JPH0262002A - Oxide metal film resistor and its manufacture - Google Patents
Oxide metal film resistor and its manufactureInfo
- Publication number
- JPH0262002A JPH0262002A JP63213339A JP21333988A JPH0262002A JP H0262002 A JPH0262002 A JP H0262002A JP 63213339 A JP63213339 A JP 63213339A JP 21333988 A JP21333988 A JP 21333988A JP H0262002 A JPH0262002 A JP H0262002A
- Authority
- JP
- Japan
- Prior art keywords
- mol
- resistance
- range
- film
- temperature coefficient
- 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
- 238000004519 manufacturing process Methods 0.000 title claims description 7
- 239000002184 metal Substances 0.000 title abstract description 4
- 229910052751 metal Inorganic materials 0.000 title abstract description 4
- 239000010408 film Substances 0.000 claims abstract description 54
- 229910044991 metal oxide Inorganic materials 0.000 claims abstract description 16
- 150000004706 metal oxides Chemical class 0.000 claims abstract description 16
- 238000000034 method Methods 0.000 claims abstract description 12
- 239000002131 composite material Substances 0.000 claims abstract description 8
- 239000000203 mixture Substances 0.000 claims abstract description 7
- 239000010409 thin film Substances 0.000 claims abstract description 6
- 239000002994 raw material Substances 0.000 claims description 8
- 239000007788 liquid Substances 0.000 claims description 5
- 239000003960 organic solvent Substances 0.000 claims description 3
- 239000000758 substrate Substances 0.000 claims description 3
- 238000002156 mixing Methods 0.000 claims description 2
- 150000001875 compounds Chemical class 0.000 claims 1
- 239000000126 substance Substances 0.000 claims 1
- ZKATWMILCYLAPD-UHFFFAOYSA-N niobium pentoxide Chemical compound O=[Nb](=O)O[Nb](=O)=O ZKATWMILCYLAPD-UHFFFAOYSA-N 0.000 abstract description 32
- XOLBLPGZBRYERU-UHFFFAOYSA-N tin dioxide Chemical compound O=[Sn]=O XOLBLPGZBRYERU-UHFFFAOYSA-N 0.000 abstract description 16
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N titanium dioxide Inorganic materials O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 abstract description 9
- LJCFOYOSGPHIOO-UHFFFAOYSA-N antimony pentoxide Inorganic materials O=[Sb](=O)O[Sb](=O)=O LJCFOYOSGPHIOO-UHFFFAOYSA-N 0.000 abstract description 4
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 6
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 4
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 2
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 2
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 description 2
- 229910019704 Nb2O Inorganic materials 0.000 description 2
- 239000005388 borosilicate glass Substances 0.000 description 2
- 239000000470 constituent Substances 0.000 description 2
- 238000005118 spray pyrolysis Methods 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 1
- 150000001805 chlorine compounds Chemical class 0.000 description 1
- 101150091051 cit-1 gene Proteins 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000000151 deposition Methods 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 239000002019 doping agent Substances 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- -1 propatool Chemical compound 0.000 description 1
- 239000000523 sample Substances 0.000 description 1
- 238000005507 spraying Methods 0.000 description 1
- 238000004544 sputter deposition Methods 0.000 description 1
- 229910052718 tin Inorganic materials 0.000 description 1
- QHGNHLZPVBIIPX-UHFFFAOYSA-N tin(II) oxide Inorganic materials [Sn]=O QHGNHLZPVBIIPX-UHFFFAOYSA-N 0.000 description 1
- 238000007740 vapor deposition Methods 0.000 description 1
- 238000004876 x-ray fluorescence Methods 0.000 description 1
Landscapes
- Non-Adjustable Resistors (AREA)
- Apparatuses And Processes For Manufacturing Resistors (AREA)
Abstract
Description
【発明の詳細な説明】
［産業上の利用分野］
本発明は酸化金属皮膜抵抗体に関し、さらに詳しくは、
Ｉ Ｘ １０’Ω・ｃＩＴ１〜１×１０３Ω・師の範囲
の比抵抗値と±２００ｐｐａ＋／”Ｃの範囲の抵抗温度
係数とを併せ持ツＳ ｎ ＯＴ ｔ Ｏ２Ｓ ｂ ２０
ｓＮｂ２Ｏ，系酸化金属皮膜抵抗体およびその製法に
関する。[Detailed Description of the Invention] [Industrial Application Field] The present invention relates to a metal oxide film resistor, and more specifically,
I X 10'Ω・cIT1~1×103Ω・Has both a specific resistance value in the range of 1 and a resistance temperature coefficient in the range of ±200ppa+/”C.S n OT t O2S b 20
This invention relates to a sNb2O, metal oxide film resistor and its manufacturing method.
［従来の技術〕
Ｓ ｎ Ｏ２皮膜抵抗体は耐熱性が高く、抵抗温度係数
も金属皮膜抵抗器に匹敵する小さな値であるものが低コ
ストで得られるため、各種電子機器に幅広く用いられて
いる。また、精密抵抗器としての用途も広く、±（５０
〜２００）Ｉ）ｐＩＩＩ／’Ｃの範囲の抵抗温度係数を
もつＳ ｎ ０２皮膜抵抗器として電子計算機、通信機
その他の産業機器にあまねく使用されている。これらの
用途に使われる抵抗器は主として１０Ω〜ＩＯＭΩの範
囲の抵抗値をもつものである。これらのＳ ｎ Ｏ２膜
は、一般に、スパッタ法、スプレー熱分解法、蒸着法、
ＣＯＤ法などにより作られるが、Ｓ ｎ Ｏ２皮膜抵抗
体の場合は、特性および製造コストの点から、主として
スプレー熱分解法が採用されている。この方法によるＳ
ｎ Ｏ２皮膜抵抗体の製造に際し抵抗値および抵抗温
度特性の設定は、Ｓｂ、Ｆ等のドーパントの添加量を変
えることや膜厚を調節すること等によって行なわれてい
る。しかしながら、Ｓ ｎ Ｏ２単独の皮膜では通常、
比抵抗が１０−２Ω・ｃｍ以下の皮膜しか得られないの
で比抵抗が１０−２Ω・ｍ以上となるような高い抵抗値
をもつ膜を得るためには、ＴＩの添加によりＳ ｎ Ｏ
Ｔ １０２系複合膜とするなどの方法がとられている。[Prior art] S n O2 film resistors have high heat resistance and a low temperature coefficient of resistance comparable to that of metal film resistors, and can be obtained at low cost, so they are widely used in various electronic devices. . It is also widely used as a precision resistor, ±(50
~200) I) S n 02 film resistors with a temperature coefficient of resistance in the range of pIII/'C are widely used in electronic computers, communications equipment, and other industrial equipment. Resistors used in these applications primarily have resistance values in the range of 10Ω to IOMΩ. These SnO2 films are generally produced by sputtering, spray pyrolysis, vapor deposition,
Although it is manufactured by the COD method, etc., in the case of SnO2 film resistors, the spray pyrolysis method is mainly adopted from the viewpoint of characteristics and manufacturing cost. S by this method
In manufacturing nO2 film resistors, the resistance value and resistance temperature characteristics are set by changing the amount of dopants such as Sb and F, and by adjusting the film thickness. However, in a film made of SnO2 alone,
Since only films with a specific resistance of 10-2 Ω・cm or less can be obtained, in order to obtain a film with a high resistance value of 10-2 Ω・m or more, S n O is added by adding TI.
Methods such as forming a T 102-based composite film are being used.
しかしこのＴ ｉＯ２を加える方法では抵抗温度係数が
±２００ｐｐＩＩｌ／℃以内の膜をつくることはできな
かった。However, with this method of adding TiO2, it was not possible to form a film with a temperature coefficient of resistance within ±200 ppII/°C.
［発明が解決しようとする課題］
ＳｂまたはＦを添加して改良したものでもＳ ｎ Ｏ２
膜の比抵抗は約５×ｌＯ〜２ＸｌＯΩ・印の範囲に過ぎ
ないため、膜厚を変えることにより抵抗値を調節する方
法では、安定して歩留り良く作成できる２０００Å以上
の膜厚の膜としたい場合には、１にΩ／ｓｑ以上の抵抗
値を得ることは困難であった。[Problem to be solved by the invention] S n O2 even when improved by adding Sb or F
Since the specific resistance of the film is only in the range of approximately 5×lO to 2×lOΩ・mark, in the method of adjusting the resistance value by changing the film thickness, it is desirable to use a film with a thickness of 2000 Å or more, which can be produced stably and with a high yield. In some cases, it has been difficult to obtain a resistance value of 1Ω/sq or more.
一方、ＳｎＯにＴｉＯを添加し、Ｓ ｎ Ｏ２、ＴｉＯ
３系複合酸化物皮膜とすることにより、もっと高い抵抗
値を持つ皮膜抵抗体をつくれることが知られているが、
この場合は、ＳｂやＦの添加によりもたらされる抵抗温
度特性の改善効果がバラツキの大きい不安定なものであ
るため、抵抗温度特性を±２００ｐｐａ＋／ ’Ｃの範
囲内に設定することが困難であった。On the other hand, by adding TiO to SnO, SnO2, TiO
It is known that a film resistor with a higher resistance value can be created by using a 3-based composite oxide film.
In this case, the effect of improving the resistance-temperature characteristics brought about by the addition of Sb or F is unstable with large variations, so it is difficult to set the resistance-temperature characteristics within the range of ±200ppa+/'C. Ta.
上記の諸欠点を改善し、抵抗器を抵抗値１にΩ〜１０Ｍ
Ωのものとできることに相当する比抵抗値１０ Ω・
ｃ＋ｎ−１０３Ω・（至）を持ち、さらに±２００１）
Ｉ）ｌ／”Ｃ以内の抵抗温度係数を持つ改良されたＳ
ｎ ＯＺ系酸化金属皮膜抵抗体の製造を可能とすること
か本発明の解決しようとする課題である。The above-mentioned defects have been improved, and the resistor has a resistance value of 1Ω to 10M.
The specific resistance value is 10 Ω, which corresponds to that of Ω.
c+n-103Ω・(to), plus ±2001)
I) Improved S with temperature coefficient of resistance within l/”C
The problem to be solved by the present invention is to make it possible to manufacture nOZ-based metal oxide film resistors.
［課題を解決するための手段］
ＳｐＯにＴ ｉ Ｏ２を加えたＳ ｎ Ｏ２Ｔ ｉ Ｏ
２系にさらにＳｂ ＯおよびＮｂ２Ｏ５を加えて、（Ｓ
ｎＯ）−（ＴｉＯ）−（Ｓｂ２０５）２２ｘ
２ｙ
（Ｎｂ２０５）ｖという組成の複合金属酸化物皮膜を作
成することにより、Ｉ Ｘ １０’Ω・ｃＩＴ１〜１×
１０３Ω・印の範囲の比抵抗と、±２００ｐｐｎ＋／
’Ｃの範囲の抵抗温度係数とを併せ持つ薄膜抵抗体を得
ることが可能であることを見出し、前記の課題を解決し
た。ここに、上記組成式中のＸ＋ Ｙ−Ｚ＋ および
Ｗは、ＳｎＯ２，ＴｉＯ２゜Ｓｂ ＯおよびＮ ｂ ２
０５それぞれのモル数をＳｎＯとＴｌＯ２との合計モル
数に対して％で表わした数値である。すなわち、Ｘおよ
びｙはＳｎＯ−Ｔｉｌｌ、系の各構成成分のモル％であ
す、２およびＷはこの系に添加した５ｂ２０５およびＮ
ｂ２Ｏ５それぞれのモル数を添加前におけるこの系の各
構成成分の合計モル数に対して％で表わしたものである
。この意味で以下の記載において、Ｘおよびｙの表イ）
すモル％は単に「モル％」と呼び、２およびＷの表わす
モル％は「添加モル％」と呼ぶことにする。ｘ＋ｙ−１
００であり、Ｘ。[Means for solving the problem] S n O2T i O obtained by adding T i O2 to SpO
By further adding SbO and Nb2O5 to the 2 system, (S
nO)-(TiO)-(Sb205)22x
By creating a composite metal oxide film with a composition of 2y (Nb205)v, I
Specific resistance in the range of 103Ω・mark and ±200ppn+/
The inventors have discovered that it is possible to obtain a thin film resistor having a temperature coefficient of resistance in the range of 'C, and have solved the above-mentioned problems. Here, X+ Y-Z+ and W in the above compositional formula are SnO2, TiO2゜SbO and Nb2
The number of moles of each of SnO and TlO2 is expressed as a percentage of the total number of moles of SnO and TlO2. That is, X and y are SnO-Till, mol% of each component of the system, 2 and W are 5b205 and N added to this system.
The number of moles of each b2O5 is expressed as a percentage of the total number of moles of each component of the system before addition. In this sense, in the following description, the table of X and y)
The mol % represented by 2 and W will be simply referred to as "mol %", and the mol % represented by 2 and W will be referred to as "added mol %". x+y-1
00 and X.
ｙ、ｚおよびＷは下記の式（１） 、 （２）および（
３）を同時に満たす数値であることが必要である。y, z and W are expressed by the following formulas (1), (2) and (
It is necessary that the value satisfies 3) at the same time.
［作 用］
Ｓ ｎ Ｏ２単独の金属酸化物皮膜では比抵抗は約５×
１０〜２ Ｘ １０’Ω・印の範囲の値となるに過ぎな
いが、ＴｉＯを加えて５ｎＯ２−Ｔ１０２系とすること
により、その値を１０−２Ω・ｃｍから約１０５Ω・（
至）程度まで直線的に増加させることができる。しかし
ながら、５ｎＯ２−ＴｉＯ２系皮膜の抵抗温度係数は一
２００ｐＮ＋／ ”Ｃより小さい値にしかならない。そ
こでＳ ｎ ０２ Ｔ ｔ ０２系に０，５モル％の
５ｂ２０５を加えてＳ ｎ Ｏ２ＴｉＯ−８ｂ２０５系
とすると、抵抗温度係数（ｐｐＩＩ／ ’ｃ ）は第１
ａ図の直線Ａのようになり、さらにＮｂ Ｏを加えて
Ｓ ｎ Ｏ２Ｔ Ｌ ０２Ｓ ｂ ２０５ Ｎ ｂ
２０５とすると、Ｎｂ２Ｏ５の量をそれぞれ０．５モル
％、１．２５モル％、２，５モル％とするとき、これら
の系の抵抗温度係数はそれぞれ第１ａ図の直線または曲
線Ｂ、 Ｃ，Ｄのようになり、抵抗温度係数が±２０
０ｐｐａ＋／’Ｃの範囲内の皮膜が得られる。Ｎｂ２Ｏ
，の添加量を３．０モル％とした場合の５ｎ０２−Ｔｉ
Ｏ２Ｓｂ Ｏ−Ｎｂ２０５系皮膜の抵抗温度係数は、第
１ａ図下部に黒く塗りつぶした小さな円で示すように、
−３００ｐｐｍ／ ’Ｃより小さい値となり、明らかに
±２００ｐｐｒＡ／”Ｃの範囲から大きくはずれる。Ｓ
ｂ ２０ ｉ、の添加量を２モル９６としたときのＳ
ｎＯ−ＴｉＯ２−８ｂ２０５系皮膜の抵抗温度係数は第
２ａ図の直線Ｅに示す通りとなり、±２００ｐｐ１１／
”Ｃの範囲からはずれるが、さらにＮｂ２Ｏ５を、そ
れぞれ０．５モル％、１．２５モル％、２．５モル％添
加したＳ ｎ Ｏ２−Ｔ ｉ ０２Ｓｂ Ｏ−Ｎｂ２０
５系皮膜の抵抗温度係数は、第２ａ図の直線または曲線
Ｆ、 Ｇ、 Ｈのようになり±２００ｐＩｔｓ／ ”Ｃ
の範囲内となる。Ｎｂ２Ｏ５の添加量を３．０モル％と
したときの抵抗温度係数は第２ａ図下部に黒く塗りつぶ
した円で示すように、明らかに一２００ｐｐ１１７℃よ
り小さい値となり、±２００ｐｐｍ／ ”Ｃの範囲から
はずれる。[Function] In the metal oxide film of S n O2 alone, the specific resistance is approximately 5×
Although the value is only in the range of 10 to 2 x 10'Ω・mark, by adding TiO to create a 5nO2-T102 system, the value can be increased from 10−2Ω・cm to approximately 105Ω・(
can be increased linearly up to However, the temperature coefficient of resistance of the 5nO2-TiO2-based film is only a value smaller than -200 pN+/''C.Therefore, 0.5 mol% of 5b205 was added to the Sn02Tt02-based film to form the SnO2TiO-8b205-based film. Then, the temperature coefficient of resistance (ppII/'c) is the first
It becomes like straight line A in figure a, and by adding Nb O, it becomes S n O2T L 02S b 205 N b
205 and the amounts of Nb2O5 are 0.5 mol%, 1.25 mol%, and 2.5 mol%, respectively, the temperature coefficients of resistance of these systems are the straight lines or curves B, C, and C in Figure 1a, respectively. D, and the temperature coefficient of resistance is ±20
A film within the range of 0 ppa+/'C is obtained. Nb2O
5n02-Ti when the amount of addition is 3.0 mol%
The temperature coefficient of resistance of the O2Sb O-Nb205 film is as shown by the small black circle at the bottom of Figure 1a.
The value is smaller than -300ppm/'C, which clearly deviates significantly from the range of ±200pprA/'C.S
S when the addition amount of b 20 i is 2 mol 96
The temperature coefficient of resistance of the nO-TiO2-8b205 film is as shown by the straight line E in Figure 2a, which is ±200pp11/
"Although outside the range of C, 0.5 mol%, 1.25 mol%, and 2.5 mol% of Nb2O5 were added, respectively.SnO2-Ti02SbO-Nb20
The temperature coefficient of resistance of the 5-series film is as shown in the straight lines or curves F, G, and H in Figure 2a, and is ±200 pIts/''C.
Within the range of When the amount of Nb2O5 added is 3.0 mol%, the temperature coefficient of resistance is clearly smaller than -200 ppm/117°C, as shown by the black circle at the bottom of Figure 2a, and is within the range of ±200 ppm/''C. It comes off.
上記それぞれの場合の比抵抗（Ω・ｃｍ）の変化は、そ
れぞれ第１ｂ図および第２ｂ図に示すようになり、直線
りまたはＭに従うか、またはそれに近いものとなる。し
たがって、それぞれの５ｎＯ−ＴｉＯ２−８ｂ２０５−
Ｎｂ２０５系皮膜が、１×ｌＯ〜ｌＸ１０３Ω・印の範
囲内の比抵抗値をとり得ることは明らかである。上記の
ことから、各酸化物成分のモル％を調節してＳ ｎ Ｏ
２ＴｉＯ−８ｂ２０５−Ｎｂ２０５系複合金属酸化物皮
膜をつくることにより、Ｉ Ｘ ｔｏ’〜ｌＸ１０”Ω
・印の範囲の比抵抗と±２００ｐｐｍ／ ”Ｃの範囲内
の抵抗温度係数とを併せ持つ皮膜抵抗体を製造すること
が可能であることが理解されよう。The changes in specific resistance (Ω·cm) in each of the above cases are as shown in FIGS. 1b and 2b, respectively, and follow a straight line or M, or are close to it. Therefore, each 5nO-TiO2-8b205-
It is clear that the Nb205-based film can have a specific resistance value within the range of 1×10 to 1×10 3 Ω·mark. From the above, by adjusting the mol% of each oxide component, S n O
By creating a 2TiO-8b205-Nb205-based composite metal oxide film, I
It will be appreciated that it is possible to produce a film resistor having both a resistivity in the range marked and a temperature coefficient of resistance in the range ±200 ppm/''C.
本発明の酸化金属皮膜抵抗体は、たとえば各成分金属の
塩化物を所定のモル比で有機溶媒に溶解して得た原料液
を、加熱したホウケイ酸ガラス等の基材の表面、に圧力
噴霧して着膜させる方法によって容易につくることがで
きる。原料配合時のモル比は必ずしも成膜された酸化物
皮膜の構成成分のモル比と一致しないので、製造に先立
ち簡単な試験を行なって、それぞれの場合のモル比の関
係を調べておき、所望の成膜が得られるような原料配合
を行なうことが必要である。成膜の構成成分であるＳｎ
ＯＴｉＯ２，５ｂ２０５゜２′
Ｎｂ２Ｏ５のモル比は、得られた薄膜の構成成分Ｓｎ、
Ｔｉ 、Ｓｂ、Ｎｂの原子比を蛍光Ｘ線法により求め、
それぞれの酸化物のモル数に換算して求めることができ
る。The metal oxide film resistor of the present invention is produced by pressure spraying a raw material liquid obtained by dissolving chlorides of each component metal in an organic solvent at a predetermined molar ratio onto the surface of a heated substrate such as borosilicate glass. It can be easily produced by a method of depositing a film. The molar ratio at the time of blending the raw materials does not necessarily match the molar ratio of the constituent components of the formed oxide film, so prior to manufacturing, a simple test is conducted to find out the relationship between the molar ratios in each case, and the desired It is necessary to mix the raw materials in such a way that the film can be formed. Sn, a component of film formation
The molar ratio of OTiO2,5b205°2' Nb2O5 is the constituents of the obtained thin film, Sn,
The atomic ratio of Ti, Sb, and Nb was determined by fluorescent X-ray method,
It can be calculated by converting it into the number of moles of each oxide.
比抵抗および抵抗温度係数は実施例に記載の方法で求め
ることができる。Specific resistance and temperature coefficient of resistance can be determined by the method described in Examples.
実施例
Ｓ ｎ Ｃ，Ｑ ４ ２４．７５ｇ ＳＴ ｔ ＣΩ４
４．７４ｇ。Example S n C, Q 4 24.75g ST t CΩ4
4.74g.
ｓｂｃΩ３０．２３ｇ、 Ｎ ｂ （１！５０．２７ｇ
をエタノール５２０ｇに溶解し、Ｓｎ：ＴＩ：Ｓｂ：Ｎ
ｂ ＝９５： ２５： １ ：１（モル比）となる原料
液（１）をつくった。sbcΩ30.23g, N b (1!50.27g
was dissolved in 520 g of ethanol, and Sn:TI:Sb:N
A raw material solution (1) having a molar ratio of b = 95:25:1:1 was prepared.
ホットプレートで５００℃に加熱したホウケイ酸ガラス
基板（Ｃｏｒｎｌｎｇ” ７０５９）上に３ｋｇ／ｃｄ
の圧力で上記の溶液（１）を６０秒間噴霧し、厚さ約５
０００への薄膜を形成した。3 kg/cd on a borosilicate glass substrate (Cornlng” 7059) heated to 500°C on a hot plate.
The above solution (1) was sprayed for 60 seconds at a pressure of
000 was formed.
上記薄膜の面抵抗を４端子法で測定し、面抵抗と膜厚か
ら比抵抗を求めた。また、２０℃および１５５℃で面抵
抗を測定し、次の式により抵抗温度係数を求めた。The sheet resistance of the thin film was measured by a four-probe method, and the specific resistance was determined from the sheet resistance and film thickness. Further, the sheet resistance was measured at 20° C. and 155° C., and the temperature coefficient of resistance was determined using the following formula.
（ｐｐｍ／’Ｃ〕
ここに、Ｒ１５５およびＲ２Ｏは１５５℃および２０℃
における面抵抗の値をそれぞれ表わす。(ppm/'C) Here, R155 and R2O are 155℃ and 20℃
represents the value of sheet resistance at .
次いで薄膜組成におけるＳｎ、ＴＩ、Ｓｂ。Next, Sn, TI, and Sb in the thin film composition.
Ｎｂの原子比を蛍光Ｘ線法により求め、Ｓ ｎ Ｏ２。The atomic ratio of Nb was determined by X-ray fluorescence method, and SnO2.
ＴｉＯ２，５ｂ２０５．Ｎｂ２Ｏ５のモル比に換算した
値を第１表中Ｎｏ、２の列に示した。同様のことを多数
の別の組成の原料液を用いて行ない、同表中Ｎｏ、１お
よびＮｏ、３〜５３の列に同様の換算値を示した。TiO2,5b205. The values converted to the molar ratio of Nb2O5 are shown in the No. and 2 columns in Table 1. Similar results were carried out using a number of raw material liquids with different compositions, and similar converted values were shown in the columns No. 1 and No. 3 to No. 53 in the same table.
第１表中、尚ｔｌ、ＮＯ，５、Ｎｏ、６． Ｎｏ、ＬＯ
，Ｎｏ、１４〜２３゜Ｎｏ、２８． Ｎａ、２９． Ｎ
ｏ、３３． Ｎｏ、３４． Ｎｏ、３７〜５３に示す膜
組成を持つものは、
のいずれかの条件を満たさない。その結果、所望の比抵
抗と抵抗温度係数とを有する皮膜とはならない。したが
って、これらの列に示した酸化金属皮膜抵抗体は本発明
を例示するものではなく、比較例である。In Table 1, tl, NO, 5, No, 6. No, L.O.
, No, 14~23°No, 28. Na, 29. N
o, 33. No, 34. No. Those having film compositions shown in 37 to 53 do not satisfy any of the following conditions. As a result, the film does not have the desired resistivity and temperature coefficient of resistance. Therefore, the metal oxide film resistors shown in these columns are not illustrative of the present invention, but are comparative examples.
その他の列に示す膜組成を持つものは、上記（１）。Those having the film compositions shown in the other columns are (1) above.
（２）および（３）の条件を同時に満足する酸化金属皮
膜抵抗体であり、いずれもｌＸｌ０’Ω・ｃｍ〜１×１
０３Ω・（１）の範囲の比抵抗値と、±２００ｐｐｍ／
”Ｃの範囲内の抵抗温度係数とを併せ持つＳ ｎ Ｏ
２ＴｉＯ−８ｂ２０５−Ｎｂ２０５系酸化金属皮膜抵抗
体である。すなわち、これらは本発明の実施例である。It is a metal oxide film resistor that satisfies the conditions (2) and (3) at the same time, and both are lXl0'Ω・cm~1×1
Specific resistance value in the range of 03Ω・(1) and ±200ppm/
“S n O with a temperature coefficient of resistance within the range of C
This is a 2TiO-8b205-Nb205 metal oxide film resistor. That is, these are examples of the present invention.
〔ただし、ｘ、ｙ、ｚ、ｗはそれぞれＳ ｎ Ｏ２＋Ｔ
ｉＯのモル％および、５ｂ２０５．Ｎｂ２Ｏ５の添加モ
ル％であり、ｘ ＋ ｙ ＝ １００を基準とし、ｚ、
ｗはこの基準に基づいて定めた値である。〕未満のとき
は比抵抗がｌロー２Ω・印より小さく、０．７０より大
きいときはに５．Ｎｏ、６に示すように１０３Ω・（１
）より大きくなるため所望の皮膜が得られない。[However, x, y, z, and w are each S n O2+T
Mol% of iO and 5b205. Addition mol% of Nb2O5, based on x + y = 100, z,
w is a value determined based on this standard. ] When the resistivity is less than 10, the resistivity is less than the 2Ω mark, and when it is greater than 0.70, the resistivity is 5. As shown in No.6, 103Ω・(1
), the desired film cannot be obtained.
Ｎｏ、４７〜５１および第３図に示すように原料液中の
Ｓｂ量に対する抵抗温度係数のバラツキが大きく安定し
た特性が得られない。また、０．０２より大きいときは
Ｎｏ、３８〜４６に示すように抵抗温度係数が±２００
ｐｐｍ／℃の範囲に入らないため所望の皮膜が得られな
い。As shown in Nos. 47 to 51 and FIG. 3, the temperature coefficient of resistance varied greatly with respect to the amount of Sb in the raw material liquid, making it impossible to obtain stable characteristics. Also, if it is larger than 0.02, it is No, and the resistance temperature coefficient is ±200 as shown in 38 to 46.
Since it does not fall within the range of ppm/°C, the desired film cannot be obtained.
安定であり、Ｏ，［１２５より大きいときは、第１表Ｎ
ｏ。stable, O, [When larger than 125, Table 1 N
o.
１５、 ＮｏＪ８に示すように抵抗温度係数が±２００
ｐｐｍ／℃の範囲に入らないため所望の皮膜が得られな
い。15. As shown in NoJ8, the temperature coefficient of resistance is ±200
Since it does not fall within the range of ppm/°C, the desired film cannot be obtained.
また上記実施例では有機溶媒としてエタノールを用いた
が、本発明はこれに限定されるものではなく、エタノー
ルのかわりにメタノール、プロパツール、ブタノール、
アセトン、トルエン、エーテル等を用いることもできる
。Further, in the above examples, ethanol was used as the organic solvent, but the present invention is not limited to this, and instead of ethanol, methanol, propatool, butanol, etc.
Acetone, toluene, ether, etc. can also be used.
第１ａ図はＳ ｎ Ｏ＋ Ｔ ｉＯ２−１００モル％を
基準として、５ｂ２０５が０．５モル％添加されたＳｎ
Ｏ−ＴｉＯ２−８ｂ２０５系に、それぞれ、上記と同じ
基準で０モル％、０．５モル％、１．２５モル％、２．
５モル％および３．０モル％のＮｂ２Ｏ５が添加された
５ｎＯ２−ＴｉＯ２−８ｂ２０５Ｎｂ２０５系複合金属
酸化物皮膜抵抗体におけるＮｂ２Ｏ５含有量と抵抗温度
係数との関係を示すグラフである。
第１ｂ図は、第１ａ図に説明した皮膜抵抗体におけるＮ
ｂ２Ｏ５含有量と非抵抗との関係を示すグラフである。
第２ａ図はＳ ｎ Ｏ＋ Ｔ ｉ Ｏ２−１００モル％
を基準としてＳ ｂ ２０ ｉ、が２モル％添加された
ＳｎＯ−ＴｉＯ−８ｂ２０５系に、それぞれ上記と同じ
基準で０モル％、０．５モル％、１．２５モル％、２．
５モル％および３．０モル％のＮ ｂ ２０５が添加さ
れたＳｎＯ−ＴｉＯ２−３ｂ２０５Ｎｂ２Ｏ５系複合金
属酸化物皮膜抵抗体におけるＮｂ２Ｏ，含有量と抵抗温
度係数との関係を示すグラフである。
第２ｂ図は、ｍ２ａ図に関して説明した皮膜抵抗体にお
けるＮ ｂ ２０５含有量と比抵抗との関係を示すグラ
フである。
第３図は、原料液中の５ｂＣｊ１１３量と抵抗温度係数
との関係を示すグラフである。
図中の記号は次のものをそれぞれ表わす。
Ｎｂ２Ｏ５含有量Ｗ
（添加モル％）
・・・・ ３．０
×・・・ ２，５
０・・・１．２５
△・・・ ０，５
０・・・ ０Figure 1a shows Sn to which 0.5 mol% of 5b205 is added based on SnO+TiO2-100 mol%.
To the O-TiO2-8b205 system, 0 mol%, 0.5 mol%, 1.25 mol%, 2.
2 is a graph showing the relationship between the Nb2O5 content and the temperature coefficient of resistance in 5nO2-TiO2-8b205Nb205-based composite metal oxide film resistors to which 5 mol% and 3.0 mol% of Nb2O5 are added. Figure 1b shows the N in the film resistor described in Figure 1a.
It is a graph showing the relationship between b2O5 content and non-resistance. Figure 2a shows S n O+ T i O2-100 mol%
Based on the above, to the SnO-TiO-8b205 system to which 2 mol% of S b 20 i was added, 0 mol%, 0.5 mol%, 1.25 mol%, 2.
2 is a graph showing the relationship between the Nb2O content and the temperature coefficient of resistance in SnO-TiO2-3b205Nb2O5-based composite metal oxide film resistors to which 5 mol% and 3.0 mol% of Nb205 are added. FIG. 2b is a graph showing the relationship between the N b 205 content and specific resistance in the film resistor described in connection with the m2a diagram. FIG. 3 is a graph showing the relationship between the amount of 5bCj113 in the raw material liquid and the temperature coefficient of resistance. The symbols in the figure represent the following, respectively. Nb2O5 content W (additional mol%)... 3.0 ×... 2,5 0...1.25 △... 0,5 0... 0
Claims (2)
（Ｓｂ＿２Ｏ＿５）＿ｚ−（Ｎｂ＿２Ｏ＿５）＿ｗで表
わされる組成をもつ複合金属酸化物の薄膜〔ただし、ｘ
，ｙ，ｚ，ｗはそれぞれ、ＳｎＯ＿２，ＴｉＯ＿２のモ
ル％およびＳｂ＿２Ｏ＿５，Ｎｂ＿２Ｏ＿５の添加モル
％を表わし、ｘ＋ｙ＝１００を基準として、ｚ，ｗの値
を定め、かつ ▲数式、化学式、表等があります▼ を満足する数値である。〕 からなる酸化金属皮膜抵抗体。(1) Formula: (SnO_2)_x-(TiO_2)_y-
(Sb_2O_5)_z-(Nb_2O_5)_w [However, x
, y, z, and w represent the mol% of SnO_2 and TiO_2 and the added mol% of Sb_2O_5 and Nb_2O_5, respectively, and the values of z and w are determined based on x+y=100, and ▲ mathematical formulas, chemical formulas, tables, etc. It is a value that satisfies ▼. ] A metal oxide film resistor consisting of
びＮｂＣｌ＿５を所定のモル比で有機溶媒に添加混合し
て得た原料液を、加熱した基材表面に圧力噴霧して、式
：（ＳｎＯ＿２）＿ｘ−（ＴｉＯ＿２）＿ｙ−（Ｓｂ＿
２Ｏ＿５）＿ｚ−（Ｎｂ＿２Ｏ＿５）＿ｗで表わされる
組成をもつ複合金属酸化物の薄膜を形成する〔ただし、
ｘ，ｙ，ｚ，ｗは上に同じ。〕ことからなる酸化金属皮
膜抵抗体の製法。(2) A raw material liquid obtained by adding and mixing SnCl_4, TiCl_4, SbCl_3 and NbCl_5 to an organic solvent at a predetermined molar ratio is pressure sprayed onto the heated substrate surface to form a compound with the formula: (SnO_2)_x-(TiO_2). _y-(Sb_
A thin film of a composite metal oxide having a composition represented by 2O_5)_z-(Nb_2O_5)_w is formed [However,
x, y, z, w are the same as above. ] A method for manufacturing a metal oxide film resistor.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP63213339A JPH0262002A (en) | 1988-08-27 | 1988-08-27 | Oxide metal film resistor and its manufacture |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP63213339A JPH0262002A (en) | 1988-08-27 | 1988-08-27 | Oxide metal film resistor and its manufacture |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPH0262002A true JPH0262002A (en) | 1990-03-01 |
Family
ID=16637515
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP63213339A Pending JPH0262002A (en) | 1988-08-27 | 1988-08-27 | Oxide metal film resistor and its manufacture |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH0262002A (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| KR100398019B1 (en) * | 2001-08-30 | 2003-09-19 | 정영찬 | Method for manufacturing the film of a high capacity and high property metal oxide film resistor which insulation substrate is substituted with low content alumina |
-
1988
- 1988-08-27 JP JP63213339A patent/JPH0262002A/en active Pending
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| KR100398019B1 (en) * | 2001-08-30 | 2003-09-19 | 정영찬 | Method for manufacturing the film of a high capacity and high property metal oxide film resistor which insulation substrate is substituted with low content alumina |
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