JP5045804B2 - Sputtering target for forming a resistance thin film, resistance thin film, thin film resistor, and manufacturing method thereof - Google Patents
Sputtering target for forming a resistance thin film, resistance thin film, thin film resistor, and manufacturing method thereof Download PDFInfo
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Description
本発明は、電子部品としての薄膜抵抗器、および該薄膜抵抗器を得るために用いられる抵抗薄膜、該抵抗薄膜形成用スパッタリングターゲット、該スパッタリングターゲットとなる抵抗体材料、さらにはこれらの製造方法に関する。 The present invention relates to a thin film resistor as an electronic component, a resistance thin film used for obtaining the thin film resistor, a sputtering target for forming the resistance thin film, a resistor material to be the sputtering target, and a method for producing these. .
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、側温抵抗体、感温抵抗器などの温度センサ、ならびにハイブリッド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 side temperature resistors, temperature sensitive resistors, and electronic components such as hybrid ICs and their composite module products Thin film resistors using thin films are used.
薄膜抵抗器には、（１）抵抗温度係数（ＴＣＲ）の絶対値が０に近いという抵抗温度特性、（２）高温保持における経時的抵抗変化率が小さいという高温安定性、（３）人の汗や海水などに対する耐食性（耐塩水性）、（４）高い比抵抗といった４つの特性が要求されている。 Thin film resistors include (1) resistance-temperature characteristics in which the absolute value of the temperature coefficient of resistance (TCR) is close to 0, (2) high-temperature stability in which the rate of change in resistance over time during high-temperature holding is small, and (3) human resistance Four characteristics such as corrosion resistance (salt water resistance) against sweat and seawater, and (4) high specific resistance are required.
電気・電子製品の小型化に伴い、薄膜抵抗器を小型化することが求められているが、この薄膜抵抗器の小型化には、上記の特性を維持しつつ、抵抗薄膜を構成する抵抗体材料の比抵抗をさらに高くすることが必要である。 With the miniaturization of electrical and electronic products, there is a demand for miniaturization of thin film resistors. For miniaturization of this thin film resistor, a resistor that constitutes a resistive thin film while maintaining the above characteristics. It is necessary to further increase the specific resistance of the material.
薄膜抵抗器においては、多くの場合、抵抗薄膜を形成するための抵抗体材料として、Ｔａ合金、ＴａＮ化合物、Ｎｉ−Ｃｒ系合金などが主に用いられている。 In many thin film resistors, Ta alloy, TaN compound, Ni—Cr alloy, etc. are mainly used as a resistor material for forming a resistive thin film.
このうち、Ｎｉ−Ｃｒ系合金を用いた抵抗薄膜は、金属の特性であるオーミック特性を有し、雰囲気温度の変化に対して抵抗値の変化が少なく、熱的安定性が高いという特徴を有するため、薄膜抵抗器に一般的に使用されている。しかしながら、Ｎｉ−Ｃｒ系合金には、抵抗体材料としては比抵抗が低いという問題がある。 Among these, a resistance thin film using a Ni-Cr alloy has an ohmic characteristic that is a characteristic of a metal, has a feature that there is little change in resistance value with respect to a change in ambient temperature, and high thermal stability. Therefore, it is generally used for thin film resistors. However, the Ni—Cr alloy has a problem of low specific resistance as a resistor material.
このため、Ｎｉ−Ｃｒ系合金にＴａ、Ａｌ、Ｍｏを添加して、比抵抗を高めた抵抗薄膜が提案されている（特許文献１参照）。このＴａ、Ａｌ、Ｍｏが添加されたＮｉ−Ｃｒ系合金による抵抗薄膜は、従来のＮｉ−Ｃｒ系合金を用いた抵抗薄膜に比べれば、耐食性に優れているものの、酸性人工汗液（ＪＩＳ Ｌ０８４８）を用いた電食試験における溶解開始電圧が６Ｖ未満であり、より一層耐食性に優れた抵抗薄膜が望まれている。 For this reason, a resistance thin film has been proposed in which Ta, Al, and Mo are added to a Ni—Cr alloy to increase the specific resistance (see Patent Document 1). The resistance thin film made of a Ni—Cr alloy to which Ta, Al, and Mo are added is superior in corrosion resistance to a resistance thin film using a conventional Ni—Cr alloy, but is an artificial artificial sweat (JIS L0848). There is a demand for a resistance thin film that has a dissolution initiation voltage of less than 6 V in an electrolytic corrosion test using, and is further excellent in corrosion resistance.
また、当該Ｎｉ−Ｃｒ系合金は、所定の特性を得るために熱処理が施されるが、要求される特性によっては５００℃を超える高温での熱処理が要求される。このため、かかる熱処理温度をさらに低くすることも要求されている。 In addition, the Ni—Cr-based alloy is subjected to heat treatment in order to obtain predetermined characteristics, but depending on the required characteristics, heat treatment at a high temperature exceeding 500 ° C. is required. For this reason, it is also required to further lower the heat treatment temperature.
よって、本発明は、抵抗薄膜の熱処理が比較的低い温度でなされた場合でも、上記のＴａ、Ａｌ、Ｍｏが添加されたＮｉ−Ｃｒ系合金と同様の高い比抵抗、優れた抵抗温度特性、高温安定性を保持しつつ、さらに高い耐食性をも備える、薄膜抵抗器を提供することを目的とする。 Therefore, even when the heat treatment of the resistance thin film is performed at a relatively low temperature, the present invention has the same high specific resistance as that of the Ni—Cr alloy to which Ta, Al, and Mo are added, excellent resistance temperature characteristics, An object of the present invention is to provide a thin film resistor having high corrosion resistance while maintaining high temperature stability.
本発明の抵抗体材料は、Ｃｒ、ＡｌおよびＹから選択される１種以上の添加元素を１０〜６０質量％含有し、残部がＮｉと不可避不純物からなるＮｉ合金に、ＳｉＯ2（シリカ）を主成分とし、Ｂ、Ｍｇ、Ｃａ、Ｂａ、Ａｌ、Ｚｒおよびこれらの酸化物から選択される１種以上を０〜９０質量％含有するシリケート系ガラスが３〜２０質量％添加されていることを特徴とする。 The resistor material of the present invention contains 10 to 60% by mass of one or more additive elements selected from Cr, Al, and Y, and a SiO 2 (silica) is added to a Ni alloy consisting of Ni and inevitable impurities. 3-20% by mass of silicate glass containing 0-90% by mass of one or more selected from B, Mg, Ca, Ba, Al, Zr and their oxides as a main component is added. Features.
本発明の抵抗薄膜形成用スパッタリングターゲットは、ＳｉＯ2を主成分とし、Ｂ、Ｍｇ、Ｃａ、Ｂａ、Ａｌ、Ｚｒおよびこれらの酸化物から選択される１種以上が０〜９０質量％添加されたシリケート系ガラス粉末と、Ｃｒ、ＡｌおよびＹから選択される１種以上の添加元素を１０〜６０質量％含有し、残部がＮｉと不可避不純物からなるＮｉ合金粉末とを、前記シリケート系ガラス粉末が３〜２０質量％となるように混合し、得られた混合粉末を所望形状に成形し、得られた成形体を、真空または不活性雰囲気中にて、５０ｋｇ／ｃｍ2以上の加圧下において、５００〜１４００℃で焼結することにより得られる。 The sputtering target for forming a resistance thin film of the present invention contains SiO 2 as a main component, and 0 to 90% by mass of one or more selected from B, Mg, Ca, Ba, Al, Zr and oxides thereof are added. The silicate glass powder contains a silicate glass powder and a Ni alloy powder containing 10 to 60% by mass of one or more additive elements selected from Cr, Al and Y, with the balance being Ni and inevitable impurities. Mixing so as to be 3 to 20% by mass, molding the obtained mixed powder into a desired shape, and the obtained molded body in a vacuum or an inert atmosphere under a pressure of 50 kg / cm 2 or more, It is obtained by sintering at 500-1400 ° C.
かかるスパッタリングターゲットの組成は、前記抵抗体材料と実質的に同じである。 The composition of such a sputtering target is substantially the same as that of the resistor material.
本発明の抵抗薄膜は、上記の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、絶縁材料基板上に薄膜を形成し、得られた薄膜を、大気中または不活性ガス雰囲気中において、２００〜５００℃で、１〜１０時間の熱処理を行うことにより得られる。 The resistive thin film of the present invention is formed by forming a thin film on an insulating material substrate by the sputtering method using the above sputtering target, and the obtained thin film is 200 to 500 ° C. in the atmosphere or in an inert gas atmosphere. It is obtained by performing a heat treatment for 1 to 10 hours.
かかる抵抗薄膜の組成も、前記スパッタリグターゲットを構成する抵抗体材料と実質的に同じである。 The composition of the resistive thin film is also substantially the same as the resistive material constituting the sputtering rig target.
本発明の抵抗薄膜は、比抵抗が３００〜１５００μΩ・ｃｍであり、抵抗温度係数が−２５〜＋２５ｐｐｍ／℃の範囲にあり、１５５℃で１０００時間の高温保持における経時的抵抗変化率が０．１％以下であり、かつ、酸性人工汗液（ＪIＳ Ｌ０８４８）を用いた電食試験における溶解開始電圧が９Ｖ以上という特性を有する。 The resistance thin film of the present invention has a specific resistance of 300 to 1500 μΩ · cm, a temperature coefficient of resistance in the range of −25 to +25 ppm / ° C., and the rate of change in resistance with time at high temperature holding at 155 ° C. for 1000 hours is 0.1. 1% or less, and the dissolution start voltage in the electrolytic corrosion test using acidic artificial sweat (JIS L0848) is 9 V or more.
本発明の薄膜抵抗器は、絶縁材料基板と、該絶縁材料基板上に形成された抵抗薄膜と、該絶縁材料基板上で該抵抗薄膜の両側に形成された電極とからなり、前記抵抗薄膜が上記の抵抗薄膜特性を有することを特徴とする。 The thin film resistor of the present invention comprises an insulating material substrate, a resistive thin film formed on the insulating material substrate, and electrodes formed on both sides of the resistive thin film on the insulating material substrate. It has the above-mentioned resistance thin film characteristic.
本発明の抵抗薄膜材料をスパッタリングターゲットとして用い、スパッタリング法により成膜することにより得られた抵抗薄膜を使用する薄膜抵抗器は、３００〜１５００μΩ・ｃｍという高い比抵抗、抵抗温度係数の絶対値が±２５ｐｐｍ／℃の範囲にあるという優れた抵抗温度特性、１５５℃で１０００時間の高温保持における経時的抵抗変化率が０．１％以下であるという高い高温安定性、さらには、酸性人工汗液（ＪIＳ Ｌ０８４８）を用いた電食試験における溶解開始電圧が９Ｖ以上という高い耐食性（耐塩水性）を同時に満たすことが可能である。 A thin film resistor using a resistance thin film obtained by forming a film by sputtering using the resistance thin film material of the present invention as a sputtering target has a high specific resistance of 300 to 1500 μΩ · cm and an absolute value of a temperature coefficient of resistance. Excellent resistance temperature characteristics in the range of ± 25 ppm / ° C. High temperature stability with a time-dependent resistance change rate of 0.1% or less at 155 ° C. holding for 1000 hours at a high temperature. It is possible to simultaneously satisfy high corrosion resistance (salt water resistance) with a dissolution starting voltage of 9 V or more in an electrolytic corrosion test using JIS L0848).
すなわち、本発明により、高抵抗で高温安定性に優れた電子部品を、従前より優れた耐食性が要求される厳しい環境下で使用することが可能となると共に、上記特性を従前より低い側の温度の熱処理で得られることから、本発明は薄膜抵抗器の製造の低コスト化にも寄与する。 That is, according to the present invention, an electronic component having high resistance and excellent high-temperature stability can be used in a severe environment where corrosion resistance better than before is required, and the above characteristics are reduced to a lower temperature. Therefore, the present invention also contributes to cost reduction in the manufacture of the thin film resistor.
薄膜抵抗器には、高抵抗、安定した抵抗温度特性、優れた高温安定性および高い耐食性（耐塩水性）という４つの特性が要求され、Ｎｉ−Ｃｒ系合金を中心として、その改善のためのさまざまな試みがなされてきている。 Thin film resistors are required to have four characteristics: high resistance, stable resistance temperature characteristics, excellent high temperature stability, and high corrosion resistance (salt water resistance). Attempts have been made.
Ｎｉ−Ｃｒ系合金のうち、Ｔａ、ＡｌおよびＭｏを添加したＮｉ−Ｃｒ系合金は、従来のものと比較して、抵抗温度特性および高温安定性を維持したまま、抵抗および耐食性の改善が図られている。しかしながら、上述の通り、このような特性を得る、特に抵抗温度係数を所定の範囲とするためには、上記抵抗体材料を用いて成膜された薄膜を２００〜６００℃の温度で、１〜１０時間の熱処理を施す必要があり、所望される特性によっては、高温側の温度での熱処理が必要となり、上記特性の維持もしくはさらなる改善を図りつつ、より低温側での熱処理を可能とする抵抗体材料が要望されている。 Of the Ni-Cr alloys, the Ni-Cr alloys to which Ta, Al and Mo are added have improved resistance and corrosion resistance while maintaining the resistance-temperature characteristics and high-temperature stability. It has been. However, as described above, in order to obtain such characteristics, particularly in order to set the temperature coefficient of resistance within a predetermined range, a thin film formed using the resistor material is formed at a temperature of 200 to 600 ° C. It is necessary to perform a heat treatment for 10 hours, and depending on the desired characteristics, a heat treatment at a high temperature side is required, and a resistance that enables a heat treatment at a lower temperature side while maintaining or further improving the above characteristics. Body materials are desired.
本発明者らは、鋭意研究を重ねた結果、従来の電子部品用の薄膜抵抗器に用いられる抵抗体材料としては利用されていなかった、シリケート系ガラスをＮｉ合金に所定量だけ添加することにより、所望の特性を得るための熱処理温度を相対的に低下させることができ、かつ、上記の特性、特に耐食性のさらなる改善を図れるとの知見を得て、本発明を完成させたものである。 As a result of intensive research, the inventors have added a predetermined amount of silicate glass, which has not been used as a resistor material used in a thin film resistor for a conventional electronic component, to a Ni alloy. The present invention has been completed by obtaining the knowledge that the heat treatment temperature for obtaining desired characteristics can be relatively lowered and that the above characteristics, particularly corrosion resistance, can be further improved.
本発明の抵抗体材料は、Ｃｒ、ＡｌおよびＹから選択される１種以上の添加元素を１０〜６０質量％含有し、残部がＮｉと不可避不純物からなるＮｉ合金に、ＳｉＯ2（シリカ）を主成分とし、Ｂ、Ｍｇ、Ｃａ、Ｂａ、Ａｌ、Ｚｒおよびこれらの酸化物から選択される１種以上を０〜９０質量％含有するシリケート系ガラスが３〜２０質量％添加されていることを特徴とする。 The resistor material of the present invention contains 10 to 60% by mass of one or more additive elements selected from Cr, Al, and Y, and a SiO 2 (silica) is added to a Ni alloy consisting of Ni and inevitable impurities. 3-20% by mass of silicate glass containing 0-90% by mass of one or more selected from B, Mg, Ca, Ba, Al, Zr and their oxides as a main component is added. Features.
なお、かかる抵抗体材料は、上記の組成に特徴を有しているものであり、実質的に同じ組成を有する限り、その形態には制限されるものではない。よって、抵抗体材料の用語は、抵抗薄膜形成の過程における、原材料から抵抗薄膜までのすべての形態を総称するものである。 Such a resistor material is characterized by the above composition and is not limited to the form as long as it has substantially the same composition. Therefore, the term resistor material is a general term for all forms from the raw material to the resistive thin film in the process of forming the resistive thin film.
本発明の抵抗体材料を基本的に構成するものは、Ｎｉ合金である。かかるＮｉ合金は、Ｃｒ、ＡｌおよびＹから選択される１種以上の添加元素を１０〜６０質量％含有し、残部がＮｉと不可避不純物からなっている。 The basic constituent of the resistor material of the present invention is a Ni alloy. Such Ni alloy contains 10 to 60% by mass of one or more additive elements selected from Cr, Al and Y, and the balance is made of Ni and inevitable impurities.
添加元素にはそれぞれ効果があり、Ｃｒは抵抗温度係数の絶対値の低減に、Ａｌは耐食性の向上に、ＹはＮｉ合金とガラス粉末の密着性の向上にそれぞれ寄与するものである。これらの添加元素は、要求される特性に応じて必要量だけ添加されるものであるが、本願発明の薄膜抵抗器における特性を具備するためには、すべての添加元素を含有していることが好ましい。それぞれの特性を発揮するためには、Ｃｒは１０質量％以上、Ａｌは１０質量％以上、Ｙは０．３質量％以上、それぞれ含有される必要があり、かつ、総量で１０質量％以上とする必要がある。添加元素の添加量が総量で１０質量％未満となると、得られる抵抗薄膜の比抵抗が十分に大きくならない。一方、これらの添加元素は過多になると成膜、加熱後の安定性が悪くなり、再現性が悪くなってしまうため、総量で６０質量％以下とする必要がある。好ましくは、抵抗温度係数の絶対値を小さくする観点から、添加元素の総量は、４０〜５０質量％の範囲とする。抵抗温度係数は、後述するガラスの組成でも変化するが、Ｎｉ合金の組成でも変化する。この点を考慮すると、Ｎｉ合金への添加元素の総量は、４０〜５０質量％が好ましい。 Each additive element has an effect, Cr contributes to the reduction of the absolute value of the resistance temperature coefficient, Al contributes to the improvement of corrosion resistance, and Y contributes to the improvement of the adhesion between the Ni alloy and the glass powder. These additive elements are added in a necessary amount according to the required characteristics, but in order to have the characteristics in the thin film resistor of the present invention, it is necessary to contain all the additive elements. preferable. In order to exhibit the respective characteristics, Cr must be contained by 10% by mass or more, Al by 10% by mass or more, and Y by 0.3% by mass or more, respectively, and the total amount is 10% by mass or more. There is a need to. When the total amount of additive elements is less than 10% by mass, the specific resistance of the resulting resistance thin film is not sufficiently increased. On the other hand, if these additive elements are excessive, the stability after film formation and heating deteriorates and the reproducibility deteriorates, so the total amount needs to be 60% by mass or less. Preferably, from the viewpoint of reducing the absolute value of the resistance temperature coefficient, the total amount of additive elements is in the range of 40 to 50% by mass. The temperature coefficient of resistance varies depending on the glass composition described later, but also varies depending on the composition of the Ni alloy. Considering this point, the total amount of additive elements to the Ni alloy is preferably 40 to 50% by mass.
本発明の抵抗体材料は、かかるＮｉ合金に、ＳｉＯ2（シリカ）を主成分とし、Ｂ、Ｍｇ、Ｃａ、Ｂａ、Ａｌ、Ｚｒ、およびこれらの酸化物から選択される１種以上を０〜９０質量％含有するシリケート系ガラスが３〜２０質量％添加されていることに特徴がある。 The resistor material of the present invention contains, in such a Ni alloy, one or more selected from B, Mg, Ca, Ba, Al, Zr, and oxides thereof, containing SiO 2 (silica) as a main component. It is characterized in that 3 to 20% by mass of silicate glass containing 90% by mass is added.
シリケート系ガラスは、主として抵抗薄膜の抵抗値を上昇させる効果がある。また、抵抗薄膜の耐食性を向上させる効果もある。さらに、シリケート系ガラスを含有することにより、所望の特性を得るため成膜後の薄膜に対する熱処理温度を相対的に低下させることができる。 Silicate glass mainly has the effect of increasing the resistance value of the resistive thin film. In addition, there is an effect of improving the corrosion resistance of the resistance thin film. Further, by containing silicate glass, the heat treatment temperature for the thin film after film formation can be relatively lowered in order to obtain desired characteristics.
シリケート系ガラスは絶縁体であるため、３質量％以上と少量の添加でもその効果を得ることは可能である。反対に、添加量が２０質量％を超えると絶縁体となり、ＤＣスパッタリングによる成膜ができなくなるため、コスト面で問題が生ずる。なお、シリケート系ガラスの添加量は、５〜１０質量％の範囲が好ましい。 Since the silicate glass is an insulator, the effect can be obtained even with a small amount of addition of 3% by mass or more. On the other hand, if the added amount exceeds 20% by mass, an insulator is formed, and film formation by DC sputtering becomes impossible, which causes a problem in cost. In addition, the addition amount of silicate glass has the preferable range of 5-10 mass%.
シリケート系ガラスには、添加物として、Ｂ、Ｍｇ、Ｃａ、Ｂａ、Ａｌ、Ｚｒ、およびこれらの酸化物から選択される１種以上が含まれている。ただし、これらの添加物の含有量は、９０質量％以下とする。かかる添加物の含有量が９０質量％を超えてしまうと、抵抗温度係数の絶対値を±２５ｐｐｍ／℃の範囲内とすることができなくなってしまう。 The silicate glass contains at least one selected from B, Mg, Ca, Ba, Al, Zr, and oxides thereof as an additive. However, the content of these additives is 90% by mass or less. If the content of such additives exceeds 90% by mass, the absolute value of the resistance temperature coefficient cannot be made within the range of ± 25 ppm / ° C.
これらのＢ、Ｍｇ、Ｃａ、Ｂａ、Ａｌ、Ｚｒ、またはこれらの酸化物の添加により、抵抗薄膜の融着温度、耐水性の微調整を行うことが可能となる。また、Ａｌまたはアルミナ（Ａｌ2Ｏ3）の添加により抵抗薄膜の分相が生じてしまうことが抑制される。ただし、本発明は、これらの添加物によって影響を受けるものではなく、上記はシリケート系ガラスが含有しうる添加物を例示したものにすぎず、これらの添加物がまったく含まれないシリケート系ガラスも本発明に適用することができる。なお、シリケートガラスの結晶性の観点から、かかる添加物を添加する場合には、Ｂ、Ｍｇ、Ｃａ、Ｂａ、Ａｌ、Ｚｒのすべてが含まれることが好ましい。また、同様の理由から、これらが酸化物である場合も含めて、その総量が３０〜７０質量％の範囲とすることが望ましい。 By adding these B, Mg, Ca, Ba, Al, Zr, or their oxides, it becomes possible to finely adjust the fusion temperature and water resistance of the resistance thin film. Further, the addition of Al or alumina (Al 2 O 3 ) suppresses the occurrence of phase separation of the resistance thin film. However, the present invention is not affected by these additives, and the above is merely an example of additives that the silicate glass can contain, and silicate glasses that do not contain these additives are also included. It can be applied to the present invention. In addition, from the viewpoint of crystallinity of the silicate glass, when adding such an additive, it is preferable that all of B, Mg, Ca, Ba, Al, and Zr are included. For the same reason, it is desirable that the total amount is 30 to 70% by mass, including the case where these are oxides.
必要に応じて、後述のホットプレスにて焼結を行った後、シリケート系ガラスが結晶化しないように、これらの添加物および添加量を調整することが望ましい場合がある。シリケート系ガラスが結晶化してしまうと、抵抗体材料の密度が上がらず、強度が低下してしまい、スパッタリングによる成膜に支障が出る場合があるためである。 If necessary, it may be desirable to adjust these additives and amounts so that the silicate glass does not crystallize after sintering in a hot press described below. This is because if the silicate glass is crystallized, the density of the resistor material does not increase and the strength decreases, which may hinder the film formation by sputtering.
次に、本発明の抵抗薄膜形成用スパッタリングターゲットの作製について説明する。かかるスパッタリングターゲットの原材料には、ＳｉＯ2を主成分とし、Ｂ、Ｍｇ、Ｃａ、Ｂａ、Ａｌ、Ｚｒ、およびこれらの酸化物から選択される１種以上が０〜９０質量％添加されたシリケート系ガラス粉末と、Ｃｒ、ＡｌおよびＹから選択される１種以上の添加元素を１０〜６０質量％（好ましくは、４０〜５０質量％）含有し、残部がＮｉと不可避不純物からなるＮｉ合金粉末とを用いる。 Next, preparation of the sputtering target for forming a resistance thin film of the present invention will be described. The raw material of such a sputtering target is a silicate system containing SiO 2 as a main component and 0 to 90% by mass of one or more selected from B, Mg, Ca, Ba, Al, Zr, and oxides thereof. A glass powder and a Ni alloy powder containing 10 to 60% by mass (preferably 40 to 50% by mass) of one or more additive elements selected from Cr, Al and Y, with the balance being Ni and inevitable impurities Is used.
原料粉末であるＮｉ合金粉末としては、平均粒径が１０〜２００μｍ、好ましくは３０〜１５０μｍの範囲内にある、さらに好ましくは１００μｍ程度である、球状のアトマイズ粉を用いることが望ましい。また、シリケート系ガラス粉末としては、平均粒径が０．５〜５０μｍ、好ましくは１〜３０μｍの範囲内にある、さらに好ましくは１０μｍ程度である、粉末を用いることが望ましい。 As the Ni alloy powder which is a raw material powder, it is desirable to use a spherical atomized powder having an average particle diameter in the range of 10 to 200 μm, preferably in the range of 30 to 150 μm, more preferably about 100 μm. As the silicate glass powder, it is desirable to use a powder having an average particle diameter of 0.5 to 50 μm, preferably 1 to 30 μm, more preferably about 10 μm.
原料粉末を焼結させることから、通常は原料粉末の粒径は細かい方が望ましい。しかしながら、ホットプレスで焼結を行う場合は、その限りではない。ホットプレスを行う際に、カーボン型に原料粉末を充填するが、カーボン型にはつなぎ目に隙間が存在するため、原料粉末が細かすぎると隙間から原料粉末が漏れ出し、作業性が低下するためである。 Since the raw material powder is sintered, it is usually desirable that the particle size of the raw material powder is fine. However, this is not the case when sintering is performed by hot pressing. When performing hot pressing, the carbon mold is filled with the raw material powder. Since there is a gap at the joint in the carbon mold, if the raw material powder is too fine, the raw material powder will leak out from the gap and workability will be reduced. is there.
一方、Ｎｉ合金粉末の平均粒径が２００μｍを超えたり、シリケート系ガラス粉末の平均粒径が５０μｍを超えたりした場合には、ターゲットの密度が低下するという問題が生ずる。 On the other hand, when the average particle diameter of the Ni alloy powder exceeds 200 μm or the average particle diameter of the silicate glass powder exceeds 50 μm, there arises a problem that the density of the target is lowered.
これらの原材料を、前記シリケート系ガラス粉末が３〜２０質量％（好ましくは、５〜１０質量％）となるように乾式混合し、原料粉末としての混合粉末を得て、得られた混合粉末を所望形状に成形し、得られた成形体を、好ましくはホットプレス法により、焼結させることにより、前記スパッタリングターゲットを得ることができる。具体的な焼結条件として、真空または不活性雰囲気中にて、５０ｋｇ／ｃｍ2以上の加圧下において、５００〜１４００℃で、１〜５時間の焼成により焼結させることが好ましい。なお、本明細書におけるホットプレス法には、ＨＩＰ（熱間静水圧プレス）法も含まれる。５０ｋｇ／ｃｍ2未満や、焼成時間が１時間未満の場合には、高密度のターゲットが得られない。一方、５時間を超えるホットプレスを行っても、密度をさらに向上させる効果は得られない。 These raw materials are dry-mixed so that the silicate glass powder is 3 to 20% by mass (preferably 5 to 10% by mass) to obtain a mixed powder as a raw material powder. The said sputtering target can be obtained by shape | molding in a desired shape and sintering the obtained molded object, Preferably by the hot press method. As specific sintering conditions, it is preferable to sinter by firing at 500 to 1400 ° C. for 1 to 5 hours under a pressure of 50 kg / cm 2 or more in a vacuum or an inert atmosphere. The hot pressing method in this specification includes a HIP (hot isostatic pressing) method. If it is less than 50 kg / cm 2 or the firing time is less than 1 hour, a high-density target cannot be obtained. On the other hand, even if hot pressing is performed for more than 5 hours, the effect of further improving the density cannot be obtained.
焼結温度はガラス粉末の軟化点よりは高く、Ｎｉ合金の融点よりは低いことが望ましい。こうして得られた焼結体を必要に応じて寸法を調製し、ボンディングなどを行うことにより、スパッタリングターゲットが得られる。 The sintering temperature is preferably higher than the softening point of the glass powder and lower than the melting point of the Ni alloy. The sputtering target can be obtained by adjusting the dimensions of the sintered body thus obtained and performing bonding or the like.
次に、本発明の抵抗薄膜の作製について説明する。上記のようにして得られたスパッタリングターゲットを使用して、スパッタリング法により成膜を行うと、抵抗体材料と実質的に同じ組成の薄膜が得られる。このときの基板としては、Ａｌ2Ｏ3、ＳｉＯ2などの絶縁体基板が望ましい。なお、スパッタリング法のほか、本発明の抵抗体材料を蒸着用タブレットに加工して、真空蒸着などの蒸着法により抵抗薄膜を成膜することも可能である。 Next, production of the resistive thin film of the present invention will be described. When a film is formed by sputtering using the sputtering target obtained as described above, a thin film having substantially the same composition as that of the resistor material is obtained. As the substrate at this time, an insulating substrate such as Al 2 O 3 or SiO 2 is desirable. In addition to the sputtering method, the resistor material of the present invention can be processed into a deposition tablet, and a resistive thin film can be formed by a deposition method such as vacuum deposition.
スパッタリング法については、その種類による制限はないが、コスト面および量産性の観点からＤＣスパッタリングを用いることが好ましい。スパッタリング条件は、スパッタリング装置にもよるが、たとえば、ターゲットサイズ：φ７５ｍｍ×３ｍｍのスパッタリングターゲットを用いて、出力：２００Ｗ（固定）のスパッタリング装置を用いる場合、電圧：４００〜６００Ｖ、電流：０．３〜０．５Ａ、Ａｒ流量：１５〜２５ＳＣＣＭ、全圧力：０．４〜０．６Ｐａ、ＴＳ距離（ターゲットから基板までの距離）：８５ｍｍの条件で成膜する。 Although there is no restriction | limiting by the kind about sputtering method, It is preferable to use DC sputtering from a viewpoint of cost and mass-productivity. Sputtering conditions vary depending on the sputtering apparatus. For example, when using a sputtering target with a target size of φ75 mm × 3 mm and an output of 200 W (fixed), voltage: 400 to 600 V, current: 0.3 The film is formed under the conditions of ˜0.5 A, Ar flow rate: 15 to 25 SCCM, total pressure: 0.4 to 0.6 Pa, TS distance (distance from the target to the substrate): 85 mm.
スパッタリング成膜を行っただけの薄膜は、抵抗温度係数が負に大きく、さらに高温における抵抗安定性が不十分である。このため、成膜後の薄膜の組成に応じて、大気中または不活性ガス中において、２００〜５００℃で、１〜１０時間の熱処理を行う必要がある。かかる熱処理により、抵抗温度係数の絶対値が±２５ｐｐｍ／℃よりも小さい抵抗薄膜を得ることができる。 A thin film formed by sputtering only has a large negative temperature coefficient of resistance, and resistance resistance at high temperatures is insufficient. For this reason, it is necessary to perform heat treatment at 200 to 500 ° C. for 1 to 10 hours in the air or in an inert gas depending on the composition of the thin film after film formation. By such heat treatment, a resistance thin film having an absolute value of a resistance temperature coefficient smaller than ± 25 ppm / ° C. can be obtained.
熱処理の温度が２００℃未満では、得られる抵抗薄膜の抵抗温度係数が安定せず、一方、５００℃を超えると、抵抗薄膜の抵抗温度係数が正に大きくなってしまう。また、熱処理時間が１時間未満では、得られる抵抗薄膜の抵抗温度係数が安定せず、一方、１０時間を超えても、抵抗温度係数の安定性に改善効果のさらなる増大は見られないので、コストアップとなる。 When the temperature of the heat treatment is less than 200 ° C., the resistance temperature coefficient of the resulting resistance thin film is not stable. On the other hand, when the temperature exceeds 500 ° C., the resistance temperature coefficient of the resistance thin film is positively increased. In addition, when the heat treatment time is less than 1 hour, the resistance temperature coefficient of the resulting resistance thin film is not stable. On the other hand, even if it exceeds 10 hours, the stability of the resistance temperature coefficient is not further increased. Cost increases.
なお、本発明の抵抗体材料の組成においては、かかる熱処理温度は、Ｔａ、ＡｌおよびＭｏを添加したＮｉ−Ｃｒ系合金を用いた抵抗薄膜の場合と比較すると、相対的に低下する。特に、かかるＮｉ−Ｃｒ系合金では、組成によっては、所望の特性を得るために、５００℃を超える高温での熱処理が必要とされる場合があったが、本発明の抵抗体材料の組成においては、５００℃以下となり、かつ、組成範囲にわたって熱処理温度を低温側にシフトさせることができる。 In the composition of the resistor material of the present invention, the heat treatment temperature is relatively lowered as compared with the case of the resistance thin film using the Ni—Cr alloy to which Ta, Al and Mo are added. In particular, in such a Ni—Cr alloy, depending on the composition, a heat treatment at a high temperature exceeding 500 ° C. may be required in order to obtain desired characteristics. In the composition of the resistor material of the present invention, however, Is 500 ° C. or lower, and the heat treatment temperature can be shifted to the low temperature side over the composition range.
また、特性面において、本発明の抵抗薄膜は、従来と同様の特性を維持しており、特に耐食性（耐塩水性）においては、酸性人工汗液（ＪIＳ Ｌ０８４８）を用いた電食試験における溶解開始電圧が９Ｖ以上という、より優れた効果を得ることができている。 Further, in terms of characteristics, the resistive thin film of the present invention maintains the same characteristics as those of the conventional ones. In particular, in terms of corrosion resistance (salt water resistance), a dissolution start voltage in an electrolytic corrosion test using an acidic artificial sweat (JIS L0848). A more excellent effect of 9 V or more can be obtained.
本発明に係る薄膜抵抗器は、図１に示すように、絶縁材料基板（１）と、その上に形成された抵抗薄膜（２）と、絶縁材料基板（１）上で抵抗薄膜（２）の両側に形成された電極（３）とからなる。電極（３）としては、Ａｕ電極のほかにＡｌ、Ａｇ、Ｃｕ、Ｎｉ、Ｃｒなどの電極を用いることができる。かかる薄膜抵抗器は、本発明の抵抗薄膜に基づく特性を有することとなる。 As shown in FIG. 1, a thin film resistor according to the present invention comprises an insulating material substrate (1), a resistive thin film (2) formed thereon, and a resistive thin film (2) on the insulating material substrate (1). Electrode (3) formed on both sides. As the electrode (3), an electrode such as Al, Ag, Cu, Ni, or Cr can be used in addition to the Au electrode. Such a thin film resistor will have characteristics based on the resistive thin film of the present invention.
（実施例１）
Ｎｉ合金粉末として、Ｃｒ、Ａｌ、およびＹを総量で４０質量％添加（Ｃｒ：Ａｌ：Ｙ＝２９．５：１０．０：０．５（質量比））した、平均粒径が１００μｍのＮｉ合金粉末を準備した。一方、シリケート系ガラス粉末として、Ｂ、Ｍｇ、Ｃａ、Ｂａ、Ａｌ、およびＺｒを総量で５０質量％添加（Ｂ：Ｍｇ：Ｃａ：Ｂａ：Ｚｒ：Ａｌ＝２：５：１８：１８：５：２（質量比））した、平均粒径が１０μｍのＳｉＯ2粉末を準備した。
Example 1
As Ni alloy powder, Cr, Al, and Y were added in a total amount of 40% by mass (Cr: Al: Y = 29.5: 10.0: 0.5 (mass ratio)), Ni having an average particle diameter of 100 μm Alloy powder was prepared. On the other hand, as a silicate glass powder, B, Mg, Ca, Ba, Al, and Zr are added in a total amount of 50% by mass (B: Mg: Ca: Ba: Zr: Al = 2: 5: 18: 18: 5: 2 (mass ratio)), and an SiO 2 powder having an average particle diameter of 10 μm was prepared.
かかる２種類の粉末を、シリケート系ガラス粉末の添加量が５質量％となるように混合し、原料粉末とした。 These two kinds of powders were mixed so that the addition amount of the silicate glass powder was 5% by mass to obtain a raw material powder.
この原料粉末を、所望形状のカーボン型に装填し、株式会社広築製、雰囲気ホットプレス炉（ＡＨＰ）を用いてホットプレスを行った。Ａｒを２Ｌ／ｍｉｎで流す不活性雰囲気中で、２００ｋｇ／ｃｍ2の圧力、１１００℃の焼成温度、３時間の焼成時間という条件にて、該成形体を焼結させ、焼結体を得た。 This raw material powder was loaded into a carbon mold having a desired shape, and hot pressing was performed using an atmosphere hot press furnace (AHP) manufactured by Hiroki Co., Ltd. The molded body was sintered in an inert atmosphere in which Ar was flowed at 2 L / min under the conditions of a pressure of 200 kg / cm 2 , a firing temperature of 1100 ° C., and a firing time of 3 hours to obtain a sintered body. .
得られた焼結体を平面研削盤（株式会社岡本工作機械製作所製 ＰＳＧ−１０５ＤＸ）にて厚さを３．０ｍｍに加工した後、ワイヤーカット（株式会社ソディック製 ＡＱ７５０Ｌ）にて直径を７５．０ｍｍに加工した後、インジウム蝋材を使用して、バッキングプレートと焼結体をボンディングして、スパッタリングターゲットとした。 The obtained sintered body was processed to a thickness of 3.0 mm with a surface grinding machine (PSG-105DX manufactured by Okamoto Machine Tool Co., Ltd.), and then the diameter was adjusted to 75.75 mm with a wire cut (AQ750L manufactured by Sodick Co., Ltd.). After processing to 0 mm, an indium wax material was used to bond the backing plate and the sintered body to obtain a sputtering target.
このようにして得られたスパッタリングターゲットを、ＤＣスパッタリング装置（芝浦メカトロニクス株式会社製、ＣＦＳ−４ＥＳ）に、ＴＳ距離（ターゲットから基板までの距離)が８５ｍｍとなるように装着し、５×１０-4Ｐａまで排気した後、純度９９．９９９％以上のＡｒガスを導入して、０．５Ｐａの圧力に保持し、スパッタリングパワー２００Ｗ、電圧５００Ｖ、電流０．４Ａで、膜厚が１００ｎｍとなるように、スパッタリングを行い、基板上に２０ｍｍ×２５ｍｍの大きさの薄膜を成膜した。このときの基板にはＡｌ2Ｏ3を使用した。 The sputtering target obtained in this way, DC sputtering device (Shibaura Mechatronics Co., CFS-4ES) to, and mounted so as TS distance (distance from the target to the substrate) is 85 mm, 5 × 10 - After evacuating to 4 Pa, Ar gas having a purity of 99.999% or more is introduced and maintained at a pressure of 0.5 Pa so that the film thickness becomes 100 nm at a sputtering power of 200 W, a voltage of 500 V, and a current of 0.4 A. Then, sputtering was performed to form a thin film having a size of 20 mm × 25 mm on the substrate. Al 2 O 3 was used for the substrate at this time.
得られた薄膜の両端に、膜厚が５００ｎｍのＡｕ電極を、同様のＤＣスパッタリング法により成膜した。その後、大気雰囲気中、３００℃の温度で、３時間の熱処理を行い、本発明の抵抗薄膜を用いた薄膜抵抗器を得た。 Au electrodes having a thickness of 500 nm were formed on both ends of the obtained thin film by the same DC sputtering method. Thereafter, heat treatment was performed for 3 hours at a temperature of 300 ° C. in an air atmosphere to obtain a thin film resistor using the resistive thin film of the present invention.
得られた薄膜抵抗器について、以下のように、比抵抗、抵抗温度特性、高温安定性、および耐食性（耐塩水性）の評価を行った。 The obtained thin film resistor was evaluated for specific resistance, resistance temperature characteristics, high temperature stability, and corrosion resistance (salt water resistance) as follows.
比抵抗は、抵抗率計（株式会社三菱化学アナリック製、ロレスタＧＰ ＭＣＰ−Ｔ６１０型を使用）を用いて、室温において、四探針法による測定により得た。本発明においては、３００μΩ・ｃｍ以上に比抵抗を有するものを良品と判断した。 The specific resistance was obtained by measurement by a four-probe method at room temperature using a resistivity meter (manufactured by Mitsubishi Chemical Analic Co., Ltd., Loresta GP MCP-T610 type). In the present invention, those having a specific resistance of 300 μΩ · cm or more were judged as non-defective products.
抵抗温度特性については、得られた薄膜抵抗器を恒温漕に入れ、２５℃と１２５℃における抵抗値（単位：Ω）について上記抵抗率計を用いて測定し、得られた抵抗値から抵抗温度係数を算出することにより評価した。本発明においては、±２５ｐｐｍ／℃よりも小さいものを良品と判断した。 For resistance temperature characteristics, the obtained thin film resistor was placed in a thermostatic oven, and the resistance values (unit: Ω) at 25 ° C. and 125 ° C. were measured using the above resistivity meter, and the resistance temperature was determined from the obtained resistance values. Evaluation was made by calculating the coefficient. In the present invention, a product smaller than ± 25 ppm / ° C. was judged as a good product.
高温安定性については、得られた薄膜抵抗器を１５５℃の恒温槽内に１０００時間保持し、その前後における抵抗値（単位：Ω）について上記抵抗率計を用いて測定し、得られた抵抗値から抵抗変化率（１５５℃、１０００時間）を算出することにより評価した。本発明においては、恒温槽への投入前の抵抗値を基準として、投入後の抵抗値の割合が０．１％以下であるものを良品と判断した。 For high temperature stability, the obtained thin film resistor was held in a thermostatic bath at 155 ° C. for 1000 hours, and the resistance value (unit: Ω) before and after that was measured using the above resistivity meter, and the obtained resistance The resistance change rate (155 ° C., 1000 hours) was calculated from the value. In the present invention, on the basis of the resistance value before charging into the thermostatic bath, a product having a resistance value ratio after charging of 0.1% or less was judged as a non-defective product.
耐塩水性については、得られた薄膜抵抗器について、以下のような電食試験を行い、溶解開始電圧を測定することにより評価した。 About salt water resistance, about the obtained thin film resistor, the following electrolytic corrosion tests were performed and it evaluated by measuring a dissolution start voltage.
まず、抵抗薄膜（２）の初期抵抗値を、デジタルマルチメータ（岩通計測株式会社製、ＶＯＡＣ７５２１Ａ）を用いて四端子法により測定した。次に、図２に示すように、マイクロシリンジで、抵抗薄膜（２）の中央に酸性人工汗（ＪIＳ Ｌ０８４８）を３０μＬ滴下し、液滴（４）の直径およびＡｕ電極（３）の間の長さから、液滴（４）の両端に負荷される電圧（Ｖｄ）が１Ｖとなるように、Ａｕ電極（３）の間の電圧（Ｖｐ）を調製した。Ａｕ電極（３）の間の電圧（Ｖｐ）を一定として、３分間、電圧を負荷した後、水洗および乾燥を行い、四端子法により抵抗値を測定し、電圧負荷前後の抵抗変化率を測定した。 First, the initial resistance value of the resistance thin film (2) was measured by a four-terminal method using a digital multimeter (VOAC7521A, manufactured by Iwatatsu Measurement Co., Ltd.). Next, as shown in FIG. 2, 30 μL of acidic artificial sweat (JIS L0848) was dropped on the center of the resistance thin film (2) with a microsyringe, and between the diameter of the droplet (4) and the Au electrode (3). From the length, the voltage (Vp) between the Au electrodes (3) was adjusted so that the voltage (Vd) applied to both ends of the droplet (4) was 1V. The voltage (Vp) between the Au electrodes (3) is kept constant, the voltage is applied for 3 minutes, then washing and drying are performed, the resistance value is measured by the four-terminal method, and the resistance change rate before and after the voltage load is measured. did.
このような測定を、液滴（４）の両端に負荷される電圧（Ｖｄ）が１Ｖから０．２Ｖ刻みで上昇するように、Ａｕ電極（３）の間の電圧（Ｖｐ）を調整して繰り返すことにより、抵抗変化率が０．２％を超えた時の液滴（４）の両端に負荷される電圧（Ｖｄ）を得て、抵抗薄膜（２）の溶解開始電圧とした。 In such a measurement, the voltage (Vp) between the Au electrodes (3) is adjusted so that the voltage (Vd) applied to both ends of the droplet (4) rises from 1V in increments of 0.2V. By repeating, the voltage (Vd) applied to both ends of the droplet (4) when the resistance change rate exceeded 0.2% was obtained and used as the dissolution start voltage of the resistance thin film (2).
したがって、得られる溶解開始電圧は、酸性人工汗（ＪIＳ Ｌ０８４８）を滴下して両端のＡｕ電極間に一定の電圧で３分間電圧を負荷し、水洗および乾燥を行って測定される抵抗変化率が０．２％を超えるという条件を満足する際に測定される液滴両端の電圧のうちの最小値である。本発明においては、溶解開始電圧が９．０Ｖ以上であるものを良品と判断した。 Accordingly, the dissolution starting voltage obtained is the rate of change in resistance measured by dropping acidic artificial sweat (JIS L0848), applying a voltage at a constant voltage for 3 minutes between the Au electrodes at both ends, washing and drying. This is the minimum value of the voltage across the droplet measured when the condition of exceeding 0.2% is satisfied. In the present invention, a product having a melting start voltage of 9.0 V or more was judged as a non-defective product.
（実施例２）
シリケート系ガラス粉末の添加量を３質量％としたこと以外は、実施例１と同様にして、薄膜抵抗器を得て、その特性についての測定を行った。
(Example 2)
A thin film resistor was obtained in the same manner as in Example 1 except that the addition amount of the silicate glass powder was 3% by mass, and the characteristics were measured.
（実施例３）
シリケート系ガラス粉末の添加量を１０質量％としたこと以外は、実施例１と同様にして、薄膜抵抗器を得て、その特性についての測定を行った。
(Example 3)
A thin film resistor was obtained in the same manner as in Example 1 except that the addition amount of the silicate glass powder was 10% by mass, and the characteristics were measured.
（実施例４）
シリケート系ガラス粉末の添加量を２０質量％としたこと以外は、実施例１と同様にして、薄膜抵抗器を得て、その特性についての測定を行った。
Example 4
A thin film resistor was obtained in the same manner as in Example 1 except that the addition amount of the silicate glass powder was 20% by mass, and the characteristics were measured.
（実施例５）
シリケート系ガラス粉末に添加物を添加しなかった（シリケート系ガラス粉末における添加物の含有量が０質量％）こと以外は、実施例１と同様にして、薄膜抵抗器を得て、その特性についての測定を行った。
(Example 5)
A thin film resistor was obtained in the same manner as in Example 1 except that no additive was added to the silicate glass powder (the additive content in the silicate glass powder was 0% by mass). Was measured.
（実施例６）
シリケート系ガラス粉末における添加物の含有量を３０質量％としたこと以外は、実施例１と同様にして、薄膜抵抗器を得て、その特性についての測定を行った。
(Example 6)
A thin film resistor was obtained in the same manner as in Example 1 except that the content of the additive in the silicate glass powder was 30% by mass, and the characteristics were measured.
（実施例７）
シリケート系ガラス粉末における添加物の含有量を７０質量％としたこと以外は、実施例１と同様にして、薄膜抵抗器を得て、その特性についての測定を行った。
(Example 7)
A thin film resistor was obtained in the same manner as in Example 1 except that the content of the additive in the silicate glass powder was 70% by mass, and the characteristics were measured.
（実施例８）
シリケート系ガラス粉末における添加物の含有量を９０質量％としたこと以外は、実施例１と同様にして、薄膜抵抗器を得て、その特性についての測定を行った。
(Example 8)
A thin film resistor was obtained in the same manner as in Example 1 except that the content of the additive in the silicate glass powder was 90% by mass, and the characteristics were measured.
（実施例９）
Ｎｉ合金における添加元素の含有量を１０質量％としたこと以外は、実施例１と同様にして、薄膜抵抗器を得て、その特性についての測定を行った。
Example 9
A thin film resistor was obtained in the same manner as in Example 1 except that the content of the additive element in the Ni alloy was 10% by mass, and the characteristics were measured.
（実施例１０）
Ｎｉ合金における添加元素の含有量を３０質量％としたこと以外は、実施例１と同様にして、薄膜抵抗器を得て、その特性についての測定を行った。
(Example 10)
A thin film resistor was obtained in the same manner as in Example 1 except that the content of the additive element in the Ni alloy was 30% by mass, and the characteristics were measured.
（実施例１１）
Ｎｉ合金における添加元素の含有量を５０質量％としたこと以外は、実施例１と同様にして、薄膜抵抗器を得て、その特性についての測定を行った。
(Example 11)
A thin film resistor was obtained in the same manner as in Example 1 except that the content of the additive element in the Ni alloy was 50% by mass, and the characteristics were measured.
（実施例１２）
Ｎｉ合金における添加元素の含有量を６０質量％としたこと以外は、実施例１と同様にして、薄膜抵抗器を得て、その特性についての測定を行った。
(Example 12)
A thin film resistor was obtained in the same manner as in Example 1 except that the content of the additive element in the Ni alloy was 60% by mass, and the characteristics were measured.
（比較例１）
シリケート系ガラス粉末を添加しなかったこと以外は、実施例１と同様にして、薄膜抵抗器を得て、その特性についての測定を行った。比較例１の薄膜抵抗器は、比抵抗が３００μΩ・ｃｍ未満であり、抵抗変化率も０．１％を超え、かつ、溶解開始電圧がきわめて低かった。このように、抵抗薄膜を得る際の熱処理温度が相対的に低い場合には、十分な特性を備える薄膜抵抗器が得られないことが理解される。
(Comparative Example 1)
A thin film resistor was obtained in the same manner as in Example 1 except that the silicate glass powder was not added, and the characteristics were measured. The thin film resistor of Comparative Example 1 had a specific resistance of less than 300 μΩ · cm, a resistance change rate of more than 0.1%, and a very low melting start voltage. Thus, it is understood that a thin film resistor having sufficient characteristics cannot be obtained when the heat treatment temperature for obtaining a resistive thin film is relatively low.
（比較例２）
シリケート系ガラス粉末の添加量を３０質量％としたこと以外は、実施例１と同様にして、スパッタリングターゲットを得た。しかしながら、このスパッタリングターゲットを用いて、実施例１と同様に抵抗薄膜を成膜しようとしたところ、ターゲットの導電性が不十分であるため、成膜ができなかった。
(Comparative Example 2)
A sputtering target was obtained in the same manner as in Example 1 except that the addition amount of the silicate glass powder was 30% by mass. However, when an attempt was made to form a resistive thin film using this sputtering target in the same manner as in Example 1, the film could not be formed because the conductivity of the target was insufficient.
（比較例３）
シリケート系ガラス粉末における添加物の含有量を９５質量％としたこと、および、シリケート系ガラス粉末の添加量を１０質量％としたこと以外は、実施例１と同様にして、薄膜抵抗器を得て、その特性についての測定を行った。比較例３の薄膜抵抗器は、抵抗温度係数が±２５ｐｐｍ／℃を超えており、また、溶解開始電圧が９Ｖ未満であり、本発明で要求される抵抗温度特性および耐食性を達成できていないことが理解される。
(Comparative Example 3)
A thin film resistor was obtained in the same manner as in Example 1 except that the content of the additive in the silicate glass powder was 95% by mass and that the amount of the silicate glass powder was 10% by mass. Then, the characteristics were measured. The thin film resistor of Comparative Example 3 has a temperature coefficient of resistance exceeding ± 25 ppm / ° C. and a melting start voltage of less than 9 V, and cannot achieve the resistance temperature characteristics and corrosion resistance required by the present invention. Is understood.
（比較例４）
Ｎｉ合金における添加元素の含有量を０質量％としたこと以外は、実施例１と同様にして、薄膜抵抗器を得て、その特性についての測定を行った。比較例４の薄膜抵抗器も、比抵抗が３００μΩ・ｃｍ未満であり、抵抗温度係数が±２５ｐｐｍ／℃を超えており、かつ、溶解開始電圧が９Ｖ未満であり、本発明で要求される抵抗、抵抗温度特性、耐食性を達成できていないことが理解される。
(Comparative Example 4)
A thin film resistor was obtained in the same manner as in Example 1 except that the content of the additive element in the Ni alloy was 0% by mass, and the characteristics were measured. The thin film resistor of Comparative Example 4 also has a specific resistance of less than 300 μΩ · cm, a temperature coefficient of resistance exceeding ± 25 ppm / ° C., and a melting start voltage of less than 9 V. It is understood that the resistance temperature characteristic and the corrosion resistance are not achieved.
（比較例５）
Ｎｉ合金における添加元素の含有量を７０質量％としたこと以外は、実施例１と同様にして、薄膜抵抗器を得て、その特性についての測定を行った。比較例５の薄膜抵抗器は、抵抗温度係数が±２５ｐｐｍ／℃を超えており、かつ、溶解開始電圧が９ｖ未満であり、本発明で要求される抵抗温度特性および耐食性を達成できていないことが理解される。
(Comparative Example 5)
A thin film resistor was obtained in the same manner as in Example 1 except that the content of the additive element in the Ni alloy was 70% by mass, and the characteristics were measured. The thin film resistor of Comparative Example 5 has a temperature coefficient of resistance exceeding ± 25 ppm / ° C. and a melting start voltage of less than 9 v, and has not achieved the resistance temperature characteristics and corrosion resistance required by the present invention. Is understood.
各実施例における組成、ＤＣスパッタリングの可否、成膜後の薄膜の熱処理温度、および得られた薄膜抵抗器の特性の測定結果について、それぞれ表１に示す。 Table 1 shows the measurement results of the composition, the availability of DC sputtering, the heat treatment temperature of the thin film after film formation, and the characteristics of the obtained thin film resistor in each example.
（実施例１３）
原料粉末のうちのシリケート系ガラス粉末として、Ｍｇ、Ｃａ、Ｂａ、Ａｌ、およびＺｒを総量で５０質量％添加（Ｍｇ：Ｃａ：Ｂａ：Ｚｒ：Ａｌ＝５：２０：１８：５：２（質量比））した、平均粒径が１０μｍのＳｉＯ2粉末を用いたこと以外は、実施例１と同様にして、薄膜抵抗器を得て、その特性についての測定を行った。
(Example 13)
As a silicate glass powder of the raw material powder, Mg, Ca, Ba, Al, and Zr are added in a total amount of 50% by mass (Mg: Ca: Ba: Zr: Al = 5: 20: 18: 5: 2 (mass A thin film resistor was obtained in the same manner as in Example 1 except that a SiO 2 powder having an average particle diameter of 10 μm was used, and the characteristics were measured.
（実施例１４）
シリケート系ガラス粉末の添加量を７質量％としたこと以外は、実施例１３と同様にして、薄膜抵抗器を得て、その特性についての測定を行った。
(Example 14)
A thin film resistor was obtained in the same manner as in Example 13 except that the addition amount of the silicate glass powder was 7% by mass, and the characteristics were measured.
（実施例１５）
シリケート系ガラス粉末の添加量を１０質量％としたこと以外は、実施例１３と同様にして、薄膜抵抗器を得て、その特性についての測定を行った。
(Example 15)
A thin film resistor was obtained in the same manner as in Example 13 except that the addition amount of the silicate glass powder was 10% by mass, and the characteristics were measured.
（実施例１６）
シリケート系ガラス粉末に添加物を添加しなかった（シリケート系ガラス粉末における添加物の含有量が０質量％）こと以外は、実施例１３と同様にして、薄膜抵抗器を得て、その特性についての測定を行った。
(Example 16)
A thin film resistor was obtained in the same manner as in Example 13 except that no additive was added to the silicate glass powder (the additive content in the silicate glass powder was 0% by mass). Was measured.
（実施例１７）
シリケート系ガラス粉末における添加物の含有量を９０質量％としたこと以外は、実施例１３と同様にして、薄膜抵抗器を得て、その特性についての測定を行った。
(Example 17)
A thin film resistor was obtained in the same manner as in Example 13 except that the content of the additive in the silicate glass powder was 90% by mass, and the characteristics were measured.
（実施例１８）
Ｎｉ合金における添加元素の含有量を５０質量％としたこと以外は、実施例１３と同様にして、薄膜抵抗器を得て、その特性についての測定を行った。
(Example 18)
A thin film resistor was obtained in the same manner as in Example 13 except that the content of the additive element in the Ni alloy was 50% by mass, and the characteristics were measured.
（比較例６）
シリケート系ガラス粉末を添加しなかったこと以外は、実施例１３と同様にして、薄膜抵抗器を得て、その特性についての測定を行った。
(Comparative Example 6)
A thin film resistor was obtained in the same manner as in Example 13 except that the silicate glass powder was not added, and the characteristics were measured.
（比較例７）
シリケート系ガラス粉末の添加量を３０質量％としたこと以外は、実施例１３と同様にして、薄膜抵抗器を得て、その特性についての測定を行った。
(Comparative Example 7)
A thin film resistor was obtained in the same manner as in Example 13 except that the addition amount of the silicate glass powder was 30% by mass, and the characteristics were measured.
（比較例８）
シリケート系ガラス粉末における添加物の含有量を９５質量％としたこと、および、シリケート系ガラス粉末の添加量を１０質量％としたこと以外は、実施例１３と同様にして、薄膜抵抗器を得て、その特性についての測定を行った。
(Comparative Example 8)
A thin film resistor was obtained in the same manner as in Example 13 except that the content of the additive in the silicate glass powder was 95% by mass and the amount of the silicate glass powder was 10% by mass. Then, the characteristics were measured.
（比較例９）
Ｎｉ合金における添加元素の含有量を０質量％としたこと以外は、実施例１３と同様にして、薄膜抵抗器を得て、その特性についての測定を行った。
(Comparative Example 9)
A thin film resistor was obtained in the same manner as in Example 13 except that the content of the additive element in the Ni alloy was 0% by mass, and the characteristics were measured.
（比較例１０）
Ｎｉ合金における添加元素の含有量を７０質量％としたこと以外は、実施例１３と同様にして、薄膜抵抗器を得て、その特性についての測定を行った。
(Comparative Example 10)
A thin film resistor was obtained in the same manner as in Example 13 except that the content of the additive element in the Ni alloy was 70% by mass, and the characteristics were measured.
比較例６〜１０においても、比較例１〜５と同様の傾向が見られることが理解される。 In Comparative Examples 6 to 10, it is understood that the same tendency as in Comparative Examples 1 to 5 is observed.
各実施例における組成、ＤＣスパッタリングの可否、成膜後の薄膜の熱処理温度、および得られた薄膜抵抗器の特性の測定結果について、それぞれ表２に示す。 Table 2 shows the measurement results of the composition, the availability of DC sputtering, the heat treatment temperature of the thin film after film formation, and the characteristics of the obtained thin film resistor in each example.
１ 絶縁性基板（アルミナ基板）
２ 抵抗薄膜
３ 電極（Ａｕ電極）
４ 液滴
1 Insulating substrate (alumina substrate)
2 Resistance
4 droplets
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| TW099135509A TWI482870B (en) | 2009-10-29 | 2010-10-19 | Resistor material, spattering target for forming a resistor film, resistor film, film resistor, and methods for making them |
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| EP3309800B1 (en) * | 2016-10-11 | 2019-03-20 | Heraeus Deutschland GmbH & Co. KG | Method for producing a layer structure using a paste based on a resistance alloy |
| JP7087741B2 (en) * | 2018-07-05 | 2022-06-21 | 住友金属鉱山株式会社 | A method for manufacturing a resistor material, a sputtering target for forming a resistance thin film, a resistance thin film and a thin film resistor, and a method for manufacturing a sputtering target for forming a resistance thin film and a method for manufacturing a resistance thin film. |
| CN111057907A (en) * | 2019-12-21 | 2020-04-24 | 江苏骏茂新材料科技有限公司 | Preparation method of nickel-based high-temperature-resistant alloy material |
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| JP2542504B2 (en) * | 1986-12-11 | 1996-10-09 | ティーディーケイ株式会社 | Metal thin film resistor |
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