JPH03149706A - Nickel conductive paste - Google Patents
Nickel conductive pasteInfo
- Publication number
- JPH03149706A JPH03149706A JP28770489A JP28770489A JPH03149706A JP H03149706 A JPH03149706 A JP H03149706A JP 28770489 A JP28770489 A JP 28770489A JP 28770489 A JP28770489 A JP 28770489A JP H03149706 A JPH03149706 A JP H03149706A
- Authority
- JP
- Japan
- Prior art keywords
- alloy
- powder
- paste
- sheet resistance
- less
- 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
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 title claims abstract description 42
- 229910052759 nickel Inorganic materials 0.000 title claims abstract description 18
- 239000000843 powder Substances 0.000 claims abstract description 54
- 229910045601 alloy Inorganic materials 0.000 claims abstract description 34
- 239000000956 alloy Substances 0.000 claims abstract description 34
- 239000002131 composite material Substances 0.000 claims abstract description 20
- 229910052751 metal Inorganic materials 0.000 claims description 19
- 239000002184 metal Substances 0.000 claims description 19
- 229910000990 Ni alloy Inorganic materials 0.000 claims description 10
- 229910052796 boron Inorganic materials 0.000 claims description 7
- 239000011521 glass Substances 0.000 claims description 7
- 229910052738 indium Inorganic materials 0.000 claims description 6
- 229910052718 tin Inorganic materials 0.000 claims description 6
- 229910052725 zinc Inorganic materials 0.000 claims description 6
- 229910052787 antimony Inorganic materials 0.000 claims description 5
- 229910052797 bismuth Inorganic materials 0.000 claims description 4
- 229910052749 magnesium Inorganic materials 0.000 claims description 3
- 239000003960 organic solvent Substances 0.000 claims description 3
- 239000012298 atmosphere Substances 0.000 abstract description 15
- 239000000853 adhesive Substances 0.000 abstract description 12
- 230000001070 adhesive effect Effects 0.000 abstract description 12
- 238000005476 soldering Methods 0.000 abstract 2
- 238000010304 firing Methods 0.000 description 12
- 230000003647 oxidation Effects 0.000 description 12
- 238000007254 oxidation reaction Methods 0.000 description 12
- 229910000679 solder Inorganic materials 0.000 description 12
- 239000002245 particle Substances 0.000 description 10
- 239000000758 substrate Substances 0.000 description 9
- 239000000203 mixture Substances 0.000 description 8
- 150000002739 metals Chemical class 0.000 description 7
- 229910052804 chromium Inorganic materials 0.000 description 6
- 230000000052 comparative effect Effects 0.000 description 6
- 229910052742 iron Inorganic materials 0.000 description 6
- 239000000654 additive Substances 0.000 description 5
- 239000004020 conductor Substances 0.000 description 5
- 238000005245 sintering Methods 0.000 description 5
- 239000001856 Ethyl cellulose Substances 0.000 description 4
- 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 4
- 230000000996 additive effect Effects 0.000 description 4
- 239000010953 base metal Substances 0.000 description 4
- 230000000694 effects Effects 0.000 description 4
- 229920001249 ethyl cellulose Polymers 0.000 description 4
- 235000019325 ethyl cellulose Nutrition 0.000 description 4
- 239000007791 liquid phase Substances 0.000 description 4
- 238000002156 mixing Methods 0.000 description 4
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 3
- 239000011230 binding agent Substances 0.000 description 3
- 229910052746 lanthanum Inorganic materials 0.000 description 3
- 239000005361 soda-lime glass Substances 0.000 description 3
- 239000007787 solid Substances 0.000 description 3
- DAFHKNAQFPVRKR-UHFFFAOYSA-N (3-hydroxy-2,2,4-trimethylpentyl) 2-methylpropanoate Chemical compound CC(C)C(O)C(C)(C)COC(=O)C(C)C DAFHKNAQFPVRKR-UHFFFAOYSA-N 0.000 description 2
- 239000005388 borosilicate glass Substances 0.000 description 2
- 238000001035 drying Methods 0.000 description 2
- 238000011156 evaluation Methods 0.000 description 2
- 239000005357 flat glass Substances 0.000 description 2
- 229910052741 iridium Inorganic materials 0.000 description 2
- 210000003127 knee Anatomy 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 238000000034 method Methods 0.000 description 2
- 239000002904 solvent Substances 0.000 description 2
- QTBSBXVTEAMEQO-UHFFFAOYSA-M Acetate Chemical compound CC([O-])=O QTBSBXVTEAMEQO-UHFFFAOYSA-M 0.000 description 1
- 238000007718 adhesive strength test Methods 0.000 description 1
- WUOACPNHFRMFPN-UHFFFAOYSA-N alpha-terpineol Chemical compound CC1=CCC(C(C)(C)O)CC1 WUOACPNHFRMFPN-UHFFFAOYSA-N 0.000 description 1
- 230000003078 antioxidant effect Effects 0.000 description 1
- 235000013405 beer Nutrition 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 239000003990 capacitor Substances 0.000 description 1
- 239000000919 ceramic Substances 0.000 description 1
- 239000003985 ceramic capacitor Substances 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- SQIFACVGCPWBQZ-UHFFFAOYSA-N delta-terpineol Natural products CC(C)(O)C1CCC(=C)CC1 SQIFACVGCPWBQZ-UHFFFAOYSA-N 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 238000007598 dipping method Methods 0.000 description 1
- 239000003792 electrolyte Substances 0.000 description 1
- 229910052737 gold Inorganic materials 0.000 description 1
- 230000010354 integration Effects 0.000 description 1
- 239000005355 lead glass Substances 0.000 description 1
- 229910052744 lithium Inorganic materials 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- 239000000178 monomer Substances 0.000 description 1
- 239000012299 nitrogen atmosphere Substances 0.000 description 1
- 229910000510 noble metal Inorganic materials 0.000 description 1
- 239000012071 phase Substances 0.000 description 1
- 230000002250 progressing effect Effects 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 238000010008 shearing Methods 0.000 description 1
- 230000035939 shock Effects 0.000 description 1
- 239000005368 silicate glass Substances 0.000 description 1
- RMAQACBXLXPBSY-UHFFFAOYSA-N silicic acid Chemical compound O[Si](O)(O)O RMAQACBXLXPBSY-UHFFFAOYSA-N 0.000 description 1
- 235000012239 silicon dioxide Nutrition 0.000 description 1
- 229910052709 silver Inorganic materials 0.000 description 1
- 239000010935 stainless steel Substances 0.000 description 1
- 229910001256 stainless steel alloy Inorganic materials 0.000 description 1
- 229910000601 superalloy Inorganic materials 0.000 description 1
- 229940116411 terpineol Drugs 0.000 description 1
- 238000009736 wetting Methods 0.000 description 1
Classifications
-
- H—ELECTRICITY
- H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
- H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
- H05K1/00—Printed circuits
- H05K1/02—Details
- H05K1/09—Use of materials for the conductive, e.g. metallic pattern
- H05K1/092—Dispersed materials, e.g. conductive pastes or inks
Abstract
Description
【発明の詳細な説明】
１産！上の利川分野１
本青明はニッケルペースト番こ係り、特番こはんだ濡れ
性が改良され、大気中焼成が可能で低温でも焼結性が優
れており、シート抵抗の低いＦＩＷ！！導体ペーストに
好適なニッケルペーストに関するものである。[Detailed description of the invention] One production! Above Icheon field 1 This Qingmei is a nickel paste paste, has improved solder wettability, can be fired in the atmosphere, has excellent sinterability even at low temperatures, and is FIW with low sheet resistance! ! The present invention relates to a nickel paste suitable for a conductor paste.
【従来の技術Ｊ
近年、′：ｔｉ子機器の薄型化、コンパクト化は著しく
、４Ｊｍ度の増加と共番ニー段と信頼性が向上し、用途
も拡大の−達をたどっている。モルリシックＩＣでは急
速な密度の増加、小型化が進んできており、一方ハイブ
リフトＩＣの分野でも特番こ自動車用制御回路や電源装
置用等の産業ｌｌ器においては耐熱性、耐衝撃性に優れ
た大規模パイプリフトＩＣ化の傾向が強い、！１近のパ
イプリフト【Ｃでは、セラミツク基板土ａこダイオード
、トランジスタ、ニー導体ＩＣ等の能動部品の他コイル
、トランス、：Ｊンデンサ一等殆どの電気部品をＪ３截
している。集積度も一段と増加し４Ａ軸度も飛躍的＆こ
向上した混成集積回路が開発されている。[Prior Art J] In recent years, TI slave devices have become significantly thinner and more compact, with an increase in 4 Jm degrees, a common knee stage, improved reliability, and an expansion of applications. In the field of hybrid ICs, rapid increases in density and miniaturization are progressing, and on the other hand, in the field of hybrid ICs, large ICs with excellent heat resistance and shock resistance are being used for industrial devices such as automotive control circuits and power supply devices. There is a strong trend toward IC-based pipe lifts! In the nearby pipe lift [C], most of the electric parts such as ceramic substrates, active parts such as diodes, transistors, and knee conductor ICs, as well as coils, transformers, and capacitors, are cut into J3. Hybrid integrated circuits have been developed that have further increased the degree of integration and dramatically improved the 4A axis.
この場合、これら回路基板の製造法として基板表面１こ
電極や回路用のメタライズ層を従来このメタライズ層形
成材としては、η金属を梯川し、ｊｇ体、抵抗体、誘電
体ペーストを印刷して行なっていたが、ｎ金属ペースト
は導電性、基板との接着性 −１極等とのボンダビリテ
ィ−に優れてはいるが、Ａｇ、Ａｇ−Ｐｄ、Ａｇ−Ｐｔ
、Ａ−ｇ−ＰｔＰｄ、Ａｕ等の貴金属を原料として使用
されているので高価である難点があった。In this case, the manufacturing method for these circuit boards is to create a metallized layer for electrodes and circuits on the surface of the board. Conventionally, the metallized layer forming material is made of η metal and printed with a JG body, a resistor, and a dielectric paste. However, although n-metal pastes have excellent conductivity, adhesion to substrates, and bondability with single poles, etc.,
, Ag-PtPd, Au, and other noble metals are used as raw materials, which has the drawback of being expensive.
１９明が解決しようとする課ｊｍｌ このため、安価な卑金属、例えばＣｕ、Ｎｉ。19th issue that Ming is trying to solve For this reason, inexpensive base metals such as Cu and Ni are used.
八β、ｚｎ等を主体とした卑金属ペーストの開発が試み
られてきている。しかし、型金には酸化され易いため、
ｒ１金属ペーストのように大気中での焼成が出来ず、ｅ
ｘｉｔｓ度を低くｖＩ御した不活性なＮ２雰四気中で焼
成を行なうことが必要とされ。Attempts have been made to develop base metal pastes mainly containing 8β, zn, and the like. However, since mold metal is easily oxidized,
Unlike r1 metal paste, it cannot be fired in the atmosphere, and e
It is necessary to carry out the firing in an inert N2 atmosphere with low xits and controlled VI.
このため卑金属ペーストが安価でも不活性雰囲気下で焼
成するための装置あるいはＮ２ガスのコストが必要とな
るため、ペースト自体が安価である利点がト分番こｔか
されていないという四項があった。For this reason, even if base metal paste is cheap, it requires equipment for firing in an inert atmosphere or the cost of N2 gas, so the advantage of the paste itself being cheap is not fully taken into consideration. Ta.
本発明は、安価な卑金属ペーストであっても大気中での
焼成がり能なニッケル導電ペーストの開発を目的とし、
併せて大気中焼成であってもはんだ鑑れ性、シート抵抗
力、接着力、低湿焼成等各こ優れたペーストを目的とし
たものである。The purpose of the present invention is to develop a nickel conductive paste that can be fired in the atmosphere even if it is an inexpensive base metal paste.
In addition, the aim is to create a paste that has excellent solder visibility, sheet resistance, adhesive strength, low humidity firing, etc. even when fired in the air.
先ず。First.
０ 焼成雰囲気は大気中であっても耐酸化性があって抵
抗値が変化しないこと
０ シート抵抗はＡｕ、Ａｇでは通常２ｍΩ／口である
が、−桁上で２０ｍΩ／口以下であること
■ 焼成温度は通常高温のものは９００℃、低温で６０
０℃位であるが、四番こ低温で５００〜６００℃程度で
焼成できること■ 接着強度は４Ｋｇ７２．５ｍｍ口以
上あること
０ はんだ濡れ住良好なこと
を一応の目標として開発を行なった。0 The firing atmosphere must be oxidation resistant and the resistance value will not change even in the air. 0 Sheet resistance is usually 2 mΩ/unit for Au and Ag, but it must be less than 20 mΩ/unit on the negative order■ The firing temperature is usually 900℃ for high temperature and 60℃ for low temperature.
Although the temperature is around 0°C, it should be possible to bake at the lowest temperature of about 500 to 600°C (2) Adhesive strength should be 4 kg (72.5 mm) or more (0) Good solder wetting properties were the primary goals of development.
［，ｆｆＭを解決するための手段］
前記目的を達成するため、本発明者はＮｉペーストに使
用する金属粉末の耐酸化性を向上させ得る様々な添加元
素について検討し、その金属粉末を使用してペーストを
作った場合紀大気中焼成が可能で、はんだ濡れ性か良く
、低温で焼結し。[Means for solving , ffM] In order to achieve the above object, the present inventor studied various additive elements that can improve the oxidation resistance of the metal powder used in Ni paste, and used the metal powder. When a paste is made, it can be fired in the atmosphere, has good solder wettability, and can be sintered at low temperatures.
シート抵抗、接着力が改善できる方策について鋭意研究
を重ねた結果、Ｃｒおよび／またはＦｅがそれぞれ１ｗ
ｔ％以上であって、この両者の合計が２０ｗＬ％以下、
Ｂ３〜１０ｗｔ％、Ｓｉは１０％ｗｔ以下であって、Ｂ
とＳｉの合計は１５ｗｔ％以下、残りＮｉからなる合金
粉末又はメカニカルアロイ形態の複合粉末を使用したニ
ッケル導電ペースト（以下、特定発明という、）であり
、四鑑二上記の合金粉末又はメカニカルアロイ形態の複
合粉末が、さらにＳｂ、Ｂｉ、Ｉｎ、Ｍ ｇ 、 Ｐ
ｒ 、 Ｓ ｎ 、 Ｚ ｎまたはＬａの少なくともｌ
ｆＩ！を０− １〜５ ｗ Ｌ％含むニッケル導電ペー
スト（以下、第２発明という、）ｊ３よびＳｂ。As a result of intensive research on measures to improve sheet resistance and adhesive strength, we found that Cr and/or Fe were each 1w
t% or more, and the total of both is 20wL% or less,
B3 to 10 wt%, Si is 10% wt or less, and B
A nickel conductive paste (hereinafter referred to as the specified invention) using an alloy powder or mechanical alloy composite powder in which the total of The composite powder further contains Sb, Bi, In, M g , P
At least l of r, S n , Z n or La
fI! nickel conductive paste containing 0-1 to 5 wL% (hereinafter referred to as the second invention) j3 and Sb.
１１ｉ、１．ｎ、Ｍｇ、Ｐｒ、Ｓｎ、ＺｎまたはＬａの
一種又はこの金属を主体とするニッケル合金粉末（メカ
ニカルアロイ形態の複合粉末も含む、）を、これら金属
を含まない特定発明の合金粉末又はメカニカルアロイ形
態の複合粉末１００重量部＆ご対して、金属として（Ｌ
１〜５重贋部の比率で使用したニッケルＮｑ電ペー
スト（以下、第３発明という、）を提供する。11i, 1. nickel alloy powder (including composite powder in mechanical alloy form) containing one of n, Mg, Pr, Sn, Zn, or La or a nickel alloy powder (including composite powder in mechanical alloy form) containing these metals as an alloy powder or mechanical alloy form of a specified invention that does not contain these metals 100 parts by weight of composite powder & as metal (L
Provided is a nickel Nq electrolyte paste (hereinafter referred to as the third invention) used in a ratio of 1 to 5 times the number of false parts.
ここで提供された特定発明のニッケル導電ペーストは、
大気中で焼成した導体膜でもシート抵抗が低く、接着力
も非常番こ優れていることを見出した。The nickel conductive paste of the specific invention provided herein is
We have discovered that even conductor films fired in the atmosphere have low sheet resistance and excellent adhesive strength.
また。第２発明及び第３発明紀よるニッケル導電ペース
トは特定発明による大気中で焼成した導体膜の低いシー
ト抵抗値高い接着力の性質を持つだけでなく、５００℃
という低い焼結温度に右いても］−分番こ焼結し、上記
の特性を得ることを見出して本発明を完成したものであ
る。Also. The nickel conductive paste according to the second and third inventions not only has the properties of low sheet resistance and high adhesive strength of the conductor film fired in the atmosphere according to the specific invention, but also has the properties of high adhesive strength at 500℃.
The present invention was completed by discovering that the above characteristics can be obtained by sintering at low sintering temperatures.
本発明において、Ｃｒ及びＦｅはそれぞれが単独または
併用して使用するが、少なくとも１ｗｔ％の添加が必要
であり、そしてその合計量は２０ｗｔ％を越えてはなら
ない。In the present invention, Cr and Fe are used alone or in combination, but they must be added in an amount of at least 1 wt%, and their total amount must not exceed 20 wt%.
０「、Ｆｅは大気中焼成に右いてＮｉ合金粒子の耐酸化
性を向上させる効果がある。これはＮｉ合金粒子表面各
こ緻密で薄い酸化膜を形成し、Ｎｉ合金粒子自体の酸化
を防ぐ。0", Fe has the effect of improving the oxidation resistance of Ni alloy particles when fired in the atmosphere. This forms a dense and thin oxide film on each surface of the Ni alloy particles, preventing the oxidation of the Ni alloy particles themselves. .
この手法はステンレス鋼や超合金墨ご用いられているが
、これらは主に板状で比表面積が小さいので表面が酸化
することからくる構造材料としての強度には大きな影響
は与えない。This method is used for stainless steel and superalloy black, but since these are mainly plate-shaped and have a small specific surface area, oxidation of the surface does not have a large effect on the strength as a structural material.
これ１こ反し、本完明墨こおけるＮｉ合金は１０ミクロ
ン以下の粒子の状態で比表面積が大きいため、表向の酸
化膜が薄くても全体の酸化物含有量は大きくなり、シー
ト抵抗値の上昇に繋る。したがって、Ｃｒ、Ｆｅの添加
だけでは本発明の目的を達成できず、更に改良すること
が必要であることを知ったー
これの対応策として、８３〜１ Ｏｗ ｔ％。On the other hand, the Ni alloy in Honkanmei Sumiko has a large specific surface area in the form of particles of 10 microns or less, so even if the surface oxide film is thin, the overall oxide content is large, and the sheet resistance value leading to an increase in Therefore, it was found that the purpose of the present invention could not be achieved only by adding Cr and Fe, and that further improvement was necessary.As a countermeasure for this, 83 to 1 Ow t%.
５１をｌ Ｏｗ ｔ−％以下、 （Ｉ！ Ｌ １１とＳ
ｉの合計量が１５ ｗ ｔ％以下添加した合金粒子とす
ることで耐酸化性が著しく向りすることが見出された。51 less than l Ow t-%, (I! L 11 and S
It has been found that oxidation resistance is significantly improved by adding alloy particles in which the total amount of i is 15 wt% or less.
この理由は、Ｎｉペーストを大気中で焼成しているとき
にＩ１．Ｓｉが優先的に酸化され、口２０．。The reason for this is that when the Ni paste is fired in the atmosphere, I1. Si is preferentially oxidized and 20. .
８１０２が液相になってＮｉ合金粒子をまんべんなく覆
うため、大気との接触がなくなり酸化が防げるものと推
定している。It is estimated that 8102 turns into a liquid phase and evenly covers the Ni alloy particles, eliminating contact with the atmosphere and preventing oxidation.
したがって、ＮｉＪ％１子の酸化はＢ、Ｓｉ添加によろ
選択的な脱Ｗｌｌｉ：、 Ｂ、 Ｓ ｉ ＠化物の液相
生成及びＣｒ、Ｆｃの添加番こよる酸化膜形成によって
大幅に防ぐことができる。Therefore, the oxidation of NiJ% monomers can be significantly prevented by the selective removal of Wlli:, B, Si@ oxide by the addition of B and Si, and the formation of an oxide film by the addition of Cr and Fc. can.
このことはＣｒ、Ｆｅ及び■、ＳｉＪ３（方の添加によ
って初めて成立する。このと３．Ｃｘ−，Ｆｅ及びＢ、
Ｓｉの添加形態は、純金属粉末の単なる混合では上記目
的が達成されない、なぜならば。This is true only by the addition of Cr, Fe, and SiJ3.
The reason for the addition form of Si is that the above objective cannot be achieved by simply mixing pure metal powder.
Ｃｒ、Ｆｅが純金属の場合、Ｎｉ粒子表面を緻密シ二覆
うことができず、Ｂ、Ｓｉが純金属の場合でも同様であ
る。したがって、Ｃｒ、Ｆｅ及びＢ。When Cr and Fe are pure metals, the surfaces of Ni particles cannot be densely covered, and the same is true when B and Si are pure metals. Therefore, Cr, Fe and B.
Ｓｉの添加形態は単なる混合ではなく、一旦溶融してＮ
ｉと完全に合金化してしまうか、Ｉｌ械的紀噛合結合し
たメカニカルフロイ形態の複合粉末でなければならない
。The addition form of Si is not simply mixed, but once melted and N
It must be a composite powder in the form of a mechanical flow that is completely alloyed with I or mechanically interlocked with Il.
また、Ｆｅｊ５よび／又はＣｒの添加量がそれぞれが少
なくとも１％であって且つその合計が２０ｗｔ％以下と
なっているのは１％未満では表面にＩＩｋ密な酸化膜が
充分に形成されず充分な耐酸化性を付与できない、一方
、その合計量か２０ｗｌ；％を越えると酸化膜の量が多
くなり、シート抵抗が増大して導体として使用できなく
なる。In addition, the addition amount of Fej5 and/or Cr is at least 1% each and the total is 20wt% or less because if it is less than 1%, a IIk-dense oxide film will not be sufficiently formed on the surface. On the other hand, if the total amount exceeds 20%, the amount of oxide film increases, the sheet resistance increases, and it becomes impossible to use it as a conductor.
口が３ ｗ ｔ％未満では液相が均一各こＮｉ粒子表面
は覆うことができず、また基板との接着強度が低下する
。１０ｗｔ％を越えるとシート抵抗が高くなってしまう
。If the amount is less than 3 wt%, the liquid phase cannot uniformly cover the surface of each Ni particle, and the adhesive strength with the substrate decreases. If it exceeds 10 wt%, the sheet resistance will increase.
Ｓｉがｌｏｗｔ％以上ではシート抵抗が増大してしまう
−Ｓｉ（ｆ添加されな−くともＢＩｌ独で酸化防止効果
があるが、Ｓｉが添加されると接着強度が高くなるため
添加することが好ましい。If Si exceeds lowt%, the sheet resistance will increase.Even if Si(f) is not added, BIl alone has an antioxidant effect, but when Si is added, the adhesive strength increases, so it is preferable to add Si. .
しかし、これもＢとＳｊの合計がｌ ５ ｗ ｔ％を越
えた添加量はシート抵抗が増大するのでＩ５ｗＬ％以下
とすべきである。However, if the total amount of B and Sj exceeds l 5 wt%, the sheet resistance will increase, so it should be kept below I5wL%.
さら紀、この特定発明の合金粉末または複合粉末に Ｓ
ｂ、 Ｂｉ、 ｉｎ、 Ｒ４ｇ 、 Ｐ
ｒ、 Ｓｎ、 ＺｎまたはＬａの少なくとも一
種を含有する合金粉末を使用して、ニッケル導電ペース
トを作るか、あるいは特定発明の合金粉末又は複合粉末
にこれら金属の粉末又はこれらを主体としたニッケル合
金粉末（複合粉末も含む、）と併用して導電ペーストと
するときは５００℃というＩｔｓでも焼結性がよく、シ
ート抵抗値が低い導電ペーストが得られる。この理由は
解明されたわけではないが、これらの添加元票とＮｉと
が低温で液相を形成するため、ＩＩｋ密な焼結が起きて
シート抵抗値が低くなるためと推爺する。しかし、これ
ら金属の添加量が（Ｌ １ｗｔ％以下だと液相の量が
少なくて低温では焼結が進まず、５ｗｔ％以上だと添加
元素の酸化が進んでシート抵抗値の−Ｅ昇が起きてしま
うので、この範囲内にすべきであろう。Saraki, S for the alloy powder or composite powder of this particular invention.
b, Bi, in, R4g, P
A nickel conductive paste is made using an alloy powder containing at least one of r, Sn, Zn, or La, or a powder of these metals or a nickel alloy powder mainly containing these metals is added to the alloy powder or composite powder of the specified invention. (Including composite powder) When used in combination to form a conductive paste, a conductive paste with good sinterability and a low sheet resistance value can be obtained even at 500°C. Although the reason for this has not been elucidated, it is presumed that these additives and Ni form a liquid phase at low temperatures, resulting in dense sintering of IIk, resulting in a low sheet resistance value. However, if the amount of these metals added is less than (L) 1wt%, the amount of liquid phase will be small and sintering will not proceed at low temperatures, and if it is more than 5wt%, oxidation of the added elements will progress and the -E increase in sheet resistance will occur. This should be within this range since this may occur.
本発明において使用する合金粉末又は複合粉末のサイズ
は粒径１０ｕｍ以下のもの、好ましくはｆ均拉径（Ｄ□
）が０．５〜５μｍのものを使用する−１０ｕｍより大
きくなるとビヒークル中での分散性が悪くなり印刷がう
まく行かず、インキのぼた右らによる短絡やカスレ墨こ
よる断線等が起こる危険が生ずる。The alloy powder or composite powder used in the present invention has a particle size of 10 um or less, preferably f uniform diameter (D□
) is 0.5 to 5 μm. If it is larger than 10 μm, the dispersibility in the vehicle will be poor and printing will not go well, and there is a risk of short circuits due to ink droplets, disconnections due to blurred ink, etc. occurs.
有機溶媒としては限定する訳でないが、通常導電ペース
トに使用されているテルピネオール、ブチルカルピトー
ル、ブチルカルピトール、アセテートまたは２−２−４
−トリメチルート３−ペンタンジオールモノイソブチレ
ートＣテキサノール）等が使用できる。Examples of organic solvents include, but are not limited to, terpineol, butylcarpitol, butylcarpitol, acetate, or 2-2-4, which are commonly used in conductive pastes.
-trimethylto-3-pentanediol monoisobutyrate (C-texanol), etc. can be used.
バインダーとしてもｔＩｌｗｉある訳なく、通常使用さ
れているエチルセルローズで充分である。There is no such thing as a binder, and the commonly used ethyl cellulose is sufficient.
ガラスフリットも粒度も合金粉末と同程度であれば制限
がなく、通常使用されているものであれば使用できるが
、好ましくは熱膨張係数の小さい軟化点５５０℃以下の
ガラス、例えばはうけい酸鉛ガラス等を選ぶべきである
。There are no restrictions as long as the particle size of the glass frit is the same as that of the alloy powder, and any commonly used glass can be used, but it is preferable to use glass with a small coefficient of thermal expansion and a softening point of 550°C or lower, such as silicic acid. You should choose lead glass etc.
混合割合としては、例えば合金粉末８８〜９２ｗＬ％、
ガラスフリフト１２〜８ｗｔ％からなるｖ４形分８５巾
量部に有ＩＩ溶媒とビヒークルの合計：ｉｔｌ ５ ＠
！ａ部（ペーストとしての粘度２００〜３５０Ｋｃｐｓ
になるように選ぶ、）を、例えば三本ロールのごとき混
和機を用いて充分混合することにより得ることができる
。As a mixing ratio, for example, alloy powder 88-92wL%,
V4 form consisting of 12-8 wt% of glass lift, 85 width parts, total of II solvent and vehicle: itl 5 @
! Part a (viscosity as paste 200-350Kcps
), for example, by thoroughly mixing them using a mixer such as a three-roll mixer.
以下、実施例により本発明をｎ体的に部用する。EXAMPLES Hereinafter, the present invention will be explained in part by way of Examples.
１実施例１
（実施例！〜１６．比較例１〜５》
第１表番こ示す組成の粉末を準備し、有機溶媒としてテ
キサノールをバインダーとしてエチルセルロースを使用
し、合金粉末以外の同形成分としてはほうけい酸鉛ガラ
スを使用したにれらを所定のソリッド（ｖ４ＪＦｇ成分
）濃度となるように配合してペーストを得た。有Ｉｌ溶
媒と粉末及びガラスとの混合には三本ロールミルをｆｆ
用した。ペーストの粘度は印刷可能な粘度２００〜３５
０Ｋｃｐｓになるように、特番こビヒークル中のエチル
セルロースにより調整した。1 Example 1 (Example! ~ 16. Comparative Examples 1 ~ 5) Powders having the composition shown in Table 1 were prepared, Texanol was used as an organic solvent, ethylcellulose was used as a binder, and the same components other than alloy powder were used. A paste was obtained by blending silicate glass using lead borosilicate glass to a predetermined solid (v4JFg component) concentration.A three-roll mill was used to mix the solvent, powder, and glass.
used. The viscosity of the paste is printable viscosity 200-35
It was adjusted to 0Kcps using ethyl cellulose in a special vehicle.
得られたペーストを用い、通常の板ガラスであるソーダ
石灰ガラス基板及び９６％アルミナ基板の片面に標準パ
ターンを印刷した。印刷後のレベリングは１５分間とし
、乾燥は１２０℃×１５分冊とした。焼成には厚膜焼成
炉を使用し、大気中で焼成した。焼成条件は６０分プロ
ファイル。Using the obtained paste, a standard pattern was printed on one side of a soda lime glass substrate and a 96% alumina substrate, which are ordinary plate glass. Leveling after printing was carried out for 15 minutes, and drying was carried out at 120°C x 15 volumes. A thick film firing furnace was used for firing, and the firing was carried out in the atmosphere. The firing conditions are a 60 minute profile.
ピーク温度５７５〜６００℃ＸＩＯ分間（フリット入り
）−８００℃ｘ１０分間（フリットレス：実施例１６）
とした。焼成膜厚は１８〜３０６ｍであった。Peak temperature 575-600°C for XIO minutes (with frit) -800°C for 10 minutes (fritless: Example 16)
And so. The fired film thickness was 18 to 306 m.
第１Ｒ紀特性Ｗ【シート抵抗、接着強度及びはんだ濡れ
性）の評価結果を併記する。The evaluation results of the 1st R period properties W (sheet resistance, adhesive strength, and solder wettability) are also listed.
なお、接着強度の測定には第１ＦＡに示すように得られ
たソーダ石灰ガラス基板又はアルミナ基板ｌのパターン
印刷面２８こ２ ｍ ｍ口バッド３を接着し、これに（
Ｌ６ｍｍφの錫メッキ飼ワイヤ４を取りつけ、９０°ビ
ール法番こてａＳ強度を測定した。接着強度が４Ｋｇ以
上の場合を良好と評価した。In order to measure the adhesive strength, the pattern printed surface 28 of the soda-lime glass substrate or alumina substrate 1 obtained as shown in the first FA was bonded to a 2 mm opening pad 3, and (
A tin-plated wire 4 with a length of 6 mmφ was attached, and the 90° Beer method trowel aS strength was measured. A case where the adhesive strength was 4 kg or more was evaluated as good.
また。シート抵抗はデジタル−ボルトメーターによって
測定し、２０ｍΩ／口以下の場合を使用可能と評価した
。Also. The sheet resistance was measured using a digital voltmeter, and a sheet resistance of 20 mΩ/mouth or less was evaluated as usable.
はんだ濡れ性は２ｍｍ口パッドを使用し、６／４はんだ
を溶かし、２２０℃に温度ａｌｉｌしであるはんだ槽番
こディップさせ、各パッドの濡れ面積を測定して評価し
た。濡れ面積が９５％以上の場合墨こ０印、８５〜９５
％の場合にＯ印を付してそれぞれ良好と評価し、８５％
以下の場合にはｘ印を付して不合格と評価した。Solder wettability was evaluated by using a 2 mm pad, melting 6/4 solder, dipping it in a solder bath at a temperature of 220° C., and measuring the wetted area of each pad. If the wet area is 95% or more, black mark 0, 85-95
If the percentage is 85%, mark it with O and evaluate it as good.
The following cases were marked with an x mark and evaluated as failing.
第１Ｊより本発明例はいずれも酋特性が優れていること
が判る。From No. 1J, it can be seen that all of the examples of the present invention have excellent shearing characteristics.
一方、合金粉末の組成でＦｅあるいはＣｒの含＝１が２
０ｗｔ％を越えている比較例は酸化のためシー−ト抵抗
が高く、はんだ濡れ性も悪い。On the other hand, in the composition of the alloy powder, the content of Fe or Cr = 1 is 2.
Comparative examples in which the content exceeds 0 wt% have high sheet resistance due to oxidation and poor solder wettability.
また。ＢあるいはＳｉの合計が１５ｗｔ％を越える合金
組成である比較例では、＃化物成分の総量が多くなり、
シート抵抗が高くなっている。一方、■あるいはＳｉの
合計が３ｗｔ％に満たない合金組成では伯の合金成分の
酸化によりシート抵抗が高く、はんだ濡れ性も悪い。Also. In the comparative example, which has an alloy composition in which the total of B or Si exceeds 15 wt%, the total amount of # compound components increases,
Sheet resistance is high. On the other hand, in an alloy composition in which the total amount of Si or Si is less than 3 wt %, the sheet resistance is high due to the oxidation of the alloy component in B, and the solder wettability is also poor.
Ｃ以下余白） （実施例１７〜２７．比較例６〜７》 第２表に示す組成の粉末と（Ｓｂ、Ｉｌｉ。Margin below C) (Examples 17-27. Comparative Examples 6-7) Powder having the composition shown in Table 2 and (Sb, Ili.
Ｉ ｎ、 Ｍｇ、 Ｉｒ、 Ｓｎ、 Ｚｎ、 Ｌａ）
８０ｗｔ−％−Ｎｉ２０ｗｔ％合金粉末を準備し、実施
例１の場合とｊＪ様にして、有機ｊ８媒としてテキサノ
ールをバインダーとしてエチルセルロースを使用し、ガ
ラス成分としてはほうけい酸鉛ガラスを使用した。所定
のソリッド（固形成分）ｉＤ度となるように配合し、混
練してペーストを得た。In, Mg, Ir, Sn, Zn, La)
An 80wt-%-Ni20wt% alloy powder was prepared, and in the same manner as in Example 1, Texanol was used as the organic J8 medium, ethyl cellulose was used as the binder, and lead borosilicate glass was used as the glass component. They were blended to a predetermined solid (solid component) iD degree and kneaded to obtain a paste.
得られたペーストを用い、通常の板ガラスであるソーダ
石灰ガラス基板及びアルミナ基板の片面番こ標準パター
ンを印刷した。印Ｆａ後のレベリングは１５分間とし、
乾燥は１２０℃×１５分間とした。焼成番こは厚膜焼成
炉を使用し、大気中で焼成した。焼成条件は６０分プロ
ファイル、ピーク温度５００〜６００℃ＸＩＯ分間（フ
リット入り）、６００℃×１０分間（フリーｌトレス：
実施例２７）とした。焼成膜厚は１８〜３０ｕｍであっ
た。The resulting paste was used to print a standard pattern on one side of a soda-lime glass substrate and an alumina substrate, which are ordinary plate glasses. Leveling after mark Fa is 15 minutes.
Drying was carried out at 120° C. for 15 minutes. The fired plate was fired in the atmosphere using a thick film firing furnace. Firing conditions were 60 minute profile, peak temperature 500-600℃ for XIO minutes (with frit), 600℃ for 10 minutes (free trace:
Example 27). The fired film thickness was 18 to 30 um.
なお、接ファ ９ＭＪ（ｆ 、シート抵抗の測定及びは
んだ濡れ性の評価は実施例１の場合と同様である。Note that the measurement of contact resistance 9MJ (f), sheet resistance, and evaluation of solder wettability were the same as in Example 1.
第２表より本発明例はいずれも各特性が優れていること
が判る。It can be seen from Table 2 that all the examples of the present invention are excellent in each characteristic.
一方、合金粉末の組成で添加元素の組成が小さい場合の
比較例６では、＃ｉ相が少なく焼結が進まずにシート抵
抗が高くなっている。また。添加元素の組成が大きすぎ
る場合の比較例７では添加元素の酸化が進み、シート抵
抗が高く、はんだ濡れ性も思い。On the other hand, in Comparative Example 6 in which the composition of the additive element is small in the composition of the alloy powder, the #i phase is small and sintering does not proceed, resulting in a high sheet resistance. Also. In Comparative Example 7, in which the composition of the additive element was too large, the oxidation of the additive element progressed, resulting in high sheet resistance and poor solder wettability.
Ｃ以下余白）
１効 宋Ｊ
本特定発明の合金粉末又はメカニカルアロイ形態の複合
粉末を使用したニッケル導電ペーストは大ＩＡ（中位成
がｔｉｌ能であって、はんだ居れ性に優れ、シート抵抗
も少なく、またボンディングの接着強度も充分あって、
Ｒ金属を使用しない番こもかかわらず充分なペースト性
能を有している。1 effect Song J The nickel conductive paste using the alloy powder or mechanical alloy composite powder of the present specified invention has a high IA (medium tiling ability, excellent solderability, and sheet resistance. The bonding strength is low, and the bonding strength is sufficient.
It has sufficient paste performance even though it does not use R metal.
また。Ｓｂ、Ｂｉ、Ｉｎ、Ｍｇ、Ｐｒ、Ｓｎ。Also. Sb, Bi, In, Mg, Pr, Sn.
Ｚｎまたは１−ａを含むｔ記合金粉末又は複合粉末を使
川するか、特定発明の合金粉末又はへ金粉末にＳｂ、Ｉ
ｌｉ、Ｉｎ、Ｍｇ、Ｉｒ、Ｓｎ、Ｚｎまたはｌ ａの金
属を添加した合金粉末父は複合粉末、又はそのニッケル
合金粉末もしくは複合粉末を併用するときは、焼成温度
を低下させる効果があって優れたニッケル導電ペースト
を提供するものであるー
このペーストは通常のＩＩ Ｉ Ｃだけでなく、プラズ
マディスプレイパネルの電極やセラミックコンデンサー
の内部、外部電棒としても使用可能な導電 電ペース
トである。Use the alloy powder or composite powder containing Zn or 1-a, or add Sb, I to the alloy powder or hemetal powder of the specified invention.
The alloy powder to which Li, In, Mg, Ir, Sn, Zn or La metal is added is a composite powder, or when used in combination with nickel alloy powder or composite powder, it has the effect of lowering the firing temperature and is excellent. This paste provides a nickel conductive paste that can be used not only for ordinary II ICs, but also for electrodes in plasma display panels and internal and external conductive rods in ceramic capacitors.
第１図は接着強度試験の際の接着状況を示す図である。 １０基板 ２．印刷面 FIG. 1 is a diagram showing the adhesion situation during an adhesive strength test. 10 boards 2. Printing surface
Claims (4)
上であって、この両者の合計が２０ｗｔ％以下、Ｂ３〜
１０ｗｔ％、Ｓｉは１０ｗｔ％以下であって、ＢとＳｉ
の合計は１５ｗｔ％以下、残りＮｉからなる合金粉末又
はメカニカルアロイ形態の複合粉末を使用することを特
徴とするニッケル導電ペースト。(1) Cr and/or Fe are each 1 wt% or more, and the total of both is 20 wt% or less, B3~
10wt%, Si is 10wt% or less, and B and Si
A nickel conductive paste characterized by using an alloy powder or a composite powder in the form of a mechanical alloy, with a total of 15 wt% or less and the remainder being Ni.
ルアロイ形態の複合粉末が、Ｓｂ、Ｂｉ、Ｉｎ、Ｍｇ、
Ｐｒ、Ｓｎ、ＺｎまたはＬａの少なくとも１種を０．１
〜５ｗｔ％含むことを特徴とするニッケル導電ペースト
。(2) The alloy powder or mechanical alloy composite powder according to claim 1 contains Sb, Bi, In, Mg,
0.1 of at least one of Pr, Sn, Zn or La
A nickel conductive paste characterized by containing ~5wt%.
ルアロイ形態の複合粉末１００重量部に対し、Ｓｂ、Ｂ
ｉ、Ｉｎ、Ｍｇ、Ｐｒ、Ｓｎ、ＺｎまたはＬａの一種又
はこの金属を主体とするニッケル合金粉末（メカニカル
アロイ形態の複合粉末も含む。）を上記金属が０．１〜
５重量部の比率で使用したことを特徴とするニッケル導
電ペースト。(3) Sb, B
i, In, Mg, Pr, Sn, Zn, or La, or a nickel alloy powder (including composite powder in mechanical alloy form) mainly composed of this metal, in which the above metal is 0.1~
A nickel conductive paste characterized in that it is used in a ratio of 5 parts by weight.
合金粉末又はメカニカルアロイ形態の複合粉末とガラス
フリット、ビヒークルおよび有機溶媒からなるニッケル
導電ペースト。(4) A nickel conductive paste comprising the alloy powder or mechanical alloy composite powder according to any one of claims 1 to 3, a glass frit, a vehicle, and an organic solvent.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP28770489A JPH03149706A (en) | 1989-11-04 | 1989-11-04 | Nickel conductive paste |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP28770489A JPH03149706A (en) | 1989-11-04 | 1989-11-04 | Nickel conductive paste |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPH03149706A true JPH03149706A (en) | 1991-06-26 |
Family
ID=17720658
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP28770489A Pending JPH03149706A (en) | 1989-11-04 | 1989-11-04 | Nickel conductive paste |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH03149706A (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US7267713B2 (en) | 2003-04-28 | 2007-09-11 | Murata Manufacturing Co., Ltd. | Conductive paste and glass circuit structure |
| JP2010526414A (en) * | 2007-04-25 | 2010-07-29 | フエロ コーポレーション | Formation of thick film conductor made of silver and nickel, or silver and nickel alloy, and solar cell made therefrom |
-
1989
- 1989-11-04 JP JP28770489A patent/JPH03149706A/en active Pending
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US7267713B2 (en) | 2003-04-28 | 2007-09-11 | Murata Manufacturing Co., Ltd. | Conductive paste and glass circuit structure |
| JP2010526414A (en) * | 2007-04-25 | 2010-07-29 | フエロ コーポレーション | Formation of thick film conductor made of silver and nickel, or silver and nickel alloy, and solar cell made therefrom |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| KR101172723B1 (en) | Copper conductor paste, conductor circuit board and electronic part | |
| JP3209089B2 (en) | Conductive paste | |
| US4070518A (en) | Copper metallizations | |
| JPS6035405A (en) | Copper conductor composition | |
| TW200418221A (en) | Terminal electrode compositions for multilayer ceramic capacitors | |
| JPH07500450A (en) | Silver-rich conductor composition with high thermal cycle adhesion and aging adhesion | |
| JP4456612B2 (en) | Copper conductor paste, conductor circuit board and electronic components | |
| JP2000048642A (en) | Conductive paste and glass circuit substrate | |
| JP2001307547A (en) | Conductive composition and printed circuit board using the same | |
| JP3297531B2 (en) | Conductive paste | |
| JP4423832B2 (en) | Glass composition and thick film paste using the same | |
| JP4495740B2 (en) | Copper conductor paste, conductor circuit board and electronic components | |
| JPH03149706A (en) | Nickel conductive paste | |
| JPH04190502A (en) | Copper conductor paste | |
| JPH0153907B2 (en) | ||
| JPH0346705A (en) | Copper paste | |
| JPH0465011A (en) | Copper conductive paste | |
| JPH0488067A (en) | Conductor paste | |
| JPS60137847A (en) | Composition for forming thick film | |
| JPH0349108A (en) | Copper conductor composition material | |
| JPH01107592A (en) | Electric circuit board | |
| JP3862119B2 (en) | Resistance paste | |
| JPS5831509A (en) | Thick film conductor composition | |
| JPS5946703A (en) | Inorganic composition for insulating ceramic paste | |
| JP2992958B2 (en) | Conductive paste for low-temperature fired multilayer wiring boards |