JPH05335108A - Thick film resistance composition and thick film resistor using thereof - Google Patents
Thick film resistance composition and thick film resistor using thereofInfo
- Publication number
- JPH05335108A JPH05335108A JP4140287A JP14028792A JPH05335108A JP H05335108 A JPH05335108 A JP H05335108A JP 4140287 A JP4140287 A JP 4140287A JP 14028792 A JP14028792 A JP 14028792A JP H05335108 A JPH05335108 A JP H05335108A
- Authority
- JP
- Japan
- Prior art keywords
- thick film
- weight
- glass
- parts
- boride
- 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
- 239000000203 mixture Substances 0.000 title claims abstract description 37
- 239000011521 glass Substances 0.000 claims abstract description 66
- 229910052751 metal Inorganic materials 0.000 claims abstract description 48
- 239000002184 metal Substances 0.000 claims abstract description 48
- 239000011159 matrix material Substances 0.000 claims abstract description 24
- BPUBBGLMJRNUCC-UHFFFAOYSA-N oxygen(2-);tantalum(5+) Chemical compound [O-2].[O-2].[O-2].[O-2].[O-2].[Ta+5].[Ta+5] BPUBBGLMJRNUCC-UHFFFAOYSA-N 0.000 claims abstract description 22
- 229910001936 tantalum oxide Inorganic materials 0.000 claims abstract description 22
- 239000002245 particle Substances 0.000 claims abstract description 18
- XTDAIYZKROTZLD-UHFFFAOYSA-N boranylidynetantalum Chemical compound [Ta]#B XTDAIYZKROTZLD-UHFFFAOYSA-N 0.000 claims abstract description 12
- 239000000758 substrate Substances 0.000 claims abstract description 7
- 238000010304 firing Methods 0.000 claims description 10
- 229910044991 metal oxide Inorganic materials 0.000 claims description 9
- 150000004706 metal oxides Chemical class 0.000 claims description 9
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical group [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 claims description 5
- 229910052796 boron Inorganic materials 0.000 claims description 5
- 239000004020 conductor Substances 0.000 claims description 5
- 238000004519 manufacturing process Methods 0.000 claims description 3
- 230000001376 precipitating effect Effects 0.000 claims 1
- 239000000463 material Substances 0.000 abstract description 9
- 239000011261 inert gas Substances 0.000 abstract description 6
- 238000000034 method Methods 0.000 abstract description 2
- 230000000052 comparative effect Effects 0.000 description 9
- 238000010586 diagram Methods 0.000 description 6
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 5
- 229910052802 copper Inorganic materials 0.000 description 5
- 239000010949 copper Substances 0.000 description 5
- 238000000926 separation method Methods 0.000 description 5
- 238000002441 X-ray diffraction Methods 0.000 description 4
- 230000000694 effects Effects 0.000 description 4
- 239000010419 fine particle Substances 0.000 description 4
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 2
- 239000005287 barium borate glass Substances 0.000 description 2
- 239000006063 cullet Substances 0.000 description 2
- 229910001873 dinitrogen Inorganic materials 0.000 description 2
- 238000002955 isolation Methods 0.000 description 2
- 238000002844 melting Methods 0.000 description 2
- 230000008018 melting Effects 0.000 description 2
- 230000009257 reactivity Effects 0.000 description 2
- 230000006641 stabilisation Effects 0.000 description 2
- 238000011105 stabilization Methods 0.000 description 2
- VXQBJTKSVGFQOL-UHFFFAOYSA-N 2-(2-butoxyethoxy)ethyl acetate Chemical compound CCCCOCCOCCOC(C)=O VXQBJTKSVGFQOL-UHFFFAOYSA-N 0.000 description 1
- 239000004925 Acrylic resin Substances 0.000 description 1
- 229920000178 Acrylic resin Polymers 0.000 description 1
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 1
- 229910006404 SnO 2 Inorganic materials 0.000 description 1
- KGBXLFKZBHKPEV-UHFFFAOYSA-N boric acid Chemical compound OB(O)O KGBXLFKZBHKPEV-UHFFFAOYSA-N 0.000 description 1
- 239000004327 boric acid Substances 0.000 description 1
- 239000005388 borosilicate glass Substances 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
- 238000013329 compounding Methods 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 239000000075 oxide glass Substances 0.000 description 1
- 229910052761 rare earth metal Inorganic materials 0.000 description 1
- 150000002910 rare earth metals Chemical class 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
Landscapes
- Apparatuses And Processes For Manufacturing Resistors (AREA)
- Non-Adjustable Resistors (AREA)
Abstract
Description
【0001】[0001]
【産業上の利用分野】本発明は不活性ガス雰囲気中で焼
成する厚膜抵抗組成物及び該組成物からなる厚膜抵抗体
に関する。BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a thick film resistor composition which is fired in an inert gas atmosphere and a thick film resistor comprising the composition.
【0002】[0002]
【従来の技術】不活性ガス雰囲気中で焼成することによ
って形成される厚膜抵抗体の抵抗特性の安定化について
は特公平2−3524号公報に記載されている。これ
は、金属6ほう化物にTa2O5ガラスを配合した厚膜抵
抗組成物による厚膜抵抗体の抵抗特性が安定化できると
云うものである。また、特に高抵抗領域をカバーするも
のとして、10kΩ/□〜10MΩ/□についてはSn
O2−ガラス系抵抗組成物が開発されている。2. Description of the Related Art Stabilization of resistance characteristics of a thick film resistor formed by firing in an inert gas atmosphere is described in Japanese Patent Publication No. 2-3524. This means that the resistance characteristics of the thick film resistor can be stabilized by the thick film resistor composition in which metal 6 boride is mixed with Ta 2 O 5 glass. Moreover, as a material particularly covering the high resistance region, Sn is applied for 10 kΩ / □ to 10 MΩ / □.
O 2 - glass-based resistor compositions have been developed.
【0003】[0003]
【発明が解決しようとする課題】本発明者らの検討によ
れば、上記金属6ほう化物とTa2O5ガラスからなる厚
膜抵抗組成物は、厚膜ハイブリッドICの抵抗体として
要求される抵抗領域10Ω/□〜10MΩ/□、特に、
高抵抗領域10kΩ/□〜10MΩ/□の抵抗特性、抵
抗値バラツキ及び電流ノイズが十分安定しているとは云
い難い。従って、これまで高抵抗領域ではSnO2−ガ
ラス系材料が用いられてきたが、上記厚膜ハイブリッド
ICの抵抗体に要求される全抵抗領域を同系材料でカバ
ーでき、かつ、抵抗特性の安定な材料の提供については
解決されていないのが現状である。According to the studies made by the present inventors, the thick film resistor composition comprising the metal hexaboride and Ta 2 O 5 glass is required as a resistor for a thick film hybrid IC. Resistance area 10Ω / □ -10MΩ / □, especially,
It is hard to say that the resistance characteristics in the high resistance region of 10 kΩ / □ to 10 MΩ / □, resistance value variations and current noise are sufficiently stable. Therefore, the SnO 2 -glass material has been used in the high resistance region so far, but the entire resistance region required for the resistor of the thick film hybrid IC can be covered with the same material and the resistance characteristic is stable. At present, the provision of materials has not been resolved.
【0004】従来の2元系材料では、不活性ガス雰囲気
中で焼成する厚膜ハイブリットICの抵抗体として最も
要求される中間領域(1kΩ/□〜10kΩ/□)の抵
抗体の特性の安定化が達成できなかった。そのため厚膜
ハイブリットICにおいて精密回路を形成する隘路とな
っていた。With conventional binary materials, stabilization of the characteristics of the resistor in the intermediate region (1 kΩ / □ to 10 kΩ / □) most required as the resistor of the thick film hybrid IC fired in an inert gas atmosphere. Could not be achieved. Therefore, it has been a bottleneck for forming a precision circuit in the thick film hybrid IC.
【0005】本発明の目的は、同系材料により前記の広
範な全抵抗領域において、抵抗特性の安定な厚膜抵抗体
を与える抵抗組成物を提供することにある。It is an object of the present invention to provide a resistance composition which provides a thick film resistor having stable resistance characteristics in the wide range of the entire resistance range by using the similar material.
【0006】本発明の他の目的は、上記抵抗組成物を用
いた厚膜抵抗体及びその製法を提供することにある。Another object of the present invention is to provide a thick film resistor using the above resistance composition and a method for producing the same.
【0007】[0007]
【課題を解決するための手段】本発明者らは、焼成後の
抵抗体のガラスマトリックス中に微細な導電粒子を均一
に分散させ、更にはガラスマトリックス自体にも導電性
を与えれば、抵抗体の微細領域での抵抗率が均一化し、
前記課題を解決することができると考えた。そして、各
種の厚膜抵抗組成物を配合し、その抵抗特性を検討し本
発明に到達した。前記課題を解決する本発明の要旨は次
のとおりである。Means for Solving the Problems The present inventors have made it possible to uniformly disperse fine conductive particles in a glass matrix of a resistor after firing, and further to give conductivity to the glass matrix itself. Resistivity becomes uniform in the fine area of
I thought that I could solve the above problems. Then, various thick film resistance compositions were blended, and their resistance characteristics were examined to arrive at the present invention. The gist of the present invention for solving the above problems is as follows.
【0008】(1)(a)金属ほう化物をMxBy(但
し、Mは金属元素、Bはほう素、x及びyは整数を示
す)で示すときy/xが6を超える金属ほう化物0.1
〜50重量部、(b)酸化タンタルに換算して1〜50
重量部をガラス成分として含有するガラスフリット50
〜99.9重量部、(d)ペースト状とするのに有効量
の有機ビヒクル、を含むことを特徴とする厚膜抵抗組成
物及び該組成物を用いた厚膜抵抗体。(1) When (a) a metal boride is represented by MxBy (where M is a metal element, B is boron, and x and y are integers), y / x is more than 6; 1
˜50 parts by weight, (b) 1 to 50 in terms of tantalum oxide
Glass frit 50 containing parts by weight as a glass component
-99.9 parts by weight, and (d) an organic vehicle in an amount effective for forming a paste, a thick film resistor composition and a thick film resistor using the composition.
【0009】(2)厚膜抵抗組成物を無機質基板面に塗
布して所定の形状の抵抗膜を形成し、これを不活性ガス
雰囲気中で700℃〜950℃で焼成することによりガ
ラスマトリックス中に粒径0.1μm以下のほう化タン
タルを析出させるかまたはガラスに導電性を生ぜしめる
ことを特徴とする厚膜抵抗体の製法。(2) A thick film resistance composition is applied to the surface of an inorganic substrate to form a resistance film having a predetermined shape, and the resistance film is baked in an inert gas atmosphere at 700 ° C. to 950 ° C. in a glass matrix. A method for producing a thick film resistor, characterized in that tantalum boride having a grain size of 0.1 μm or less is deposited on the glass or the glass is made conductive.
【0010】本発明がその効果に最も重要な影響を与え
ると思われる因子としては、金属と配位するほう素の量
が挙げられる。これは12ほう化物のような金属ほう化
物(MxBy)においてy/xが6を超える金属ほう化
物でなくてはならない。なぜなら、y/xが6以下の金
属ほう化物を抵抗組成物に適用した場合、金属ほう化物
は酸化タンタルと反応しないか、または反応したとして
も6を超える金属ほう化物にくらべ反応は穏やかであ
り、反応生成物であるほう化タンタルを析出しにくいた
め高抵抗領域までも抵抗特性を改善するには至らないか
らである。The factor which is considered to have the most important effect on the effect of the present invention is the amount of boron which coordinates with the metal. It must be a metal boride with a y / x greater than 6 in a metal boride (MxBy) such as 12 boride. This is because when a metal boride having y / x of 6 or less is applied to the resistance composition, the metal boride does not react with tantalum oxide, or even if it reacts, the reaction is mild as compared with the metal boride having a y / x of more than 6. This is because the reaction product, tantalum boride, is hard to precipitate, so that the resistance characteristics cannot be improved even in the high resistance region.
【0011】なお、前記y/xが6を超える金属ほう化
物は、0.1〜50重量部、好ましくは5〜50重量部
配合する。The metal boride in which y / x exceeds 6 is added in an amount of 0.1 to 50 parts by weight, preferably 5 to 50 parts by weight.
【0012】また、y/xが6を超える金属ほう化物
は、酸化タンタルとの反応性に富むため、希土類6ほう
化物−Ta2O5含有ガラス系抵抗体のように、反応促進
を目的とした酸化タンタルのガラス中への添加ではな
く、結晶状態の酸化タンタルを抵抗組成物に適用した場
合もほぼ同様の特性を得ることができる。しかし、実用
的には酸化タンタルを含有したガラスを用いた抵抗組成
物のほうが抵抗特性はより安定化し易い。従って、酸化
タンタルはガラス中に含有させるのが望ましい。Further, since a metal boride having y / x exceeding 6 is highly reactive with tantalum oxide, it is intended to promote the reaction like a rare earth hexaboride-Ta 2 O 5 -containing glass-based resistor. When tantalum oxide in a crystalline state is applied to the resistance composition instead of adding the above-mentioned tantalum oxide to the glass, almost the same characteristics can be obtained. However, practically, the resistance characteristics of the resistance composition using the glass containing tantalum oxide are more easily stabilized. Therefore, it is desirable that tantalum oxide is contained in the glass.
【0013】本発明においては、金属ほう化物と反応し
て導電性粒子を析出させるかもしくはガラスマトリック
スを導電化させる反応性金属酸化物としては前記酸化タ
ンタルに限定するものではなく、IVa〜VIa族の金属酸
化物であれば同様の作用が得られる。しかし、酸化タン
タル以外のIVa〜VIa族の金属酸化物は反応性に乏しい
ため金属ほう化物は反応性に富むAlB12を用いなけれ
ば、良好な抵抗特性を得ることは難しい。In the present invention, the reactive metal oxide which reacts with the metal boride to precipitate the conductive particles or makes the glass matrix conductive is not limited to the above tantalum oxide, and it is not limited to the group IVa to VIa. The same effect can be obtained with the above metal oxide. However, since metal oxides of groups IVa to VIa other than tantalum oxide have poor reactivity, it is difficult to obtain good resistance characteristics of the metal boride unless AlB 12 having high reactivity is used.
【0014】本発明が用いる酸化タンタルを含むガラス
としては、前記金属ほう化物によって還元されないガラ
スであれば特に限定されないが、ほう硅酸ガラス、ほう
酸バリウム系ガラスが好ましい。The glass containing tantalum oxide used in the present invention is not particularly limited as long as it is not reduced by the metal boride, but borosilicate glass and barium borate glass are preferable.
【0015】ハイブリッドIC用厚膜抵抗体は、通常7
00〜950℃で焼成できることが望ましい。しかし、
高融点の酸化タンタルを含むとガラスの軟化点が上昇
し、前記温度では抵抗体を緻密に焼成できない。但し、
ガラスの軟化点を下げるとガラスが前記反応の触媒的作
用を増大するので、ほう酸等の低融点酸化物を用いてガ
ラスの軟化点を低げることが好ましい。その一例とし
て、ほう酸バリウム系ガラスの場合、配合比はTa
2O5:1〜50重量部、B2O3:25〜74重量部、B
aO:25〜74重量部が望ましい。なお、酸化タンタ
ルが1重量部未満ではほう化タンタルの析出量が少な
く、導電パスとしての効果が少ないために抵抗特性を十
分に改善できず、50重量部を超えるとガラスの軟化点
が高くなり、前記焼成温度で緻密な抵抗体の焼成が困難
になる。Thick film resistors for hybrid ICs are usually 7
It is desirable that the firing can be performed at 00 to 950 ° C. But,
If tantalum oxide having a high melting point is contained, the softening point of glass rises, and the resistor cannot be densely fired at the above temperature. However,
Since lowering the softening point of the glass increases the catalytic action of the reaction, it is preferable to use a low melting point oxide such as boric acid to lower the softening point of the glass. As an example, in the case of barium borate glass, the compounding ratio is Ta.
2 O 5 : 1 to 50 parts by weight, B 2 O 3 : 25 to 74 parts by weight, B
aO: 25 to 74 parts by weight is desirable. If the amount of tantalum oxide is less than 1 part by weight, the amount of deposited tantalum boride is small and the effect as a conductive path is small, so that the resistance characteristics cannot be sufficiently improved, and if it exceeds 50 parts by weight, the softening point of the glass becomes high. However, it becomes difficult to fire a dense resistor at the firing temperature.
【0016】[0016]
【作用】本発明の抵抗組成物が抵抗特性の安定な抵抗体
を与えるのは、抵抗組成物としてy/xが6を超える金
属ほう化物と、反応性金属酸化物として酸化タンタルを
用いた点にある。The resistance composition of the present invention provides a resistor having stable resistance characteristics because a metal boride having y / x of more than 6 is used as the resistance composition and tantalum oxide is used as the reactive metal oxide. It is in.
【0017】これを不活性ガス中で焼成すると、金属ほ
う化物と酸化タンタルが反応し、ガラスマトリックス中
にほう化タンタルの微細な粒子が析出し、ガラス自体に
導電性が生ずる。該粒子は0.1μm以下の微粒子で、
図1の模式図に示すように、ガラスマトリックス3中に
分散した前記金属ほう化物(例えばAlB12)1とガラ
スの粒界及びガラスマトリックス中にほう化タンタル粒
子2が析出する。該ほう化タンタル微粒子2が微細な導
電ネットワークを形成する。導電性ガラスは前記反応が
ガラス中の酸化タンタルまたは焼成によりガラス中に溶
解した酸化タンタルと前記金属ほう化物が反応すること
により、ガラスに原子価交換が行われて導電性を生じた
ものと考えられる。When this is fired in an inert gas, the metal boride reacts with tantalum oxide, and fine particles of tantalum boride are deposited in the glass matrix, so that the glass itself becomes conductive. The particles are fine particles of 0.1 μm or less,
As shown in the schematic diagram of FIG. 1, tantalum boride particles 2 are precipitated in the glass matrix 3 and the metal boride (for example, AlB 12 ) 1 dispersed in the glass matrix 3 and the glass grain boundaries. The tantalum boride fine particles 2 form a fine conductive network. Conductive glass is considered that the reaction caused tantalum oxide in the glass or tantalum oxide dissolved in the glass by firing to react with the metal boride, thereby causing valence exchange in the glass to cause conductivity. Be done.
【0018】これにより生じたほう化タンタル粒子2、
導電性ガラス及び前記金属ほう化物1によって導電パス
を形成することで抵抗体の抵抗率が均一化でき、抵抗特
性が安定化するものと考えられる。Tantalum boride particles 2 thus produced,
It is considered that by forming a conductive path with the conductive glass and the metal boride 1, the resistivity of the resistor can be made uniform and the resistance characteristics can be stabilized.
【0019】また、前記金属ほう化物の含有量が少ない
高抵抗体においても、同様に前記導電パスがそれなりに
形成されるために安定な抵抗特性のものが得られるもの
と考えられる。Further, it is considered that even in the case of the high resistance material containing a small amount of the metal boride, the conductive path is formed in a similar manner, so that stable resistance characteristics can be obtained.
【0020】[0020]
【実施例】本発明を実施例に基づき詳細に説明する。EXAMPLES The present invention will be described in detail based on examples.
【0021】〔実施例1〜6および比較例1〜7〕アル
ミナ基板上に銅ペーストを印刷し、窒素ガス雰囲気中で
焼成して銅導体回路を形成した。Examples 1 to 6 and Comparative Examples 1 to 7 Copper paste was printed on an alumina substrate and fired in a nitrogen gas atmosphere to form a copper conductor circuit.
【0022】次に、ガラスフリットとして表1に示す金
属酸化物の混合物を1200〜1500℃で溶融し、こ
れを空気中で乾式冷却することによりカレットを得た。
該カレットにアルコールを加えボールミル中で約48時
間粉砕して平均粒径5μm以下のガラスフリットを得
た。Next, as a glass frit, a mixture of the metal oxides shown in Table 1 was melted at 1200 to 1500 ° C., and this was dry-cooled in air to obtain a cullet.
Alcohol was added to the cullet and crushed in a ball mill for about 48 hours to obtain a glass frit having an average particle size of 5 μm or less.
【0023】[0023]
【表1】 [Table 1]
【0024】次に、市販の金属ほう化物と表1のガラス
フリットを表2に示す割合で混合し、アクリル樹脂をブ
チルカルビトールアセテートで溶解した有機ビヒクルを
所定量加えて均一混練し、本発明の抵抗組成物ペースト
を得た。Next, a commercially available metal boride and a glass frit shown in Table 1 were mixed at a ratio shown in Table 2, and a predetermined amount of an organic vehicle in which an acrylic resin was dissolved in butyl carbitol acetate was added and uniformly kneaded. A resistance composition paste of was obtained.
【0025】[0025]
【表2】 [Table 2]
【0026】次に、上記各組成物ペーストを前記銅導体
回路を形成したアルミナ基板上の所定個所に、325メ
ッシュのスクリーンを用いて1mm□の大きさの厚膜抵
抗体をスクリーン印刷し、これを120℃、10分乾燥
後、トンネル炉を用いて窒素ガス雰囲気中で900℃、
10分間の焼成を行い厚膜抵抗体を有する回路板を得
た。該厚膜抵抗体の面積抵抗値、電流ノイズ及び抵抗値
バラツキの測定結果を表2に示す。Next, each composition paste was screen-printed with a thick film resistor having a size of 1 mm square at a predetermined position on the alumina substrate having the copper conductor circuit formed thereon using a 325 mesh screen. At 120 ° C. for 10 minutes, and then 900 ° C. in a nitrogen gas atmosphere using a tunnel furnace.
Firing was performed for 10 minutes to obtain a circuit board having a thick film resistor. Table 2 shows the measurement results of the sheet resistance, current noise and resistance variation of the thick film resistor.
【0027】表2から明らかなように、金属ほう化物と
してAlB12を用いた実施例1の抵抗体は、前記y/x
が6以下の金属ほう化物(LaB6)を用いた比較例6
のものと比べて抵抗値のバラツキが小さく安定である。As is clear from Table 2, the resistor of Example 1 using AlB 12 as the metal boride has the above y / x.
Comparative Example 6 using a metal boride (LaB 6 ) having a value of 6 or less
Compared with the above, the resistance value has less variation and is stable.
【0028】一方、Ta2O5を65重量%含むNo.6
ガラスを用いた比較例2の抵抗体は、抵抗値が上昇しバ
ラツキも大きい。なお、比較例7は抵抗値が7Ω/□と
低いにもかかわらず、抵抗値バラツキが認められる。On the other hand, No. 6 containing 65% by weight of Ta 2 O 5
The resistance value of the resistor of Comparative Example 2, which uses glass, is large and has a large variation. In Comparative Example 7, although the resistance value is as low as 7Ω / □, the resistance value variation is recognized.
【0029】また、金属ほう化物としてAlB12を用い
た抵抗体とy/xが6以下の金属ほう化物(LaB6)
を用いた抵抗体の電流ノイズ及び抵抗値バラツキを比較
した。その結果を図2、図3に示す。図から本実施例の
ものは電流ノイズ及び抵抗値バラツキのいずれも小さい
ことが分かる。A resistor using AlB 12 as a metal boride and a metal boride having a y / x of 6 or less (LaB 6 )
The current noise and the resistance value variation of the resistors using are compared. The results are shown in FIGS. 2 and 3. From the figure, it can be seen that both the current noise and the resistance value variation of the present embodiment are small.
【0030】〔実施例7〜12および比較例8〜13〕
表3に示すように、y/xが異なる金属ほう化物及び結
晶性Ta2O5を用いて実施例1と同様に抵抗組成物を調
製した。表3から明らかなようにy/xが6を超える金
属ほう化物の抵抗体は、Ta2O5をガラスの一成分また
は結晶状態のどちらの状態で用いても、y/xが6以下
の金属ほう化物の抵抗体(比較例8〜13)に比べ電流
ノイズが小さい。[Examples 7 to 12 and Comparative Examples 8 to 13]
As shown in Table 3, a resistance composition was prepared in the same manner as in Example 1 using metal borides having different y / x and crystalline Ta 2 O 5 . As is apparent from Table 3, the metal boride resistor with y / x exceeding 6 has a y / x of 6 or less, regardless of whether Ta 2 O 5 is used as a component of glass or in a crystalline state. The current noise is smaller than that of the metal boride resistors (Comparative Examples 8 to 13).
【0031】また、Ta2O5をガラスの一成分として添
加する場合と結晶状態で直接添加する方法とを比較する
と、ガラスの一成分として添加する方が電流ノイズを小
さくできる。Further, comparing the case where Ta 2 O 5 is added as a component of glass and the method of directly adding it in a crystalline state, current noise can be reduced by adding as a component of glass.
【0032】[0032]
【表3】 [Table 3]
【0033】〔実施例13〜18〕Ta2O5以外の反応
性金属酸化物として、ZrO2及びW2O3をガラスの一
成分としたガラスフリット(No.7、No.8ガラス)
を用いた抵抗体の抵抗特性を表4に示す。表4からも明
らかなようにTa2O5の代わりとしてZrO2およびW2
O3を用いても優れた特性の抵抗体を得ることができ
る。[Examples 13 to 18] As a reactive metal oxide other than Ta 2 O 5 , glass frits containing ZrO 2 and W 2 O 3 as one component of glass (No. 7 and No. 8 glass).
Table 4 shows the resistance characteristics of the resistor using. As is clear from Table 4, ZrO 2 and W 2 are used instead of Ta 2 O 5.
Even if O 3 is used, a resistor having excellent characteristics can be obtained.
【0034】[0034]
【表4】 [Table 4]
【0035】〔実施例19〕実施例5の800℃〜95
0℃焼成の抵抗体のX線回折図を図4に示す。図4から
900℃でAlB12、Ta2O5のピークがなくなり抵抗
体全体がガラス化していることが確認できる。この焼成
温度において抵抗特性が安定化していることから本発明
の抵抗体はガラス状態でも抵抗特性が安定な抵抗体であ
ることがわかる。また950℃では、TaB2のピーク
が確認され、また、TaB2のピークがブロードである
ことから、析出したTaB2粒子が極めて微細な粒子で
構成されていることが分かる。[Example 19] 800 ° C to 95 of Example 5
The X-ray diffraction pattern of the resistor baked at 0 ° C. is shown in FIG. From FIG. 4, it can be confirmed that the peaks of AlB 12 and Ta 2 O 5 disappear at 900 ° C. and the entire resistor is vitrified. Since the resistance characteristics are stabilized at this firing temperature, it can be seen that the resistance element of the present invention has stable resistance characteristics even in the glass state. Further, at 950 ° C., a TaB 2 peak was confirmed, and the TaB 2 peak was broad, indicating that the precipitated TaB 2 particles were composed of extremely fine particles.
【0036】また、比較例2および実施例6の抵抗体
(焼成後)のX線回折図を図5に示す。図5から明らか
なように本発明の抵抗体は比較例のものと比べ、反応前
の結晶物は全く残っておらずTaB2のピークのみが析
出していることから非常に良く反応していることが分か
る。The X-ray diffraction patterns of the resistors of Comparative Example 2 and Example 6 (after firing) are shown in FIG. As is clear from FIG. 5, the resistor of the present invention reacts very well as compared with the resistor of the comparative example, since no crystal substance remains before the reaction and only the peak of TaB 2 is deposited. I understand.
【0037】〔実施例20〕ステレオの音声分離、ビデ
オの色再現に必要な抵抗マトリックス回路の抵抗体は、
高精度なものが要求される。例えば、ステレオ音声分離
度と抵抗値精度との関係は数1式で示される。[Embodiment 20] The resistors of the resistor matrix circuit necessary for stereo sound separation and video color reproduction are
High precision is required. For example, the relationship between the stereo sound separation degree and the resistance value accuracy is expressed by the equation (1).
【0038】[0038]
【数1】S=20log(1+α)/(1−α)(dB) 〔但し、Sは分離度、αは抵抗値精度を示す。〕 ステレオの音声分離度は、一般に40dB以上が要求さ
れる。抵抗値精度が、−1%の場合α=0.99とな
り、Sは46dBとなる。従って分離度40dB以上と
するには、抵抗値精度は±1%以内が要求される。## EQU1 ## S = 20 log (1 + .alpha.) / (1-.alpha.) (DB) [where S is the degree of separation and .alpha. Is the resistance accuracy. The stereo sound separation is generally required to be 40 dB or more. When the resistance value accuracy is -1%, α = 0.99 and S becomes 46 dB. Therefore, in order to achieve the isolation of 40 dB or more, the resistance value accuracy is required to be within ± 1%.
【0039】図6は、ステレオ音声回路を処理する抵抗
マトリックス回路の回路図である。前記音声分離度を達
成するためには、R1〜R8およびR11〜R14の各抵抗体
の抵抗値精度が±1%以内である必要がある。FIG. 6 is a circuit diagram of a resistor matrix circuit for processing a stereo audio circuit. In order to achieve the sound isolation, it is necessary that the resistance value accuracy of each of the resistors R 1 to R 8 and R 11 to R 14 be within ± 1%.
【0040】図7は、上記マトリックス回路をハイブリ
ッドIC化した回路パターンの一部を示すものである。
そこでこれらの抵抗体を前記実施例に示す抵抗組成物を
用いて作製した。その結果、優れた音声分離度のものが
得られた。なお、本発明により回路に銅系導体を用いる
ことができる。FIG. 7 shows a part of a circuit pattern obtained by forming the matrix circuit into a hybrid IC.
Therefore, these resistors were produced using the resistance composition shown in the above-mentioned example. As a result, excellent speech separation was obtained. According to the present invention, a copper-based conductor can be used in the circuit.
【0041】[0041]
【発明の効果】本発明の抵抗組成物によれば、同系材料
により広範囲な抵抗領域において抵抗特性が安定した優
れた厚膜抵抗体を得ることができる。According to the resistance composition of the present invention, an excellent thick film resistor having stable resistance characteristics in a wide resistance region can be obtained by using the same material.
【図1】本発明の抵抗体の導電機構を説明する模式図で
ある。FIG. 1 is a schematic diagram illustrating a conductive mechanism of a resistor according to the present invention.
【図2】抵抗体の抵抗値と電流ノイズとの関係を示すグ
ラフである。FIG. 2 is a graph showing the relationship between the resistance value of a resistor and current noise.
【図3】抵抗体の抵抗値と抵抗値のバラツキとの関係を
示すグラフである。FIG. 3 is a graph showing the relationship between resistance values of resistors and variations in resistance values.
【図4】800℃〜950℃焼成の抵抗体のX線回折図
である。FIG. 4 is an X-ray diffraction diagram of a resistor fired at 800 ° C. to 950 ° C.
【図5】比較例2と実施例6の抵抗体のX線回折図であ
る。5 is an X-ray diffraction diagram of resistors of Comparative Example 2 and Example 6. FIG.
【図6】本発明の一応用例である抵抗マトリックス回路
図である。FIG. 6 is a resistance matrix circuit diagram which is an application example of the present invention.
【図7】ハイブリッドICの抵抗マトリックス回路パタ
ーンの部分図である。FIG. 7 is a partial view of a resistance matrix circuit pattern of a hybrid IC.
1…金属ほう化物(AlB12)、2…ほう化タンタル
(TaB2)粒子、3…ガラスマトリックス、4…抵抗
体、5…銅導体。1 ... Metal boride (AlB 12 ), 2 ... Tantalum boride (TaB 2 ) particles, 3 ... Glass matrix, 4 ... Resistor, 5 ... Copper conductor.
───────────────────────────────────────────────────── フロントページの続き (72)発明者 小川 敏夫 茨城県日立市久慈町4026番地 株式会社日 立製作所日立研究所内 ─────────────────────────────────────────────────── ─── Continuation of the front page (72) Inventor Toshio Ogawa 4026 Kujimachi, Hitachi City, Ibaraki Prefecture Hitachi Research Laboratory, Hiritsu Manufacturing Co., Ltd.
Claims (10)
は金属元素、Bはほう素、x及びyは整数を示す)で示
すときy/xが6を超える金属ほう化物0.1〜50重
量部、(b)酸化タンタルに換算して1〜50重量部を
ガラス成分として含有するガラスフリット50〜99.
9重量部、(d)ペースト状とするのに有効量の有機ビ
ヒクル、を含むことを特徴とする厚膜抵抗組成物。1. A metal boride (a) is added to MxBy (provided that MxBy
Is a metal element, B is boron, and x and y are integers). When y / x is more than 6, 0.1 to 50 parts by weight of metal boride, (b) 1 to 50 in terms of tantalum oxide. Glass frit containing 90 parts by weight as a glass component.
A thick film resistance composition comprising 9 parts by weight of (d) an organic vehicle in an amount effective for forming a paste.
は金属元素、Bはほう素、x及びyは整数を示す)で示
すときy/xが6を超える金属ほう化物0.1〜50重
量部、(b)酸化タンタル0.1〜40重量部、(c)
ガラスフリット10〜99.8重量部、(d)ペースト
状とするのに有効量の有機ビヒクル、を含むことを特徴
とする厚膜抵抗組成物。2. A metal boride of (a) MxBy (provided that M
Is a metal element, B is boron, and x and y are integers) 0.1 to 50 parts by weight of a metal boride in which y / x exceeds 6, and (b) 0.1 to 40 parts by weight of tantalum oxide. , (C)
A thick film resistance composition comprising 10 to 99.8 parts by weight of a glass frit and (d) an organic vehicle in an amount effective for forming a paste.
ることを特徴とする請求項1または2記載の厚膜抵抗組
成物。3. The thick film resistor composition according to claim 1, wherein the metal boride is a metal 12 boride.
1または2記載の厚膜抵抗組成物。4. The thick film resistance composition according to claim 1, wherein the metal boride is AlB 12 .
(b)IVa〜VIa族の金属酸化物を1〜50重量部をガ
ラス成分として含有するガラスフリット50〜99.9
重量部、(d)ペースト状とするのに有効量の有機ビヒ
クルを含むことを特徴とする厚膜抵抗組成物。5. (a) 0.1 to 50 parts by weight of AlB 12 ,
(B) 50 to 99.9 glass frit containing 1 to 50 parts by weight of a group IVa to VIa metal oxide as a glass component.
A thick film resistance composition, characterized in that it comprises (parts by weight) of (d) an organic vehicle in an amount effective to form a paste.
(b)IVa〜VIa族の金属酸化物0.1〜40重量部、
(c)ガラスフリット10〜99.8重量部、(d)ペ
ースト状とするのに有効量の有機ビヒクル、を含むこと
を特徴とする厚膜抵抗組成物。6. (a) 0.1 to 50 parts by weight of AlB 12 ,
(B) 0.1 to 40 parts by weight of group IVa to VIa metal oxides,
A thick film resistance composition comprising (c) 10 to 99.8 parts by weight of a glass frit and (d) an organic vehicle in an amount effective for forming a paste.
(b)IVa〜VIa族の金属酸化物を1〜50重量部をガ
ラス成分として含有するガラスフリット50〜99.9
重量部、(c)ペースト状とするのに有効量の有機ビヒ
クルを含むことを特徴とする厚膜抵抗組成物。7. (a) 0.1 to 50 parts by weight of AlB 12 ,
(B) 50 to 99.9 glass frit containing 1 to 50 parts by weight of a group IVa to VIa metal oxide as a glass component.
A thick film resistance composition, characterized in that (c) a paste-like composition contains an effective amount of an organic vehicle.
厚膜抵抗体が、ガラスマトリックス中に分散された金属
ほう化物粒子、該粒子とガラスマトリックスの粒界及び
該粒子間のガラスマトリックス中に金属ほう化物と酸化
タンタルの反応により生じた粒径0.1μm以下のほう
化タンタル、前記反応により導電性が生じたガラスマト
リックスの少なくとも一つで形成された導電パスを有す
ることを特徴とする厚膜抵抗体。8. A thick film resistor obtained by printing and firing a resistance composition on an inorganic substrate, comprising metal boride particles dispersed in a glass matrix, grain boundaries between the particles and the glass matrix, and a glass matrix between the particles. Characterized in that it has a conductive path formed of at least one of a tantalum boride having a particle size of 0.1 μm or less produced by the reaction of a metal boride and tantalum oxide, and a glass matrix having an electrical conductivity produced by the reaction. Thick film resistor.
厚膜抵抗体が、ガラスマトリックス中に分散された金属
ほう化物粒子、該粒子とガラスマトリックスの粒界及び
該粒子間のガラスマトリックス中に金属ほう化物と酸化
タンタルの反応により生じた粒径0.1μm以下のほう
化タンタル、前記反応により導電性が生じたガラスマト
リックスの少なくとも一つで形成された導電パスを有す
る厚膜抵抗体が導体回路に接続構成されているハイブリ
ッドIC。9. A thick film resistor in which a resistance composition is printed and baked on an inorganic substrate, metal boride particles dispersed in a glass matrix, grain boundaries between the particles and the glass matrix, and a glass matrix between the particles. A tantalum boride having a particle size of 0.1 μm or less produced by the reaction of a metal boride and tantalum oxide, and a thick film resistor having a conductive path formed of at least one of a glass matrix having conductivity generated by the reaction. A hybrid IC connected to a conductor circuit.
Mは金属元素、Bはほう素、x及びyは整数を示す)で
示すときy/xが6を超える金属ほう化物0.1〜50
重量部、(b)酸化タンタルに換算して1〜50重量部
をガラス成分として含有するガラスフリット50〜9
9.9重量部、(d)ペースト状とするに有効量の有機
ビヒクルを含む厚膜抵抗組成物を、無機質基板面に塗布
して所定の形状の抵抗体膜を形成し、これを不活性ガス
雰囲気中で700℃〜950℃で焼成することによりガ
ラスマトリックス中に粒径0.1μm以下のほう化タン
タルを析出させるかまたはガラスに導電性を生じさせた
ことを特徴とする厚膜抵抗体の製法。10. A metal boride (a) is added to MxBy (provided that
Where M is a metal element, B is boron, and x and y are integers, and y / x is a metal boride having a value of more than 6, 0.1 to 50.
50 parts by weight of glass frit containing 1 to 50 parts by weight of (b) tantalum oxide as a glass component.
9.9 parts by weight, (d) a thick film resistor composition containing an effective amount of organic vehicle to form a paste is applied to the surface of an inorganic substrate to form a resistor film having a predetermined shape, which is inactive. Thick film resistor characterized by precipitating tantalum boride having a grain size of 0.1 μm or less in a glass matrix or by making the glass conductive by firing at 700 ° C. to 950 ° C. in a gas atmosphere. Manufacturing method.
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Cited By (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
DE3614869A1 (en) * | 1985-05-02 | 1986-11-27 | Murata Manufacturing Co., Ltd., Nagaokakyo, Kyoto | Commutator with suppression means |
-
1992
- 1992-06-01 JP JP4140287A patent/JPH05335108A/en active Pending
Cited By (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
DE3614869A1 (en) * | 1985-05-02 | 1986-11-27 | Murata Manufacturing Co., Ltd., Nagaokakyo, Kyoto | Commutator with suppression means |
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