JP4895481B2 - Resistance thin film and sputtering target for forming the resistance thin film - Google Patents
Resistance thin film and sputtering target for forming the resistance thin film Download PDFInfo
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- 239000010409 thin film Substances 0.000 title claims description 80
- 238000005477 sputtering target Methods 0.000 title claims description 11
- 229910052761 rare earth metal Inorganic materials 0.000 claims description 35
- 239000000758 substrate Substances 0.000 claims description 12
- 238000010438 heat treatment Methods 0.000 claims description 9
- 238000004544 sputter deposition Methods 0.000 claims description 8
- 229910052759 nickel Inorganic materials 0.000 claims description 7
- 229910052804 chromium Inorganic materials 0.000 claims description 6
- 238000004519 manufacturing process Methods 0.000 claims description 5
- PXHVJJICTQNCMI-UHFFFAOYSA-N nickel Substances [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 34
- 239000011651 chromium Substances 0.000 description 32
- 229910045601 alloy Inorganic materials 0.000 description 22
- 239000000956 alloy Substances 0.000 description 22
- 239000000203 mixture Substances 0.000 description 18
- 239000000463 material Substances 0.000 description 13
- 238000000034 method Methods 0.000 description 13
- 230000000052 comparative effect Effects 0.000 description 8
- 229910052751 metal Inorganic materials 0.000 description 8
- 239000002184 metal Substances 0.000 description 8
- 229910021364 Al-Si alloy Inorganic materials 0.000 description 5
- 229910001122 Mischmetal Inorganic materials 0.000 description 5
- 230000000694 effects Effects 0.000 description 5
- 229910019819 Cr—Si Inorganic materials 0.000 description 4
- 239000003153 chemical reaction reagent Substances 0.000 description 4
- 239000010408 film Substances 0.000 description 4
- 229910018487 Ni—Cr Inorganic materials 0.000 description 3
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 3
- GWXLDORMOJMVQZ-UHFFFAOYSA-N cerium Chemical compound [Ce] GWXLDORMOJMVQZ-UHFFFAOYSA-N 0.000 description 3
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 2
- 229910052684 Cerium Inorganic materials 0.000 description 2
- 229910002796 Si–Al Inorganic materials 0.000 description 2
- 229910052746 lanthanum Inorganic materials 0.000 description 2
- FZLIPJUXYLNCLC-UHFFFAOYSA-N lanthanum atom Chemical compound [La] FZLIPJUXYLNCLC-UHFFFAOYSA-N 0.000 description 2
- 238000002844 melting Methods 0.000 description 2
- 230000008018 melting Effects 0.000 description 2
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- 229910052786 argon Inorganic materials 0.000 description 1
- 229910002056 binary alloy Inorganic materials 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 229910001325 element alloy Inorganic materials 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 229910052747 lanthanoid Inorganic materials 0.000 description 1
- 150000002602 lanthanoids Chemical class 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 229910052710 silicon Inorganic materials 0.000 description 1
- 239000010703 silicon Substances 0.000 description 1
Description
本発明は、電子部品の薄膜抵抗器に用いられる抵抗薄膜およびその製造方法、並びに、この抵抗薄膜を形成するためのスパッタリングターゲットに関する。 The present invention relates to a resistive thin film used for a thin film resistor of an electronic component, a manufacturing method thereof, and a sputtering target for forming the resistive thin film.
チップ抵抗器、精密抵抗器、ネットワーク抵抗器、高圧抵抗器などの抵抗器、測温抵抗体、感温抵抗器などの温度センサ、およびハイブリットＩＣとその複合モジュール製品などの電子部品には、抵抗薄膜を使用した薄膜抵抗器が用いられている。 Resistors such as chip resistors, precision resistors, network resistors, high-voltage resistors, temperature sensors such as resistance temperature detectors, temperature sensitive resistors, and electronic components such as hybrid ICs and their combined module products Thin film resistors using thin films are used.
この薄膜抵抗器においては、多くの場合、抵抗薄膜を作製するための金属抵抗体材料として、Ｔａ金属、ＴａＮ化合物、Ｎｉ−Ｃｒ合金が用いられており、中でもＮｉ−Ｃｒ合金が、最も一般的に用いられている。 In this thin film resistor, Ta metal, TaN compound, and Ni—Cr alloy are often used as a metal resistor material for producing a resistive thin film, and Ni—Cr alloy is the most common. It is used for.
薄膜抵抗器では、その用途によっては、高温保持における経時的抵抗変化率が小さく、非常に安定であるという高温安定性と、抵抗温度係数（ＴＣＲ）とが、重要な特性となる。このため、薄膜抵抗器の材料である金属抵抗体材料がこれらの特性を実現する必要がある。一般に、ＮｉおよびＣｒのみからなる２元系合金の場合は、Ｎｉ／Ｃｒの比を変え、高温安定性と抵抗温度係数の制御を行う。しかし、抵抗値が高温で安定であること、および抵抗温度係数がほぼ０であることを、同時に実現することは困難である。そのため、特許第２５４２５０４号公報および特開平６−２０８０３号公報に記載されるように、Ｎｉ−Ｃｒ−Ａｌ−Ｓｉ合金のように４元素合金とすることにより、特性の改善が検討されてきた。 In a thin film resistor, depending on the application, the high temperature stability and the temperature coefficient of resistance (TCR) that are very stable and the resistance temperature coefficient (TCR) are important characteristics. For this reason, it is necessary for the metal resistor material, which is the material of the thin film resistor, to realize these characteristics. In general, in the case of a binary alloy composed only of Ni and Cr, the Ni / Cr ratio is changed to control the high temperature stability and the resistance temperature coefficient. However, it is difficult to simultaneously realize that the resistance value is stable at a high temperature and that the resistance temperature coefficient is substantially zero. Therefore, as described in Japanese Patent No. 25542504 and Japanese Patent Laid-Open No. 6-20803, improvement of characteristics has been studied by using a four-element alloy such as a Ni—Cr—Al—Si alloy.
しかしながら、一般に抵抗薄膜はスパッタリングにより成膜するが、このＮｉ−Ｃｒ−Ａｌ−Ｓｉ合金のようにＡｌを添加することによって鋳造性が悪化し、ターゲットの製造コストを上昇させる要因となっている。
本発明は、従来のＮｉ−Ｃｒ−Ｓｉ系合金にＡｌを添加することなく、高い高温安定性と良好な抵抗温度特性を有する電子部品用抵抗薄膜、および該電子部品用抵抗薄膜を形成するためのスパッタリングターゲットを提供することを目的とする。 The present invention, without the addition of Al to a conventional Ni-Cr-Si alloy for electronic components resistive film, and to form the electronic component resistor thin film has a high temperature stability and good resistance temperature characteristic An object of the present invention is to provide a sputtering target.
本発明の電子部品用抵抗薄膜は、Ｓｉ：０．２〜５．０質量％、希土類元素：０．０１〜０．５質量％を含み、残部がＣｒおよびＮｉからなり、Ｃｒ／Ｎｉ比が質量で０．５１〜１．１であって、大気中において、温度２００〜５００℃で、１〜１０時間の条件で熱処理が施されていることにより、抵抗温度係数が±９ｐｐｍ／℃以内であり、かつ、１７５℃で２０００時間保持した場合の高温抵抗変化率が０．２４％以下であることを特徴とする。 The resistive thin film for electronic parts of the present invention contains Si: 0.2 to 5.0 mass%, rare earth element: 0.01 to 0.5 mass%, the balance is made of Cr and Ni, and the Cr / Ni ratio is The mass temperature is 0.51 to 1.1, and the temperature coefficient of resistance is within ± 9 ppm / ° C. in the air at a temperature of 200 to 500 ° C. under conditions of 1 to 10 hours. And the high temperature resistance change rate when held at 175 ° C. for 2000 hours is 0.24 % or less.
本明細書における希土類元素とは、Ｙおよびランタノイド（典型的には、ランタン、セリウム）があげられるが、これらの中から１種類または２種類以上を選び、添加することができる。また、セリウム族希土類元素の混合物であるミッシュメタルを使用することもできる。 In this specification, the rare earth elements include Y and lanthanoids (typically lanthanum and cerium), and one or more of them can be selected and added. Misch metal which is a mixture of cerium group rare earth elements can also be used.
本発明の電子部品用抵抗薄膜を形成するためのスパッタリングターゲットは、Ｓｉ：０．２〜５．０質量％、希土類元素：０．０１〜０．５質量％を含み、残部がＣｒおよびＮｉからなり、Ｃｒ／Ｎｉ比が質量で０．５１〜１．１である。その組成は、前記抵抗薄膜材料に実質的に同じである。 The sputtering target for forming the resistive thin film for electronic parts of the present invention contains Si: 0.2 to 5.0 mass%, rare earth element: 0.01 to 0.5 mass%, and the balance is made of Cr and Ni. becomes, Cr / Ni ratio is 0.51 to 1.1 mass. Its composition is substantially the same as the resistive thin film material.
かかるスパッタリングターゲットを用いて、スパッタリング法により、絶縁基板上に、Ｎｉ−Ｃｒ−Ｓｉ−希土類元素合金からなる抵抗薄膜を生成させる。その後、前記抵抗薄膜が形成された基板に、大気中において、温度２００℃〜５００℃で、１〜１０時間の条件で熱処理を行なうことにより、高い高温安定性と良好な抵抗温度特性を備えた抵抗薄膜を得ることができる。かかる抵抗薄膜を用いることで、高温での抵抗変化率が小さく、同時に抵抗温度特性がほぼ０である薄膜抵抗器を得ることができる。 Using such a sputtering target, a resistive thin film made of a Ni—Cr—Si—rare earth element alloy is formed on an insulating substrate by sputtering. Thereafter, the substrate on which the resistance thin film was formed was heat treated in the atmosphere at a temperature of 200 ° C. to 500 ° C. for 1 to 10 hours, thereby providing high temperature stability and good resistance temperature characteristics. A resistive thin film can be obtained. By using such a resistance thin film, it is possible to obtain a thin film resistor having a small resistance change rate at a high temperature and at the same time having a resistance temperature characteristic of almost zero.
本発明のスパッタリングターゲットを用いて、抵抗薄膜を作製した場合、真空中で成膜されたままの抵抗薄膜は、抵抗温度係数が負に大きく、また高温における抵抗安定性が不十分である。当該抵抗薄膜にそれぞれの組成に応じて設定される熱処理を実施することで、抵抗薄膜の抵抗温度係数を、安定的に±９ｐｐｍ／℃以内とすることが可能となる。さらに、本発明の抵抗薄膜に大気中で熱処理をすることによって、抵抗薄膜表面に緻密な酸化膜が形成され、高温で安定な抵抗薄膜も得られる。かかる抵抗薄膜を用いた薄膜抵抗器は、従来のＮｉ−Ｃｒ−Ａｌ−Ｓｉ系合金で達成する高温における抵抗安定性および良好な抵抗温度特性が得られ、その結果、厳しい高温環境下で使用される電子部品に適するという顕著な効果を有する。また、Ａｌを含まない鋳造性のよい組成であるため、真空溶解・鋳造する合金ターゲットの生産性が改善される効果も有する。 When a resistive thin film is produced using the sputtering target of the present invention, the resistive thin film as it is formed in a vacuum has a large negative temperature coefficient of resistance and insufficient resistance stability at high temperatures. By performing heat treatment that is set according to the composition of the resistance thin film, the resistance temperature coefficient of the resistance thin film can be stably within ± 9 ppm / ° C. Further, by subjecting the resistive thin film of the present invention to heat treatment in the atmosphere, a dense oxide film is formed on the surface of the resistive thin film, and a resistive thin film that is stable at high temperatures can also be obtained. A thin film resistor using such a resistance thin film has obtained resistance stability at a high temperature and good resistance temperature characteristics achieved by a conventional Ni-Cr-Al-Si alloy, and as a result, is used in a severe high temperature environment. It has a remarkable effect that it is suitable for electronic components. In addition, since the composition does not contain Al and has good castability, it also has an effect of improving the productivity of an alloy target that is vacuum melted and cast.
発明者等は、鋭意、研究を重ねた結果、従来の抵抗薄膜材料として使用されているＮｉ−Ｃｒ−Ｓｉ系合金に特定の元素の希土類元素成分を添加することにより、当該抵抗薄膜材料をスパッタリングターゲットとして用いて、抵抗薄膜を基板上に形成した薄膜抵抗器において、抵抗温度係数がほぼ０で、高温における抵抗変化率をＮｉ−Ｃｒ−Ａｌ−Ｓｉ合金レベルと同等以下に抑えることができることを見いだし、本発明を完成させた。 As a result of intensive research, the inventors have sputtered the resistive thin film material by adding a rare earth element component of a specific element to a Ni-Cr-Si alloy used as a conventional resistive thin film material. In a thin film resistor having a resistive thin film formed on a substrate as a target, the resistance temperature coefficient is almost 0, and the rate of change in resistance at high temperatures can be suppressed to a level equal to or lower than the Ni-Cr-Al-Si alloy level. As a result, the present invention has been completed.
本発明の抵抗薄膜は、Ｃｒ／Ｎｉ比が質量で０．５１〜１．１であるＮｉ−Ｃｒ合金からなり、Ｓｉを０．２〜５．０質量％、希土類元素を０．０１〜０．５質量％、それぞれ含有している。 The resistive thin film of the present invention is made of a Ni—Cr alloy having a Cr / Ni ratio of 0.51 to 1.1 in terms of mass, with 0.2 to 5.0 mass% of Si and 0.01 to 0 of rare earth elements. .5% by mass, respectively.
Ｃｒ／Ｎｉ比が質量で０．５１未満であると、抵抗温度係数が大きくなり、好ましくない。一方、１．１を超えると、高温安定性が悪くなり、また、製造上の再現性が悪化するため、好ましくない。 If the Cr / Ni ratio is less than 0.51 , the temperature coefficient of resistance increases, which is not preferable. On the other hand, if it exceeds 1.1, the high temperature stability is deteriorated and the reproducibility in production is deteriorated, which is not preferable.
Ｓｉは、主として抵抗温度係数を改善するために添加するが、添加量が０．２質量％未満、または５質量％を超えると、抵抗温度係数が大きくなってしまい、高温安定性も悪くなるので、好ましくない。 Si is mainly added to improve the temperature coefficient of resistance. However, if the amount added is less than 0.2% by mass or exceeds 5% by mass, the temperature coefficient of resistance increases, and the high temperature stability also deteriorates. It is not preferable.
希土類元素は、主として高温安定性を改善するために添加するが、添加量が０．０１質量％未満であると、高温安定性の改善に寄与せず、好ましくない。一方、０．５質量％を超えても、格別の効果増大が期待できず、コストアップとなるので、好ましくない。 Rare earth elements are added mainly to improve high-temperature stability. However, if the addition amount is less than 0.01% by mass, it does not contribute to improvement of high-temperature stability, which is not preferable. On the other hand, even if it exceeds 0.5% by mass, a special effect increase cannot be expected and the cost is increased.
本発明による抵抗薄膜材料は、以下のようにして製造する。上記の組成の金属抵抗体材料からなるスパッタリングターゲットを用いて、スパッタリング法により、絶縁基板上にＮｉ−Ｃｒ−Ｓｉ−希土類元素合金の特定組成の抵抗薄膜を成膜し、その後、この基板を大気中において、温度２００〜５００℃で、１〜１０時間熱処理を行う。熱処理の温度が、２００℃未満では、得られた抵抗薄膜材料の抵抗温度係数が安定せず好ましくない。一方、５００℃を超えると、抵抗温度係数が大きくなり好ましくない。 The resistive thin film material according to the present invention is manufactured as follows. Using a sputtering target made of a metal resistor material having the above composition, a resistive thin film having a specific composition of Ni—Cr—Si—rare earth element alloy is formed on an insulating substrate by sputtering, and then the substrate is exposed to the atmosphere. Inside, heat treatment is performed at a temperature of 200 to 500 ° C. for 1 to 10 hours. When the temperature of the heat treatment is less than 200 ° C., the resistance temperature coefficient of the obtained resistance thin film material is not stable, which is not preferable. On the other hand, if it exceeds 500 ° C., the temperature coefficient of resistance increases, which is not preferable.
また、熱処理の時間が、１時間未満では抵抗温度係数が安定せず好ましくない。一方、１０時間を超えても、抵抗安定性に対する効果の増大はみられず、コストアップとなり好ましくない。 Further, if the heat treatment time is less than 1 hour, the temperature coefficient of resistance is not stable, which is not preferable. On the other hand, even if it exceeds 10 hours, the increase in the effect on the resistance stability is not seen, and the cost increases, which is not preferable.
（実施例、参考例、比較例の薄膜抵抗材料の製造方法）
まず、電気ニッケル、電解クロム、金属シリコン、アルミニウムメタルショット、Ｙメタル塊（試薬）、ランタンメタル（試薬）、セリウムメタル（試薬）、ミッシュメタル（試薬）を原料とし、それぞれ所定の組成となるようにそれぞれ秤量して、真空溶解炉により、約２ｋｇのＮｉ−Ｃｒ−Ｓｉ合金、Ｎｉ−Ｃｒ−Ｓｉ−Ａｌ合金またはＮｉ−Ｃｒ−Ｓｉ−希土類元素合金からなる金属抵抗体材料のインゴットを作製した。
(Methods for producing thin film resistor materials of Examples, Reference Examples, and Comparative Examples)
First, using electric nickel, electrolytic chromium, metallic silicon, aluminum metal shot, Y metal lump (reagent), lanthanum metal (reagent), cerium metal (reagent), and misch metal (reagent) as raw materials, each has a predetermined composition. Ingots of metal resistor materials made of approximately 2 kg of Ni—Cr—Si alloy, Ni—Cr—Si—Al alloy or Ni—Cr—Si—rare earth element alloy were prepared in a vacuum melting furnace. .
次に、抵抗薄膜を製造するために、それぞれのインゴットを、均質化処理の後、ワイヤカットで厚さ５ｍｍ、直径１５０ｍｍの丸板を切り出し、上下面を研削してスパッタリングターゲットとした。 Next, in order to manufacture a resistance thin film, each ingot was homogenized, and then a round plate having a thickness of 5 mm and a diameter of 150 mm was cut by wire cutting, and the upper and lower surfaces were ground to form a sputtering target.
成膜工程は、カソードスパッタリング法によって、以下のように行なった。 The film forming process was performed by the cathode sputtering method as follows.
真空室にアルミナ基板を装入し、１×１０-4Ｐａに排気した後、純度９９．９９９５％のアルゴンガスを導入して、０．３Ｐａの圧力に保ち、スパッタリングパワー０．３ｋＷで、膜厚が５００Åとなるように前記アルミナ基板上に成膜を行い、基板上に抵抗薄膜が形成された抵抗薄膜材料を得た。 An alumina substrate is charged into a vacuum chamber and evacuated to 1 × 10 −4 Pa. Then, an argon gas having a purity of 99.9995% is introduced and maintained at a pressure of 0.3 Pa, with a sputtering power of 0.3 kW. A film was formed on the alumina substrate so as to have a thickness of 500 mm to obtain a resistance thin film material in which a resistance thin film was formed on the substrate.
得られた抵抗薄膜の両側に、厚さ５０００ÅのＡｕ電極を、前述と同様に、カソードスパッタ法により成膜して、抵抗薄膜およびＡｕ電極が形成された基板を得た。抵抗薄膜材料へのＡｕ電極の成膜後、大気中３００℃で３時間の熱処理を行うことにより、それぞれの薄膜抵抗器を得た。 An Au electrode having a thickness of 5000 mm was formed on both sides of the obtained resistance thin film by the cathode sputtering method in the same manner as described above to obtain a substrate on which the resistance thin film and the Au electrode were formed. After forming the Au electrode on the resistive thin film material, each thin film resistor was obtained by performing heat treatment at 300 ° C. for 3 hours in the atmosphere.
（参考例１）
Ｎｉが８３．９質量％、Ｃｒが１４.０質量％、Ｃｒ／Ｎｉ比が質量で０．１７、Ｓｉが２．０質量％、希土類元素としてのＬａは０．１５質量％にそれぞれ秤量し、真空溶解炉により、約２ｋｇのＮｉ−Ｃｒ−Ｓｉ−希土類元素合金のインゴットを作成した。その後の工程は、上記に示したとおりに、スパッタリングターゲットを得た後、スパッタリング法でアルミナ基板に抵抗薄膜を成膜し、さらにＡｕ電極を形成した後に、大気中で３００℃で３時間熱処理を行い、薄膜抵抗器を得た。
( Reference Example 1 )
Ni is 83.9% by mass, Cr is 14.0% by mass, Cr / Ni ratio is 0.17 by mass, Si is 2.0% by mass, and La as a rare earth element is 0.15% by mass. In a vacuum melting furnace, an ingot of about 2 kg of Ni—Cr—Si—rare earth element alloy was prepared. As shown above, after the sputtering target was obtained, a resistive thin film was formed on an alumina substrate by sputtering, and an Au electrode was formed. Thereafter, a heat treatment was performed at 300 ° C. for 3 hours in the atmosphere. And a thin film resistor was obtained.
以上のようにして作製した参考例１の薄膜抵抗器について、抵抗温度特性を評価するため、恒温槽で昇温しながら、２５℃と１２５℃における抵抗測定を行い、抵抗温度係数を算出したところ、２０ｐｐｍ／℃であった。また、高温安定性を評価するため、それぞれの薄膜抵抗器を、１７５℃の恒温槽内に、２０００時間保持し、高温における抵抗変化率を測定したところ、０．２５％が得られた。 In order to evaluate the resistance temperature characteristics of the thin film resistor of Reference Example 1 produced as described above, the resistance temperature coefficient was calculated by measuring resistance at 25 ° C. and 125 ° C. while raising the temperature in a thermostatic bath. 20 ppm / ° C. Moreover, in order to evaluate high temperature stability, when each thin film resistor was hold | maintained in a 175 degreeC thermostat for 2000 hours and the resistance change rate in high temperature was measured, 0.25% was obtained.
（実施例２）
Ｎｉ−Ｃｒ−Ｓｉ−希土類元素合金のインゴットの組成を、Ｎｉが６４．８質量％、Ｃｒが３２．９質量％、Ｃｒ／Ｎｉ比が質量で０．５１、Ｓｉが２．０質量％、希土類元素としてのミッシュメタルは０．２７質量％としたこと以外は参考例１と同じ工程で、薄膜抵抗器を得た。得られた薄膜抵抗器を、参考例１と同じ条件で抵抗温度係数と高温における抵抗変化率を測定したところ、抵抗温度係数は９ｐｐｍ／℃で、高温における抵抗変化率は０．２４％が得られた。
(Example 2)
The composition of the ingot of the Ni-Cr-Si-rare earth element alloy is as follows: Ni is 64.8% by mass, Cr is 32.9% by mass, Cr / Ni ratio is 0.51 by mass, Si is 2.0% by mass, A thin film resistor was obtained by the same process as in Reference Example 1 except that the amount of misch metal as a rare earth element was 0.27% by mass. When the temperature coefficient of resistance and the rate of change in resistance at high temperature of the obtained thin film resistor were measured under the same conditions as in Reference Example 1, the resistance temperature coefficient was 9 ppm / ° C., and the rate of change in resistance at high temperature was 0.24%. It was.
（実施例３）
Ｎｉ−Ｃｒ−Ｓｉ−希土類元素合金のインゴットの組成を、Ｎｉが４９．２質量％、Ｃｒが４８．５質量％、Ｃｒ／Ｎｉ比が質量で０．９８、Ｓｉが２．０質量％、希土類元素としてのミッシュメタルは０．３５質量％としたこと以外は参考例１と同じ工程で、薄膜抵抗器を得た。得られた薄膜抵抗器を、参考例１と同じ条件で抵抗温度係数と高温における抵抗変化率を測定したところ、抵抗温度係数は７ｐｐｍ／℃で、高温における抵抗変化率は０．２４％が得られた。
(Example 3)
The composition of the ingot of the Ni—Cr—Si—rare earth element alloy is as follows: Ni is 49.2% by mass, Cr is 48.5% by mass, Cr / Ni ratio is 0.98 by mass, Si is 2.0% by mass, A thin film resistor was obtained by the same process as in Reference Example 1 except that the amount of misch metal as a rare earth element was 0.35% by mass. When the temperature coefficient of resistance and the rate of change in resistance at high temperature of the obtained thin film resistor were measured under the same conditions as in Reference Example 1, the temperature coefficient of resistance was 7 ppm / ° C, and the rate of change in resistance at high temperature was 0.24%. It was.
（実施例４）
Ｎｉ−Ｃｒ−Ｓｉ−希土類元素合金のインゴットの組成を、Ｎｉが４８．５質量％、Ｃｒが４７．５質量％、Ｃｒ／Ｎｉ比が質量で０．９８、Ｓｉが４．０質量％、希土類元素としてのＹは０．０３質量％としたこと以外は参考例１と同じ工程で、薄膜抵抗器を得た。得られた薄膜抵抗器を、参考例１と同じ条件で抵抗温度係数と高温における抵抗変化率を測定したところ、抵抗温度係数は４ｐｐｍ／℃で、高温における抵抗変化率は０．２３％が得られた。
Example 4
The composition of the ingot of the Ni—Cr—Si—rare earth element alloy is as follows: Ni is 48.5% by mass, Cr is 47.5% by mass, Cr / Ni ratio is 0.98 by mass, Si is 4.0% by mass, A thin film resistor was obtained in the same process as in Reference Example 1 except that Y as the rare earth element was 0.03% by mass. When the temperature coefficient of resistance and the rate of change in resistance at high temperature of the obtained thin film resistor were measured under the same conditions as in Reference Example 1, the resistance temperature coefficient was 4 ppm / ° C., and the rate of change in resistance at high temperature was 0.23%. It was.
（実施例５）
Ｎｉ−Ｃｒ−Ｓｉ−希土類元素合金のインゴットの組成を、Ｎｉが４７．９質量％、Ｃｒが４７．８質量％、Ｃｒ／Ｎｉ比が質量で１．０、Ｓｉが４．１質量％、希土類元素としてのＣｅは０．１７質量％としたこと以外は参考例１と同じ工程で、薄膜抵抗器を得た。得られた薄膜抵抗器を、参考例１と同じ条件で抵抗温度係数と高温における抵抗変化率を測定したところ、抵抗温度係数は４ｐｐｍ／℃で、高温における抵抗変化率は０．２３％が得られた。
(Example 5)
The composition of the ingot of the Ni—Cr—Si—rare earth element alloy is as follows: Ni 47.9% by mass, Cr 47.8% by mass, Cr / Ni ratio 1.0 by mass, Si 4.1% by mass, A thin film resistor was obtained by the same process as in Reference Example 1 except that Ce as a rare earth element was 0.17% by mass. When the temperature coefficient of resistance and the rate of change in resistance at high temperature of the obtained thin film resistor were measured under the same conditions as in Reference Example 1, the resistance temperature coefficient was 4 ppm / ° C., and the rate of change in resistance at high temperature was 0.23%. It was.
（実施例６）
Ｎｉ−Ｃｒ−Ｓｉ−希土類元素合金のインゴットの組成を、Ｎｉが４８．１質量％、Ｃｒが４７．６質量％、Ｃｒ／Ｎｉ比が質量で０．９９、Ｓｉが３．９質量％、希土類元素としてのミッシュメタルは０．４２質量％としたこと以外は参考例１と同じ工程で、薄膜抵抗器を得た。得られた薄膜抵抗器を、参考例１と同じ条件で抵抗温度係数と高温における抵抗変化率を測定したところ、抵抗温度係数は４ｐｐｍ／℃で、高温における抵抗変化率は０．２２％が得られた。
(Example 6)
The composition of the ingot of the Ni—Cr—Si—rare earth element alloy is as follows: Ni is 48.1% by mass, Cr is 47.6% by mass, Cr / Ni ratio is 0.99 by mass, Si is 3.9% by mass, A thin film resistor was obtained by the same process as in Reference Example 1 except that the amount of misch metal as a rare earth element was 0.42% by mass. When the temperature coefficient of resistance and the rate of change in resistance at high temperature of the obtained thin film resistor were measured under the same conditions as in Reference Example 1, the resistance temperature coefficient was 4 ppm / ° C., and the rate of change in resistance at high temperature was 0.22%. It was.
（実施例７）
Ｎｉ−Ｃｒ−Ｓｉ−希土類元素合金のインゴットの組成を、Ｎｉが５０．３質量％、Ｃｒが４９．３質量％、Ｃｒ／Ｎｉ比が質量で０．９８、Ｓｉが０．３質量％、希土類元素としてのＹは０．１９質量％としたこと以外は参考例１と同じ工程で、薄膜抵抗器を得た。得られた薄膜抵抗器を、参考例１と同じ条件で抵抗温度係数と高温における抵抗変化率を測定したところ、抵抗温度係数は７ｐｐｍ／℃で、高温における抵抗変化率は０．２１％が得られた。
(Example 7)
The composition of the ingot of the Ni—Cr—Si—rare earth element alloy is as follows: Ni is 50.3% by mass, Cr is 49.3% by mass, Cr / Ni ratio is 0.98 by mass, Si is 0.3% by mass, A thin film resistor was obtained by the same process as in Reference Example 1 except that Y as the rare earth element was 0.19% by mass. When the temperature coefficient of resistance and the rate of change in resistance at high temperature of the obtained thin film resistor were measured under the same conditions as in Reference Example 1, the resistance temperature coefficient was 7 ppm / ° C., and the rate of change in resistance at high temperature was 0.21%. It was.
（比較例１）
Ｎｉ−Ｃｒ−Ｓｉ−Ａｌインゴットの組成を、Ｎｉが６２．１質量％、Ｃｒが３２．４質量％、Ｃｒ／Ｎｉ比が質量で０．５２、Ｓｉが３．１質量％、Ａｌが２．４質量％としたこと以外は参考例１と同じ工程で、薄膜抵抗器を得た。得られた薄膜抵抗器を、参考例１と同じ条件で抵抗温度係数と高温における抵抗変化率を測定したところ、抵抗温度係数は２０ｐｐｍ／℃で、高温における抵抗変化率は０．２６％が得られた。
(Comparative Example 1)
The composition of the Ni—Cr—Si—Al ingot is as follows: Ni is 62.1% by mass, Cr is 32.4% by mass, Cr / Ni ratio is 0.52 by mass, Si is 3.1% by mass, and Al is 2%. A thin film resistor was obtained by the same process as in Reference Example 1 except that the content was 4% by mass. When the temperature coefficient of resistance and the rate of change in resistance at high temperature of the obtained thin film resistor were measured under the same conditions as in Reference Example 1, the temperature coefficient of resistance was 20 ppm / ° C, and the rate of change in resistance at high temperature was 0.26%. It was.
（比較例２）
Ｎｉ−Ｃｒ−Ｓｉ合金のインゴットの組成を、Ｎｉが４８．２質量％、Ｃｒが４７．６質量％、Ｃｒ／Ｎｉ比が質量で０．９９、Ｓｉが４．２質量％にする以外は参考例１と同じ工程で、薄膜抵抗器を得た。得られた薄膜抵抗器を、参考例１と同じ条件で抵抗温度係数と高温における抵抗変化率を測定したところ、抵抗温度係数は５ｐｐｍ／℃で、高温における抵抗変化率は０．３８％が得られた。
(Comparative Example 2)
The composition of the ingot of the Ni—Cr—Si alloy is 48.2% by mass of Ni, 47.6% by mass of Cr, 0.99 by mass of Cr / Ni, and 4.2% by mass of Si. In the same process as in Reference Example 1, a thin film resistor was obtained. When the temperature coefficient of resistance and the rate of change in resistance at high temperature of the obtained thin film resistor were measured under the same conditions as in Reference Example 1, the temperature coefficient of resistance was 5 ppm / ° C, and the rate of change in resistance at high temperature was 0.38%. It was.
（比較例３）
Ｎｉ−Ｃｒ−Ｓｉ−希土類元素合金のインゴットの組成を、Ｎｉが４７．７質量％、Ｃｒが４７．６質量％、Ｃｒ／Ｎｉ比が質量で１．０、Ｓｉが４．１質量％、希土類元素としてのＬａは０．６１質量％としたこと以外は参考例１と同じ工程で、薄膜抵抗器を得た。得られた薄膜抵抗器を、参考例１と同じ条件で抵抗温度係数と高温における抵抗変化率を測定したところ、抵抗温度係数は６ｐｐｍ／℃で、高温における抵抗変化率は０．２３％が得られた。本比較例のように、希土類元素が０．５質量％を超えても、コストアップとなるが、格別の効果増大は期待できない。
(Comparative Example 3)
The composition of the ingot of the Ni—Cr—Si—rare earth element alloy is as follows: Ni is 47.7% by mass, Cr is 47.6% by mass, Cr / Ni ratio is 1.0 by mass, Si is 4.1% by mass, A thin film resistor was obtained in the same process as Reference Example 1 except that La as the rare earth element was 0.61% by mass. When the temperature coefficient of resistance and the rate of change in resistance at high temperature of the obtained thin film resistor were measured under the same conditions as in Reference Example 1, the temperature coefficient of resistance was 6 ppm / ° C., and the rate of change in resistance at high temperature was 0.23%. It was. As in this comparative example, even if the rare earth element exceeds 0.5 mass%, the cost is increased, but a significant increase in the effect cannot be expected.
（比較例４）
Ｎｉ−Ｃｒ−Ｓｉ−希土類元素合金のインゴットの組成を、Ｎｉが４７．７質量％、Ｃｒが４７．６質量％、Ｃｒ／Ｎｉ比が質量で１．０、Ｓｉが６．２質量％、希土類元素としてのＬａは０．６１質量％としたこと以外は参考例１と同じ工程で、薄膜抵抗器を得た。得られた薄膜抵抗器を、参考例１と同じ条件で抵抗温度係数と高温における抵抗変化率を測定したところ、抵抗温度係数は−３０ｐｐｍ／℃で、高温における抵抗変化率は０．２３％が得られた。
(Comparative Example 4)
The composition of the ingot of the Ni—Cr—Si—rare earth element alloy is as follows: Ni 47.7% by mass, Cr 47.6% by mass, Cr / Ni ratio 1.0 by mass, Si 6.2% by mass, A thin film resistor was obtained in the same process as Reference Example 1 except that La as the rare earth element was 0.61% by mass. When the temperature coefficient of resistance and the rate of change in resistance at high temperature of the obtained thin film resistor were measured under the same conditions as in Reference Example 1, the resistance temperature coefficient was −30 ppm / ° C., and the rate of change in resistance at high temperature was 0.23%. Obtained.
（比較例５）
Ｎｉ−Ｃｒ−希土類元素合金のインゴットの組成を、Ｎｉが５１．２質量％、Ｃｒが４８．７質量％、Ｃｒ／Ｎｉ比が質量で０．９５、希土類元素としてのＹは０．０９％としたこと以外は参考例１と同じ工程で、薄膜抵抗器を得た。得られた薄膜抵抗器を、参考例１と同じ条件で抵抗温度係数と高温における抵抗変化率を測定したところ、抵抗温度係数は−３２ｐｐｍ／℃で、高温における抵抗変化率は０．７６％が得られた。
(Comparative Example 5)
The composition of the ingot of the Ni—Cr—rare earth element alloy is as follows: Ni is 51.2% by mass, Cr is 48.7% by mass, Cr / Ni ratio is 0.95 by mass, and Y as the rare earth element is 0.09%. A thin film resistor was obtained by the same process as in Reference Example 1 except that. When the temperature coefficient of resistance and the rate of change in resistance at high temperature of the obtained thin film resistor were measured under the same conditions as in Reference Example 1, the temperature coefficient of resistance was -32 ppm / ° C and the rate of change in resistance at high temperature was 0.76%. Obtained.
実施例２〜７の薄膜抵抗器は、いずれも抵抗温度係数が±９ｐｐｍ／℃の範囲にあり、良好な抵抗温度特性を示した。また、実施例２〜７の薄膜抵抗器は、いずれも抵抗変化率が０．２４％以下であり、主な従来技術であるＮｉ−Ｃｒ−Ａｌ−Ｓｉ合金系の比較例１と比較して、同等以上の高温安定性を示した。このようにＡｌを含まないＮｉ−Ｃｒ−Ｓｉ−希土類元素合金の薄膜抵抗器は、精密な精度を要求される電子機器を高温で使用するときに、信頼性が向上する。 All of the thin film resistors of Examples 2 to 7 had a resistance temperature coefficient in the range of ± 9 ppm / ° C., and exhibited good resistance temperature characteristics. In addition, the thin film resistors of Examples 2 to 7 all have a resistance change rate of 0.24 % or less, compared with the comparative example 1 of the Ni—Cr—Al—Si alloy system which is the main prior art. High temperature stability equivalent to or better. Thus, the Ni-Cr-Si-rare earth element thin film resistor not containing Al has improved reliability when an electronic device requiring precise accuracy is used at a high temperature.
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