doped product and 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％表示でガラス粉末２０〜７０とＩ
ＴＯＯ〜１００ 、Ｉｎ、０３０〜９９．９９、ｓｂを
ドープしたＳｎＯ＊＋ＳｎＯ□Ｏ〜２０からなる導電物
質粉末３０〜８０からなり、当該ガラス粉末は重量％表
示で実質的に５Ｌ０２１５〜６０． Ａｌａｏ、 ０〜
３０、 ＭｇＯ＋ＣａＯ＋ＳｒＯ＋Ｂａ０ １０〜６
０． ＭｇＯＯ〜４０゜ＣａＯＯ〜４０． ＳｒＯＯ
〜６０． ＢａＯＯ〜６０． ＬＬ、０＋ＮａａＯ＋Ｋ
ｚＯ＋Ｃ５ｚＯｏ〜ｔｏ、 ｐｂｏ Ｏ〜１０． Ｚｎ
ＯＯ〜４０、 Ｚｒ０ｚ＋Ｔｉ０ｚ Ｏ”１０． Ｂｚ
Ｏｉ ５〜４０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.
TOO~100, In, 030~99.99, sb-doped SnO*+SnO□O~20 conductive material powder 30~80, and the glass powder is substantially 5L0215~60. Alao, 0~
30, MgO+CaO+SrO+Ba0 10~6
0. MgOO~40°CaOO~40. SrOO
~60. BaOO~60. LL, 0+NaaO+K
zO+C5zOo~to, pbo O~10. Zn
OO~40, Zr0z+Ti0z O”10. Bz
The present invention provides a resistor paste having an Oi of 5 to 40.
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
されるものに適したものである。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 formed by a method such as printing on a solidified ceramic substrate such as an alumina substrate after single-layer or multilayer firing, or a green sheet for a ceramic substrate, and then placed in a non-oxidizing atmosphere such as a nitrogen atmosphere. It is suitable for things that are fired in 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 sequence.
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、焼成時に上記導電物質粉末を覆って充分
に濡らし、かつ焼結するＳｉＯ□−Ｂ、０３系ガラスの
ものが好ましい。The glass powder is preferably SiO□-B, 03-based glass that has sufficient fluidity at low temperatures (e.g., 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％より少ないと導電物
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、又抵抗値の
安定性が低下するので好ましくなく、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, so that the sintered layer will have many pores, and the resistor obtained by firing the resistor paste of the present invention will suffer. This is not preferable because the strength becomes weak and the stability of the resistance value decreases, and if it exceeds 70%, the adhesion between the conductive material powders decreases and the resistance value becomes 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、
ＳｎをＩｎｚＯ３にドープしたもの（以下ＩＴＯという
） ０〜１００％
ＩｎｔＬ Ｏ〜９９．９９％ｓｂをドー
プした５ｎｏ２＋ Ｓｎｏ□（］〜２０％（Ｓｂをドー
プしたＳｎＯ□０〜２０％、ＳｎＯ□０〜２０％）から
なるものが好ましい。On the other hand, the conductive material powders include InzO3 doped with Sn (hereinafter referred to as ITO), 0~100% IntLO~99.99%sb-doped 5no2+ Sno□(]~20% (Sb-doped SnO□) 0 to 20% and SnO□0 to 20%) is preferable.
該Ｉｎ２０ｇ粉末は９９．９９％を超えると、抵抗値調
整の効果が少なく好ましくなく、ｓｂをドープしたＳｎ
Ｏ□＋ＳｎＯ□粉末は２０％を超えると抵抗値が大きく
なり好ましくない。望ましくは。If the In 20g powder exceeds 99.99%, the effect of adjusting the resistance value will be small and undesirable, and the sb-doped Sn
If the content of O□+SnO□ powder exceeds 20%, the resistance value increases, which is not preferable. Preferably.
ＩＴＯ粉末 ０〜１００％
ＩｎＪ−粉末 ０〜９９．９％
ｓｂをドープした５ｎＯｚ ＋ Ｓｎｏ□粉末０〜１５
％特に望ましくは、
ＩＴＯ粉末 ０〜１００％
ＩｎｚＯｓ粉末 ０〜９９％
ｓｂをドープしたＳｎＯ□＋ＳｎＯ□粉末０〜１０％で
ある。ITO powder 0-100% InJ-powder 0-99.9% sb doped 5nOz + Sno□ powder 0-15
Particularly preferred are: ITO powder 0-100% InzOs powder 0-99% sb-doped SnO□+SnO□ powder 0-10%.
上記導電物質粉末を使用する理由は、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かかる抵抗体
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。The reason for using the above-mentioned conductive material powder is that such a material has a property of high conductivity, that is, low resistivity. This is because it is possible to make them match.
ＩＴＯはドープしないＩｎ２０ｉに比較して抵抗値が低
くなり、ドープ量が多くなり過ぎると抵抗値が高くなる
。ITO has a lower resistance value than undoped In20i, and when the amount of doping is too large, the resistance value increases.
上記ドープ量は５ｎｏ２の酸化物重量換算でＩｎ２０ａ
８０〜９９．９９％に対して５ｎＯｚ ０．０１〜２
０％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〜ｌＯ％である。The above doping amount is In20a in terms of 5no2 oxide weight.
5nOz 0.01-2 for 80-99.99%
0% is an appropriate range, and a desirable range is 0.1 to 15
%, a particularly desirable range is 1 to 10%.
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、抵抗値が低くなり、ドープ量が多くな
り過ぎると抵抗値が高くなる。上記ドープ量はＳｂ２０
ｇ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〜ｌ
Ｏ％である。sb doped into SnO□, undoped Sn
Compared to O□, the resistance value is lower, and if the amount of doping is too large, the resistance value becomes high. The above doping amount is Sb20
An appropriate range is 0 to 20% in terms of g of oxide, a desirable range is 0.1 to 15%, and a particularly desirable range is 1 to 1
It is 0%.
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
抵抗値が大きくなり過ぎ好ましくなく、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の範囲が必要な範囲であり、望ましい範囲は０．０
５〜３μｍ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 too large, which is undesirable, and if it is too large, the particle size will become non-uniform on the ceramic substrate, resulting in large variations in the resistance value, which is not preferable. Average particle size is 0.01-5
The required range is μm, and the desirable range is 0.0
It is 5 to 3 μm.
本発明にかかるガラス粉末は、実質的にＳｉＯ□
１５〜６０％Ａ１□０３０〜３０％
ＭｇＯ＋ＣａＯ＋ＳｒＯ＋Ｂａ０ １０〜６０％（Ｍ
ｇＯ（］〜４０．ＣａＯＯ〜４０．ＳｒＯＯ〜６０゜Ｂ
ａＯＯ〜６０）
Ｌｉ２０＋ＮａａＯ＋に２０＋Ｃｓ２Ｏｏ〜ｉ０％ｐｂ
ｏ ｏ〜１０％Ｚｎ
ＯＯ〜４０％
Ｚｒ０ｚ＋Ｔｉ０ｚ Ｏ〜１０％
Ｂｉａｓ ５〜４０％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 is substantially SiO□
15~60%A1□030~30% MgO+CaO+SrO+Ba0 10~60% (M
gO(]~40.CaOO~40.SrOO~60°B
aOO~60) 20+Cs2Oo~i0%pb for Li20+NaaO+
o o~10%Zn
OO~40% Zr0z+Ti0z O~10%
It consists of 5 to 40% bias, and these will be explained in order.
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、１５％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くな
るので好ましくない。−方５ｉＯａが６０％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、２０〜５５％の範囲である。In such a composition, SiO□ is a glass network former, and if it is less than 15%, the softening point becomes too low, the heat resistance decreases, and deformation is likely to occur during re-firing, which is not preferable. - If 5iOa is more than 60%, the softening point will be too high, the flow of the glass will be poor during firing, it will not be possible to cover and wet the conductive material powder, the sintered layer will have too many pores, and the resistance will increase. This is not appropriate as it will result in poor stability. Desirably, it is in the range of 20 to 55%.
Ａｌｌ０．は必須ではないが、添加することにより、耐
湿性の向上に効果がある。３０％を越えるとガラスの軟
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２５％以下である。All0. Although not essential, its addition is effective in improving moisture resistance. If it exceeds 30%, the softening temperature of the glass will become high and the sinterability will deteriorate, making it unsuitable. It is preferably 25% or less.
ＭｇＯ＋ＣａＯ＋ＳｒＯ＋ＢａＯ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目的で
添加する。１０％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く、６０
％を越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 is added for the purpose of improving solubility during glass powder production and adjusting the thermal expansion coefficient. If it is less than 10%, the above-mentioned solubility will not be improved sufficiently, and devitrification will easily occur during glass production.
%, the coefficient of thermal expansion becomes too large, and neither is suitable. Desirably, it is in the range of 15 to 55%.
また上記ＭｇＯ＋ＣａＯ＋ＳｒＯ＋ＢａＯの内のＭｇＯ
、ＣａＯ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０〜３
５％である。上記ＭｇＯ＋ＣａＯ＋ＳｒＯ＋ＢａＯの内
のＳｒＯ，ＢａＯはそれぞれ６０％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
それぞれ０〜５５％である。Also, MgO in the above MgO + CaO + SrO + BaO
, CaO of 40% or more, the coefficient of thermal expansion becomes too large, which is inappropriate. Desirable range is 0-3
It is 5%. If SrO and BaO in the MgO+CaO+SrO+BaO are each 60% or more, the coefficient of thermal expansion becomes too large, which is inappropriate. The desirable range is 0-55% for each.
ＬｉｚＯ＋ＮａｚＯ＋ＫｚＯ＋Ｃ５ｚＯは必須ではない
が、添加することによりガラスの溶解性の向上を図るこ
とができる。１０％を越えると、熱膨張係数が大きくな
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 LizO+NazO+KzO+C5zO is not essential, the solubility of the glass can be improved by adding it. 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 increases, which is not suitable. It 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
ての効果がある、１０％を越えると抵抗値が不安定にな
り適当でない。望ましくは５％以下である。Although PbO is not essential, it has an effect as a flux component of the glass, and if it exceeds 10%, the resistance value becomes unstable and is not suitable. 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４０％まで添加することが可能であり、３５％以下が
望ましい範囲である。Although ZnO is not essential, it can be added up to 40% to improve the solubility of the glass, with a desirable range of 35% 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％までが可能であるが、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 up to 10%, but is preferably 7% or less.
ＢｚＯｓ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％を越えるとガラスの耐
水性が低下し適当でない。望ましくは７〜３５％の範囲
である。BzOs 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 35%.
以上記載した望ましい範囲についてまとめると以下の通
りとなる。The desirable ranges described above are summarized as follows.
ＳｉＯ□
Ａ１□Ｏ３
ＭｇＯ＋ＣａＯ＋ＳｒＯ＋ＢａＯ
（Ｍｇ０ ０〜３５． ＣａＯ
ＢａＯ（１〜５５）
ＬｉｚＯ＋ＮａｚＯ＋ＫｇＯ＋Ｃｓ２Ｏ（１〜８％ｐｂ
ｏ ｏ〜５％Ｚｎ（１０〜３
５％
ＺｒＯ２＋Ｔｉ０ｚ （１〜７％Ｂ
、Ｏａ ７〜３５％本発明の
抵抗体ペーストの組成物は、各粉末が前記割合に混合さ
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。SiO□ A1□O3 MgO+CaO+SrO+BaO (Mg0 0~35. CaO BaO (1~55) LizO+NazO+KgO+Cs2O (1~8%pb
o o~5%Zn(10~3
5% ZrO2+Ti0z (1~7%B
, Oa 7 to 35% The composition of the resistor paste of the present invention is one in which each powder is mixed in the above ratio.The method for producing the resistor paste of the present invention and the thick film circuit using the same are described below. An example of manufacturing will be described.
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、乾燥し、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２０〜５５％
０〜２５％
１５〜５５％
ＳｒＯＯ〜５５゜
０〜３５゜
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−トリメチルペンタンジオ−ルー
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 dried to form a paste. The organic binder includes ethyl cellulose, acrylic resin, ethylene-vinyl acetate copolymer resin, poly 20-55% 0-25% 15-55% SrOO-55° 0-35° α-methylstyrene resin, and the solvent includes: α-terpineol, butyl carpitol acetate, butyl carpitol, 2,2,4-trimethylpentanedio-ru 1,3. -monoisobutyrate, diethylene glycol di-n-butyl ether, etc. are 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ペーストを所定の回路に印刷、乾燥後、
酸素濃度２０ ｐｐｍ以下の窒素雰囲気中で８５０〜９
５０℃、５〜２０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。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。Next, in order to create a conductor on a solidified alumina substrate after firing or a ceramic substrate such as a glass-ceramic substrate, Cu paste is printed on a predetermined circuit, and after drying,
850-9 in a nitrogen atmosphere with an oxygen concentration of 20 ppm or less
Bake at 50°C for 5 to 20 minutes. The preferred range of firing conditions is 880 to 920°C and 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, and then dried in the nitrogen atmosphere.
８５０〜９５０℃、５〜２０分で焼成する。この焼成条
件の望ましい範囲は８８０で〜９２０℃ ７〜１５分で
ある。Bake at 850-950°C for 5-20 minutes. The preferred range of firing conditions is 880° C. to 920° C. for 7 to 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リーンシートを熱圧着後積
層し、上記窒素雰囲気中で８５０〜９５０℃、数分〜数
時間で一括焼成し、多層セラミックス基板を作成する。In the case of bulk firing of multilayer ceramic substrates, green sheets of ceramics such as those for ceramic substrates printed with the Cu paste and the resistor paste of the present invention are laminated after thermocompression bonding, and heated at 850 to 950°C for several seconds in the nitrogen atmosphere. A multilayer ceramic substrate is created by batch firing in minutes to several hours.
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、ガラス溶解時に清澄剤、溶融促進剤として硝酸塩
、亜ヒ酸、酸化アンチモン、硫酸塩、フッ化物、塩化物
等を０〜５％添加することができる。Further, during glass melting, 0 to 5% of nitrates, arsenous acid, antimony oxide, 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−
ｌ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表−１に示
す目標組成のＳｎドープＩｎｚＯｉ （ＩＴＯ）粉末と
目標組成比のＩｎｚＯｓ粉末とｓｂドープ５ｎｏ２粉末
とＳｎＯ□粉末の混合粉末を平均粒径０．０１〜５μｍ
になるように調整した。ＳｎドープＩｎｚＯ８（ＩＴＯ
）粉末は次の様にして製造した。[Example] Each raw material of the glass powder according to the present invention is shown in terms of oxides.
Blend in the proportion shown in l, place this in a platinum crucible,
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, as a conductive material, a mixed powder of Sn-doped InzOi (ITO) powder with the target composition shown in Table 1, InzOs powder with the target composition ratio, sb-doped 5no2 powder, and SnO□ powder was mixed with an average particle size of 0.01 to 5 μm.
I adjusted it so that Sn-doped InzO8 (ITO
) The powder was produced as follows.
ＩｎＪａ粉末８０〜９９．９９％と５ｎＣ１ｚ ０．０
１〜２０％を５００〜１５００℃で焼成し、焼成物を粉
砕して粉末を製造した。InJa powder 80-99.99% and 5nC1z 0.0
1 to 20% was calcined at 500 to 1500°C, and the calcined product was pulverized to produce powder.
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。Next, these glass powders and the above-mentioned conductive material powders are shown in Table-1.
were mixed in the proportions described in , 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２０ ｐｐｍ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な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
０ ｐｐｍ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 above resistor paste was screen printed on a predetermined location of the resistor using a 200 mesh screen, dried, and the oxygen concentration was 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、抵抗値温度係数（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に記載した。表−１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 (TCR),
The resistance value drift due to high temperature storage was measured. These results are listed in Table-1. As is clear from Table 1, it is recognized that the resistor paste according to the present invention has excellent resistance characteristics and has 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同時に表−１に記載
した。As a comparative example, similar evaluations were conducted on materials other than the resistor paste according to the present invention, which are also 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（Ｒｚｓ。i) Resistance value and temperature coefficient of resistance (TCR) 25℃ -5
Resistance value at 5℃, +125℃ (Rzs.
Ｒ−ｓｓ、Ｒ＋□、）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。R-ss, R+□,) was measured with 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
Ｒ１゜。、＝ １００時間後の抵抗値
Ｒｏ＝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るとともに焼結性、耐水性
がよく、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。In the above formula, R1°. , = Resistance value after 100 hours Ro = 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 provides a stable and reliable resistor to a ceramic substrate. It is also recognized that it can be formed on top of the substrate, has good sinterability and water resistance, and is particularly excellent in resistance value drift characteristics when left at high temperatures.
Claims (2)
ＩＴＯ ０〜１００、Ｉｎ＿２Ｏ＿３ ０〜９９．９９
、ＳｂをドープしたＳｎＯ＿２＋ＳｎＯ＿２ ０〜２０
からなる導電物質粉末３０〜８０からなり、当該ガラス
粉末は重量％表示で実質的にＳｉＯ＿２ １５〜６０，
Ａｌ＿２Ｏ＿３０〜３０，ＭｇＯ＋ＣａＯ＋ＳｒＯ＋Ｂ
ａＯ １０〜６０，ＭｇＯ ０〜４０，ＣａＯ ０〜４
０，ＳｒＯ ０〜６０，ＢａＯ ０〜６０，Ｌｉ＿２Ｏ
＋Ｎａ＿２Ｏ＋Ｋ＿２Ｏ＋Ｃｓ＿２Ｏ ０〜１０，Ｐｂ
Ｏ ０〜１０，ＺｎＯ ０〜４０，ＺｒＯ＿２＋ＴｉＯ
＿２ ０〜１０，Ｂ＿２Ｏ＿２ ５〜４０からなる抵抗
体ペースト。(1) Inorganic components expressed in weight%: glass powder 20-70, ITO 0-100, In_2O_3 0-99.99
, Sb-doped SnO_2+SnO_2 0-20
The glass powder consists of 30 to 80% conductive material powder consisting of SiO_2 of 15 to 60% by weight.
Al_2O_30~30, MgO+CaO+SrO+B
aO 10-60, MgO 0-40, CaO 0-4
0, SrO 0-60, BaO 0-60, Li_2O
+Na_2O+K_2O+Cs_2O 0-10, Pb
O 0~10, ZnO 0~40, ZrO_2+TiO
Resistor paste consisting of _2 0-10, B_2O_2 5-40.
たセラミックス基板。(2) A ceramic substrate fired using the resistor paste described in item 1.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP1215038A JPH0380591A (en) | 1989-08-23 | 1989-08-23 | Resistor paste and ceramic substrate |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP1215038A JPH0380591A (en) | 1989-08-23 | 1989-08-23 | Resistor paste and ceramic substrate |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPH0380591A true JPH0380591A (en) | 1991-04-05 |
Family
ID=16665728
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP1215038A Pending JPH0380591A (en) | 1989-08-23 | 1989-08-23 | Resistor paste and ceramic substrate |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH0380591A (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2008103372A (en) * | 2006-10-17 | 2008-05-01 | Murata Mfg Co Ltd | Method of adjusting specific resistance of thick-film resistor |
-
1989
- 1989-08-23 JP JP1215038A patent/JPH0380591A/en active Pending
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2008103372A (en) * | 2006-10-17 | 2008-05-01 | Murata Mfg Co Ltd | Method of adjusting specific resistance of thick-film resistor |
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