TW200523386A - Metallic resistance material, sputtering target, resistance thin flim, and method for making the resistance thin film - Google Patents

Abstract

This invention provides a metallic resistance material, of which the resistance temperature coefficient is about O, having a high temperature stability superior than Ni-Cr-Al-Si series alloy. The resistance thin film is formed by sputtering method using a sputtering target which contains: 1.0~15.0% wt of Al, and 0.01~0.5% wt of a rare earth element, and Cr and Ni at a ratio 0.15~1.1 (Cr/Ni) as remainder. The resistance thin film is further subject to heat treatment in an atmosphere under the temperature of 200 DEG C~500 DEG C for 1~10 hours.

Description

200523386 IX. Description of the invention: [Technical field to which the invention belongs] The present invention relates to a metal resistor material that can be used as a thin film resistor for electronic parts, a sputtering target for resistive film molding, a resistive film, and A method for manufacturing a resistance film using the sputtering target. [Previous technology] Resistors such as chip resistors, precision resistors, network resistors, high-voltage resistors, and temperature sensors such as temperature-measuring resistors and temperature-sense resistors; and integrated circuit (hybrid 1C) Thin film resistors using resistive films are used in electronic components such as composite module products. In this kind of thin film resistor, in order to make the metal resistor material of the resistance film, Ta (button) metal, TaN (tantalum nitride) compound, Ni-Cr (nickel chromium) alloy are mostly used, among which Ni-Cr alloy is the most Often used. Depending on the application, thin film resistors are characterized by high temperature stability and low temperature stability and low temperature coefficient of resistance (TCR) even at high temperatures, which are important characteristics. Therefore, for applications that require these characteristics, metal resistor materials that are inherently thin film resistor materials need to have these characteristics. Generally, when a two-element alloy consisting of Ni and Cr is used, Bay 11 changes the Ni / Cr ratio to control high temperature stability and temperature coefficient of resistance. However, it is difficult to simultaneously realize the characteristics that the resistance change rate with time is small even at a high temperature, and the characteristic that the temperature coefficient of resistance is almost zero. Therefore, as shown in Patent Document 1 (Patent No. 2542504) and Patent Document 316421 200523386 2 (Japanese Patent Laid-Open Publication No. 6_20803, etc.), alloys are included in the alloy, and the manufacturing characteristics are improved. However, in recent years, the requirements for the use of ambient temperature have become more stringent, and the rate of change in resistance requires a characteristic of almost zero. It is not yet possible to meet this demand. Thin film resistors installed in flying cars and the like have a smaller resistance to high temperature stability, which is an indicator of high temperature stability, with respect to resistance characteristics, especially high temperature stability. At the same time, the resistance temperature system is also needed. But in the aforementioned metal resistance materials,

NlC A; Resistive thin films are generally formed by sputtering. However, the addition of A1 'to the aforementioned chemical gold has deteriorated the castability when used as an alloy, which has become the cause of rising target manufacturing costs. (Patent Document 1) Japanese Patent No. 2542504 (Patent Document 2) Japanese Patent Laid-Open No. 6-20803 [Summary of the Invention] · (Problems Solved by the Invention) The present invention was developed in view of such problems Its purpose is to provide a metal resistor material, which has better temperature stability than Nlm% alloy, and the temperature coefficient of resistance (TCR: Temper_e Coefficient) is almost zero. In addition, the purpose is to provide a metal resistor material that has excellent high-temperature stability without adding μ to the existing Nl_Cr_Si-based alloy and has a temperature coefficient of resistance of 316421 6 200523386 zero. (Means for solving the problem) The metal resistor material according to the first aspect of the present invention contains A1.1.0 to 15.0% by weight, and a rare earth element: 0Q1 to 05% by weight, and the rest are substantially It is composed of Cr & Nl, and the weight ratio of heart / qin is 0.15 1 1 · 1 纟. The sputtering target according to the first aspect of the present invention also has the same composition. Here, the rare earth elements in the book of the present situation include, for example, Y (Ji) and Lantanold (typically lanthanum and thallium), and i or two or more kinds can be selected from them. A rhenium alloy (Miisch metal) which is a mixture of rare earth elements belonging to the Group VIII can also be used. In addition, the resistive film is formed by using the aforementioned sputtering target, and a resistive film composed of Nl_Cr_A1_rare earth element alloy) is formed on an insulating material substrate according to the sputtering method, and then the resistive film is exposed to the atmosphere and temperature. 20. 0 to 50 (rc) produced by heat treatment for 1 to 10 hours. The characteristics of the resistive film: i 0 to 150% by weight of rare earth elements; 0.01 to 0.5% by weight 'the rest are essentially It is composed of c and Qin, the weight ratio of Cr / Nl is 015 to U, and the temperature coefficient of resistance is within the range of ± 25 卯 4, which is maintained for 175tx2000 hours. The resistance change rate is less than 0.10%. The metal resistor material according to the second aspect of the present invention includes shoulder t1: two to 14.5 weight, Sl: 0.2 to 5.0% by weight, dilute: day-like. To 0.5% by weight, and the rest In fact, it is made of Cr and its location, and the weight ratio of Cr / Nl is 0 · 7 ... 31642 of the present invention. 7 200523386 The standard form of machine shooting for the second form is also the same. And on the substrate of insulating material: :: using the above-mentioned standard shot dry, and according to the resistance film composed of _, and then-like 1-rare earth element alloy 2000 ° C to 50 (TC implementation : The characteristics of the resistance film in the atmosphere, the temperature L Bu Hu, heat treatment for 1 hour, the characteristics of the resistance film.

Si: 0.2 5 〇 #-0 / ^ 3 with A1, 5.0 to 14.5% by weight, Wang) · 0 weight, the rest of the rare earths are in fact ## ^^ 素 .G.G1 to W% by weight, Composed of 0.75 to u ^ Nl, the weight ratio of heart / guilty is mainly 1 · 1 ′, and the resistance temperature is in the range of -15 PPm / ° C for the helmet with 7 捭 彳 〇r, and it is guaranteed to be 175 CX for 2000 hours The electricity ^ related to the third aspect of the present invention: the second rate. Below ground. Two in = wt%, rare earth elements :. 〇 .... 5% by weight, 〇: 15 t: the upper part is composed of ... 1, and the weight ratio of the coffee is the same composition. H evil money shooting standard Geba also

Also, the resistive film is made of a standard film for projection before use, and is filled with a resistive film made of Nb Cr_sl_ rare earth element alloy on the insulating material substrate. The resistive film is pure, and the resistive film is in the atmosphere. Temperature: obtained by applying heat treatment to 500 ° C. for 1 to 10 hours. The characteristics of the obtained resistive film: containing Si: 〇2 to 50% by weight, rare earth elements: 0.01 to 0.5% by weight, and the rest are essentially composed of & ^ Nl, Cr / Nl weight ratio It is from 0 · ΐ5 to U, and the resistance temperature coefficient is ± 25 Ppm / t: within a range of '175 ^ χ 2000 hours'. The resistance change rate is 0.25% or less. 316421 8 200523386 (Effect of invention) As in the metal of invention! When the resistor material is used to make a resistive film, the value of 1 is η- 丄, and the value of the resistance temperature coefficient of the version is very large, and the resistance stability of the wiper is related to the heat treatment of the present invention, which can reduce the resistance. Bo Lei, and, the absolute value of Factory A. Specifically, in the jealousy resistance of the present invention, the degree coefficient is made within ± 25 ppmrC, and the resistance temperature is made within the soil and the heart, and within this ::: sadness, it is within the heart ^. In addition, the implementation of this month === can be used to make the old amine resistance; Jl / L ^ ..., treatment 'can form a fine oxide film on the surface of the second display, because of the stability of resistance. Specifically, in the first aspect of the present invention, it is possible to maintain 175t: x 2000 hours # and the brother-morphology, and in the second aspect of the present invention: the conversion rate is made _ to „ The spear can be made less than 0.25%. The resistance of the present invention is thinner than that of the conventional amine resistance resistors with the thickness of the conventional Nΐ4ΑΚς · u resistance, which cannot be achieved by resistance stability and small resistance, w ° gold Electronic parts used in the environment of electric horse temperature at high temperature. This is also applicable to the relevant invention of Yan Ke> Chu — NpCr A1 s • wider metal resistor material than the past, although it has a stable resistance at high temperature1 The property Hi is the temperature coefficient of resistance of Λ. However, the resistance material does not contain A] to the extent that it is laughable. However, because the metal state is full, it is more relevant to the first and second aspects of the present invention. Productivity when used as a target for barrier materials. 1 is 乜, which can improve production as a splash. [Embodiment] 316421 9 200523386: 1 · Has: the first form of the metal resistor leather of the present invention The inventors of Bar, the resistance film, and the standard for resistance radiation As a result, it was found that N = used as a metal resistor material is in a specific + + phase-* τ / Tega's given amount of k rare earth elements:., Is 7, and even if kept at high temperature The fact that the electric power is increased and the value of f_ $ is still small has led to the completion of the present invention. The resistance-to-resistance ratio is related to the target of the first form of the present invention for the sputtering of the metal resistor material, and the resistance is thin. K + rejection | and the production method of the plate material [, [metal resistor material and resistor film will be described. :::: The metal resistor material of the first form of the invention is in the range of ⑽wt% ^ 崎 合 ^, Those with u to 0.5% by weight of rare earth elements are added respectively. The weight ratio of "," :: / Nl is 0.15 or less, or the absolute value of the resistance 1 degree iT and the number will increase. , 5 series are mainly added to improve the temperature coefficient of resistance (TCR). If ΪΓ: 1% by weight or less, or 15% by weight, the resistance temperature increases to a negative value at the same time, and 175. . The rate of change in resistance also increases by 0.3%, which in this specification refers to those in which γ (epoch) and steel elements are mainly added to improve high-temperature stability. If it is added in an amount of 〇ιι: li% or less, it will not help to improve the stability of Shangwen. On the other hand, even if it exceeds 0.5 *% by weight, it is still unpredictable. It is unfavorable to wait for a significant increase in high temperature stability to increase the cost. 316421 10 200523386 [Target for sputtering] Regarding the sputtering target of the first aspect of the present invention, the resistor material is used as the target material, and its composition is substantially the same [resistive film] And manufacturing method of resistive film] :? The first form of the metal resistor material used in the present invention is "light, and when the resistive film is produced by the subtractive emission method, the temperature coefficient of resistance of the resistive film in the vacuum film state will The negative value increases, and the resistance stability in the South temperature is insufficient. However, if a resistance film formed by using the metal electrode material according to the first aspect of the present invention is used, the resistance film is cut by 200 C to the atmosphere 50．〇 ， 1 ～ 10 〇Continuously applying heat treatment to the conditions of 1 ～ 10 〇, you can praise 1 + p # 9ς I j clothing temperature coefficient of resistance within the range of + = PPm / C, and maintain 1 75 ° CX 200 (M. Constant obedience, resistance film with small electric current with cross rate of less than 0.10 / 〇. The coefficient of temperature and high temperature stability are such. The __ 篦 & Γ's resistive film will depend on the Films made on the substrate of insulating slabs and slabs by injection molding are heat-treated under conditions of large «r, 1 r // cube 200 C to 500 c 1 to small 。. If the heat treatment temperature is 200 ℃ or less When ^ ^ ^ j, the temperature coefficient of resistance (TCR) (TCR) will become larger. C P is the temperature coefficient of resistance, and if the processing time is less than 1 hour, the temperature coefficient of resistance (TCR) will not be determined. On the other hand, that is #if. IV π ^ ^ ^ for 1 hour, the resistance temperature is known and the resistance change rate + when it is maintained at 咼 temperature will not become smaller, which increases the cost of 316421 11 200523386 'and is therefore not appropriate. In addition, in terms of the film formation method, in addition to the cathode sputtering method, an electron beam or a resistance heating deposition method is used. Xiao may use electricity [2. A metal resistor body according to the second aspect of the present invention. , Geba, resistive film and manufacturing method of resistive film] ... The standard for gas injection is related to the first form of the gold Nl-Cr- alloy of the present invention. The addition of a specific amount of a specific dilute material to the ground is related to the invention. The second form of metal resistance: the elementary element, which is added to the alloy The following is a description of the second aspect of the present invention: the soil and the element. 丨 Targets for extinction, resistive films and resistive thin second resistor materials, [metal resistor material] clothing & method Explanation. The weight ratio of gold in the second aspect of the present invention is' based on ⑽1 H.5 weight. / Of the eighth ^ by weight ^: knife do not add force "."% Of rare earth elements. 1. The weight from 01 to 0.5, such as the weight ratio of Cr / Ni, is less than or equal to 0.75, and < and at the same time, the temperature coefficient of resistance will increase. On the other hand, when the qualitative characteristics of the female are deteriorated, the reproducibility in manufacturing is also improved: 1 In addition to improving the high-temperature stability, it is also added to the degree coefficient. If its added amount is: the stability of the temperature will not be enough. In addition, when the weight of taxis and days is less than 0, if the U-mouth of the high-resistance temperature childbirth exceeds 14.5% by weight, the resistance / disc coefficient will increase to a negative value. When 316421 12 200523386 is wide or exceeds 5% by weight, the temperature coefficient of resistance is deteriorated. (〇 Trang, high temperature stability and rare earth elements are mainly used to improve the high temperature & amp σ is not helpful when the amount of addition is less than 0.01% by weight. On the other hand, even if the amount exceeds 0: 7; In terms of a significant increase in temperature stability, the cost is increased. [Sputtering target] The second aspect of the present invention is used as the target of the sputtering resistor material. Π, When the above-mentioned metal [resistance film and manufacturing method of resistance film] is used to make the resistance film according to the second embodiment of the present invention, the resistance film is made according to the standard shooting method. The temperature coefficient of resistance will believe that the stability of the resistance in the medium and quasi-holding film formation state is insufficient.

Yier 'such as the resistance film formed by using the I material of the present invention, the ~-is a resistor body 0Γ, 15 in ί in the big milk, according to 200C to 500! To 10 small days When the heat treatment is performed under the replacement conditions, the coefficient is within the range of ± Upp ^ c, and the resistance change rate at the fM resistance temperature is less than 0.1%. CX2_hour temperature stability resistance film. The temperature coefficient of resistance is so high that the second form of the present invention is applied to the second-pancreas of the present invention, which is to be insulated according to the method of reducing the firing rate of the standard firing bar to 316421 13 200523386. The D, r guarded on the material substrate is placed in large milk, and the heat treatment is performed at a temperature of 200 ° C to 500 c for 1 to 1 G hours. itb 5; ten, "ν", to change the stability of the resistance of the thin film in a vacuum to maintain the stability of the cover #, control of the temperature coefficient of the pen resistance and high temperature production for direct / random resistance temperature coefficient is controlled by heat treatment At this time, the ring Γ second middle and second milk are feasible, but the improvement of high temperature stability can only be achieved by heat treatment in large milk. In addition, in the case of N ^ Γ_Α123 element alloy, although large electric heat treatment can be used to simultaneously achieve the control of electric power ^, Chengdian B Μ degree ^ number and improve the stability of high temperature, but because Α1 and s 彳 1 are allowed to dry β and Sl have a negative effect on the temperature coefficient of resistance. Therefore, when Ni-Pr Δ 1 / _ Cr_A1_Sl is a 4-element alloy, if the amount of A1 is too large, S i is added in the same time. The daily temperature coefficient of day and day is y, then the temperature coefficient of resistance increases toward the negative value. On the other hand, if the heat treatment in the atmosphere is made into a high temperature coefficient, it will increase in the positive direction. Tian μμ is like a door. Therefore, before heat treatment in the atmosphere, it is necessary to perform heat treatment in a vacuum to control the temperature coefficient of resistance. For example, if the heat treatment temperature in the atmosphere is 20 (rca coefficient will be unstable, and the other ancient products + heart resistance, the degree is a son-in-law, and on the other hand, if it exceeds 50 (rc, the resistance severity coefficient will go to The positive direction increases. Also, if the heat treatment time is under working hours ^, the temperature coefficient of resistance is unstable, and on the other hand, even if it exceeds 10 hours, the effect of increasing the temperature coefficient of resistance will not appear, and the cost will increase. For example, when the vacuum heat treatment before heat treatment is performed in the atmosphere, the temperature coefficient of resistance will be unstable when the temperature is below 300 ° C. On the other hand, if it exceeds 700 ° C, the temperature coefficient of resistance will be positive. In addition, when the heat treatment time is less than 1 hour, the temperature coefficient of resistance will be unstable, 316421 14 200523386. In addition, even if it exceeds 10 hours, the anti-corrosion effect will not appear, and the cost will increase. The temperature coefficient of resistance will increase. • In terms of the plate-forming method, 'in addition to the cathode sputtering method, a private beam or a resistance heating deposition method.' In addition, sputtering can be used with the mark [has: 'resistance to the third aspect of the invention's metal electricity_ target Manufacturing method of resistance rhenium film and resistance thin film] A1 is added to the first and second shapes of the present invention, but to the Cr = Si alloy of the third material of the present invention, special features are added to the vein Cr-Si alloy. The metal resistor body material, but did not add A1. Therefore, the ancient and rare earth element component resistor body materials have good castability, the third form of metal material, compared to the use of the present invention; The production of the body material during the production of Pakistan has been improved. And the following-the shape of the metal resistance, the third shape of the target of the present invention, the resistance film, and the resistor material, [metal resistor material], The method of clothing t will be described. The weight ratio of the second i of the present invention is from 0.15 to 丨 87, A is a resistor material, which is based on Cr / Ni 5.0% by weight 丨, 〇.〇1 In the alloy, 0.2% to rare earth elements such as Cr / Ni by weight and 0.5 reset% are added. The rye ratio is 〇] sv. On the other hand, such as super ^ llai a , The temperature coefficient of resistance will increase in manufacturing, the reproducibility will be generalized, and the temperature stability will be poor. At the same time, it is added at 仏 2% by weight with a resistance temperature coefficient of ^, D '. If the amount is more than 5.0% by weight, the temperature coefficient of resistance 316421 is increased. At the same time, the high-temperature stability also changes. Poor. The main element of the rare earth element series is added at 0.001 wt./%; β, which is added by the south temperature stability, but it does not help. In addition, Γ :, it is about high temperature stability. , Even if it exceeds 0.5 weight, the significant effect increases and the cost rises.

[Standard Geba J] For the third form of this hair, the resistor material for sputtering is used as standard Geba user. ^ The above-mentioned Meng [the manufacturing method of the resistive film and the resistive film] For example, a metal resistive material using #palladium and H, which is related to the present invention, is produced by a sputtering target using a sputtering method. Electricity 1 乂 耵 ", $, the resistance temperature coefficient of the private blocking frequency in the real state of maintaining the film formation state will be insufficient, and the resistance stability at temperature will be insufficient. In the atmosphere, the electrical film of the metal resistor body is in the atmosphere, according to the fan. C to Gang. C, i to Xiaori, when the two conditions are continuously heat treated, the resistance temperature can be made within the range of 25pPm / C. And, it is produced by a product / Π 7. A resistive film with a small temperature coefficient of resistance with a resistance cross-over rate of 175CX at 2000 hours (below U / 0). Μ Γ is so 'related to the third form of the present invention's resistance The thin film is a thin film produced on a substrate of an insulating material in accordance with the standard method of sputtering of the second embodiment of the present & Ming, and is used in the atmosphere. ^ To c, 1 Those who perform heat treatment to 10 hours. Taxi ... when the hunger degree is below 200 C, the resistance The temperature coefficient will not be 316421 16 200523386 2 疋. On the other hand, if it exceeds 500 ° C, the temperature coefficient of resistance will increase and 'if the heat treatment time is less than 1 hour, the temperature coefficient of resistance = 弋 another-aspect, even Over hours, the temperature coefficient of resistance and the rate of change of resistance at high temperatures do not remain small, which increases the cost and is not suitable. In addition, in terms of the film formation method, in addition to the cathode sputtering method, a private sputtering method can also be used. Sub-beam or resistance heating deposition method. [Example] Six examples of car = Garden examples 1 to 24 are examples related to the first form of the present invention, and 25 1 3 are comparative examples related to the first form of the present invention. Examples 5 to 35 are examples related to the second aspect of the present invention, Comparative Example I #

This is a comparative example related to the second aspect of the present invention. Examples% to C are examples of the second embodiment of the present invention, which are the second embodiment of the present invention. The comparative examples 24 to 28 are comparative examples of the third embodiment. (Examples 1 to 24, Comparative Examples 1 to 13)

Metal (1 = Electrolytic recording, electrolysis, and metal particles (_al㈣, Y w city, La metal (test), Ce all belong to d 薤, mp, people use medicine), metal silicon (属 乐), 钸Lanthanum alloy (try drying as raw material 'enables to be as shown in Table 1 and Table 2

The NlC type was weighed separately, and a vacuum melting furnace was used to make about 2kg of N: rare earth alloy ... a gold-rich lean core (h〇1 is used to manufacture a resistance film, and each ingot was homogenized (〇mogenizlng) treatment, 5mm > 15〇The gate uses a steel wire male (and e _ is called cut to a thickness of 0 sheet, and the upper and lower sides are ground to make a standard leather 316421 17 200523386 (target). The film formation process is based on the cathode sputtering method, The method is as follows: After loading an aluminum substrate in a vacuum chamber and extracting it at lx l0_4Pa, argon gas having a purity of 99.9995% is introduced and maintained at a pressure of 0.3Pa. According to the sputtering power of 0.3kW, the film thickness can be changed to The film formation on the aforementioned substrate was performed at 500 A. On both sides of the obtained resistive film, the Au (gold) electrode with a film thickness of 5000 A was also formed by the cathode sputtering method to form a resistive film on an aluminum substrate. And Au electrode thin film resistors. Then, heat treatment was performed in the atmosphere at 300 ° C for 3 hours to complete each thin film resistor. In order to evaluate Examples 1 to 24 and Comparative Examples 1 to 13 manufactured in this way, Temperature coefficient of resistance of thin film resistor The resistance measurement was performed at the same time as the temperature was raised to measure the temperature coefficient of resistance at 25 ° C and 125 ° C. The high temperature stability was evaluated as follows. Each thin film resistor was held in a constant temperature bath at 175 ° C for 2000 The resistance value was measured before and after it was held to measure the resistance change rate. The results are shown in Tables 1 and 2. 316421 200523386 [Table i] Composition (mass%) Cr / Ni specific resistance temperature coefficient (ppnV ° C) ) Resistance change rate (%) 175 ° Cx 20001ir Judging Nom Ci · A1 Rare element Si Comparative Example 1 81.7 8.1 10.1 Y0.08 — 0.10 45 0.21 X Example 1 78.2 11.6 10.1 Y0.09 — 0.15 24 0.08 Example 2 68.6 21.3 10.0 Y0.09 — 0.31 18 0.06 Example 3 58.1 31.9 9.9 Y0.10 — 0.55 15 0.07 Example 4 53.3 36.7 9.9 Y0.10 — 0.69 17 0.08 Example 5 45.0 44.9 10.0 Y0.07 — 1.00 2 0.04 Comparison Example 2 41.8 48.1 10.0 Y0.10 — 1.15 27 0.08 X Comparative Example 3 51.2 48.7 0.0 Y0.09 — 0.95 -32 0.76 X Example 6 48.0 48.7 3.2 Y0.11 — 1.01 8 0.07 Example 7 47.8 47.0 5.1 Y0.09 — 0.98 6 0.06 Example 8 42,1 43.0 14 .8 Y0.10 — 1.02 -20 0.06 Comparative Example 4 41.9 41.2 16.8 Y0.10 — 0.98 -68 0.11 X Comparative Example 5 44.7 45.2 10.1 Y < 0.01 — 1.01 3 0.19 X Example 9 43.9 46.2 9.9 Υ 0.01 — 1.05 5 0.06 Example 10 44.8 45.3 9.8 Y0.06 — 1.01 3 0.05 Example 11 45.4 44.5 10.0 Y0.18 — 0.98 8 0.04 Example 12 44.8 44.7 10.1 Y0.32 — 1.00 13 0.05 Comparative Example 6 45.5 43.7 10.1 Y0.61 — 0.96 12 0.05 19 316421 200523386 [Table 2]

As shown in Tables 1 and 2, examples! The thin film resistors 2 to 24 have a temperature coefficient of resistance (TCR) in the range of ± 25 ppm / t, and the temperature of resistance (TCR) is good. Also, apricot > 175. …: The resistance change ratios of the thin film resistors 1 through 4 to 24 are all below 0.1 ()%, as in Comparative Example 13 of the NhCwU-y alloy. "The first month ^ is good. Figure 1 shows the time-dependent change of the resistance change rate of the thin film resistor manufactured from the example ^ L 5, 13 =, and the temperature of 175 C is called second. The figure shows the change with time of the resistance change rate of the thin film resistors manufactured from the resistive films of Examples 316421 20 200523386 17 and Comparative Example 13 in a still-temperature tank of us C. ',,. Figure 1 and Figure 2 show that the time in the still temperature bath of 175 C in Examples 5 and 17 is between 0 and 2000 hours, which is less than that of Comparative Examples 3, 5, and 13. At any time, at this time, the resistance change rate is relatively small (Examples 25 to 35, Comparative Examples 14 to 23). First, "electrolytic nickel, electrolytic chromium, aluminum metal particles, metal blocks (reagents), La Metal (test reagent), Ce metal (test sheep), Jinbazhiyao) as raw materials, can be used as a composition shown in Table 3 fractional two-purpose vacuum melting furnace About 2kg & Nl_Cr_A1_Si Rigo r si-rare earth element alloy ingots. The crop electricity implementation Γ is to grind each ingot (metal electricity _ ^^, grinding to make a target for sputtering. Cathode sputtering The method is implemented as follows. After the U ”work underwear is put into the aluminum substrate and pumped to lx 10-4pa, the purity is 99.9995% of argon 10, and then it is introduced into the film with a thickness of 300. The method of A is applied on both sides of the obtained resistive film on the aforementioned substrate, and the film thickness of the A_uu electrode is 5 A, and the bond is realized by the cathode sputtering method-the substrate of the electrode. After film formation, the ratio is 2: 4 = Shape, J 14 is in the atmosphere 2 8 0 5 5 316 421 21 2005 23 386 hours, after the heat treatment of Comparative Example 22 and Comparative Examples, 3 0 0 in the atmosphere at 400 0 C in vacuum for 1 hour and Example 25 To 35 series 3 hours under large slabs' Comparative Examples 15 to 21 were processed to make each thin film electric H3Ot 3 hours at 25 hours and Examples 25 to 35 and Comparative Examples were produced in this way The resistance-temperature characteristic of the resistor to 23 is at the same time, at 25 ° Γ fen 1 — the temperature coefficient of tetris. Also, Γ. Measure and calculate the resistance temperature. In order to suppress the temperature stability, each thin film resistor was placed in a strange temperature bath at 175 C for 2,000 hours to measure the electrical σ. The results are shown in Table 3. Reduction rate. 316421 22 200523386 [Table 3] Νι Composition (% by mass)

Cr / Ni ratio

Cr A1 Si Rare Earth Resistance Temperature Coefficient (ppm / ° C) Comparative Example 14 62.1 32.4 2.4 3.1 Resistance change rate (%) 175 ° Cx 20001η * Judgment 0.52 Comparative Example 15 55 · 8 36.9 5.0 2.2 Υ0.11 _〇66 ^ Example 25 52.2 ~~ 40.3 ~ 5.2 ~ λ0 ~~ MM 0.27 〇77 ~ Example 26 49.8 ~~ 4Z9 " " " " 53 L9 La 0.11 〇86 ~ Example 27 Comparative Example 16 47.6 42.2 45.0 50 : 7 MM 0.35 Y0.12 0.95 20 2 -4 0.26 0.20 0.09 0.07 0.06

X

X

X 5.1 ~ 5Λ 2.0 Τ9 ~ -10 Comparative Example 17 43.3 43.5 Y, La, MM < 0.01 1.20 1.00 -30 0.10 0.22

Tianyi 3 knows that the resistance coefficients of 1 ~~ 'inch m resistors are in the range of ± 15ppm / C, and show good resistance, and w productivity. In addition, the resistance change of the thin film resistors of Examples 25 to 35 ;: 0.10% or less, when compared with Comparative Example 14 of the main prior art, it shows extremely high temperature stability. On the other hand, Comparative Example 15 has insufficient high temperature stability because Cr / Ni is 0.66, which is outside the range of Ming, while Comparative Example 16 is composed of 316421 23 200523386.

Cr / Ni of 1.20 is outside the scope of the present invention. Therefore, the high-temperature coefficient of resistance increases in the negative direction. Comparative Example 17 is because the content of rare earth elements is 0.01% by weight or less outside the scope of the present invention. Therefore, The high-temperature stability is insufficient. Although the content of the rare earth element of Comparative Example 18 is 061 wt%, which exceeds 0.5 wt% of the range of this month, its resistance temperature coefficient and high-temperature stability are higher than those of Example 3j. There is no significant effect, and Comparative Example 19 is due to the absence of Si, and Comparative Example 20 is due to the weight. / 0 is outside the scope of the present invention, and therefore, the temperature coefficient of resistance is not within the range of & Comparative Example 21 is because the content of A1 is D weight. ^ Is outside the scope of the present invention, so the high temperature stability is insufficient, and the ratio: 22 and 23 are due to AI content of 14.8% by weight, 16.! Out of the scope of the present invention, therefore, the temperature coefficient of resistance, "-each figure shows the time history of the change rate of the resistance of the thin film resistor strict example 14 produced from the electric Ra film of Example 31 and Comparative Example 14 The change in electricity Γ is maintained in the 175C to the temperature bath ... According to the figure 3, it can be seen that in Examples 5 and 17, it is maintained. Γ \ The time in the south temperature bath is 0 ° C; Comparative Example 3 of C 、 5 、 13 日 士 # At any time in the range of the small-day generation, it is more than (Examples ... 2, 2, the fact that the resistance change rate is quite small., 1 Comparative Examples 24 to 28) belong to the block (test 7 chromium, metal Silicon, aluminum metal grains, and Y gold are separately measured in the way created by the vacuum angle. The furnace is made of about 2kg of N1_C1, S1 alloy, 316421 24 200523386.

Ingots of Ni-Cr-Si-Al alloy or Ni-Cr-Si-ene earth element alloy. Next, in order to manufacture the resistive film, each ingot was subjected to homogenization treatment, and then cut into a circular plate having a thickness of 5 mm and a diameter of 150 mm using a steel wire, and grinding the upper and lower surfaces to make a target. The film formation process is performed by the cathode sputtering method as follows. After loading an aluminum substrate in a vacuum chamber and extracting it to lx l0_4Pa, introduce 99.9995% argon gas and maintain a pressure of 0.3Pa, and implement the foregoing method to achieve a film thickness of 500 A according to a sputtering power of 0.3kW. Film formation on an aluminum substrate. On both sides of the obtained resistive thin film, as described above, a Au electrode with a film thickness of 5000 A was formed by a cathode sputtering method to obtain a substrate on which the resistive thin film and the Au electrode were formed. After film formation, heat treatment was performed at 300 ° C in the atmosphere for 3 hours to prepare each thin film resistor. In order to evaluate the resistance temperature characteristics of the thin film resistors of Examples 36 to 42 and Comparative Examples 24 to 28 produced in this manner, the temperature was raised in a constant temperature bath, and resistance measurements at 25 ° C and 125 ° C were performed simultaneously to calculate Temperature coefficient of resistance. In order to evaluate the high-temperature stability, each thin film resistor was held in a constant temperature bath at 175 ° C for 2000 hours to measure the resistance change rate. The results are shown in Table 4. 25 316421 200523386 [Table 4]

It can be seen from Table 4 that the thinness coefficients of Examples 36 to 42 are all in the range of ± 25ppm / ° C, and the wide electric resistance is dried. The resistance temperature and sound characteristics are not good. In addition, the examples; the thin film electrical resistances of 36 to 42 Λ 9ς // the resistance change rate of the resistance state are all ^ 0.25 /. In the following, when compared with the main prior art Ni_crji_ ^ alloy Comparative Example 24, the same high-temperature stability is shown. ', Contrary to this', although Comparative Example 24 is different from the second aspect ratio of the present invention, it is not less than 0.75 and as small as 0.52, but because it contains A1, the electrical conversion rate becomes- It is slightly higher than 0.25%. Since Comparative Example 25 contains rare earths, the resistance change rate becomes 0.38%, which is a significant p.25. /. . Comparative Example 26 contains a rare earth element of 61% by weight, which is equal to 0.05% by weight of the upper limit of the range of the third aspect of the present invention. The temperature coefficient and the rate of change of resistance have no effect, and are not cost effective. Comparative Example 27 contains filial piety 31642] 26 200523386 s! 6.2%, which is 50% by weight of the standard value of the third aspect of the present invention. Therefore, the temperature coefficient of resistance is established, but it is not within ± 25Ppm / cC range. In Comparative Example 28, since Si was not contained, the resistance change rate was 0.76%, which was significantly higher than 0.25%, and the resistance 2 degree coefficient was also -32Ppm / t: without entering the range of ± 25ppm / < t. [Schematic description] Figure 1 is a graph showing the resistance change rate when the thin film resistors manufactured from the resistive films of Example 5 and Comparative Examples 3, 5, and 13 are held in a high temperature bath of 175 ×: 2 Graph of temporal changes. Fig. 2 'is a graph showing the change with time of the resistance change rate when the thin film resistors manufactured from the resistive films of Example 17 and Comparative Example 13 are held in a high temperature bath of 7 51. FIG. 3 is a graph showing the time-dependent change of electricity with the rate of change when a thin film resistor manufactured from the resistor thin moon fruit of Example 1 and Comparative Example 14 is held in a high temperature bath of 75 °. Illustration. 27 31642}

Claims (1)

200523386 10. Scope of patent application: h A metal resistor material, which contains A1: 1.0 to 150% by weight, rare earth vanillin: 0.001 to 0.5% by weight, and the rest are in real life Composition, and the weight ratio of Cr / Nl consists of 2 :: a standard bar for shooting, which contains A1: 1.0 to 15.0% by weight, rare earth element 〇.01 to 0.5% by weight, and the rest It is essentially composed of Cr and Nl, and the weight ratio of Cr / Ni is 0.15 to u. 3. A resistive film, characterized in that it contains eight 1:10 to 15 weight percent rare earth 7L elements: 0.001 to 0.5 weight percent, and the remainder consists essentially of Cr and Nl. The weight ratio of Cr / Ni is from 0.15 to υ, and the coefficient of privacy is within a range of ± 25 ppm / ° C, and is maintained at 175. 〇 The rate of change in resistance at 2000 hours is 0.10% or less. 4. A method for manufacturing a resistive film, characterized in that it uses A1: to 15.0% by weight, rare earth elements: 0.01 to 0.5% by weight, and the rest are composed of Cr and Ni on males and shells. , And the weight ratio of Cr / Ni is up to 1.1 mbar, the resistance film made of Ni-Cr-Al-rare earth element alloy is formed on the insulating material substrate according to the sputtering method, and then ' The resistive film is subjected to a heat treatment in the atmosphere at a temperature of 200 ° C to 500 ° C for 1 to 10 hours. 5. Kinds of metal resistor materials, which contain A1: 5.0 to 14.5% by weight, Sl · 0.2 to 5.0% by weight, rare earth elements: 0.001 to 0.5% by weight. It is composed of Cr and Ni, and the weight ratio of Cr / Ni is 0.75 to. 6. · A target for sputtering, which contains A1: 5.0 to 14.5% by weight, Si: 28 316421 200523386 0.2 to 5.0% by weight, and rare earth elements: 0 to 5% by weight. The remainder is essentially caused by Cl. And Nl, and ⑽ = 0.75 to L1. This kind of resistance thin 朕 'is characterized by containing A1: 5.0 to 14.5% by weight :: 0.2 to 5.0% by weight, rare earth elements: 〇 · (Π to 0.5 by weight of two or more by CqNi The composition, the weight of ⑽! = 75 to u 'and the temperature coefficient of resistance within ± 15ppmrc ^ =' The resistance change rate at the time of holding I75tx2_ hours is ㈣ ^ lower 0 8. = manufacturing method of Tao film 'its characteristics : Use ai: 5 = will weigh 5 / ° 'Sl: ° .2 to 5. ·% by weight, rare earth element center = Γ / Ν Dan, the rest is essentially composed of ^ and ^ jin. Targets for reduction of 0.75 to 1,1, depending on hiding: ^ generated on the substrate, Ni_G_ai_Si_ rare earth,: = .: resistive film, and then the resistive film in In the atmosphere: you 9 ^^ to your staff to perform a heat treatment for 1 hour and 0 hours. Hi is a resistor material, which contains ^ == ^^% by weight 'The weight ratio of Cr / N! On the remaining braid is 0.15 To j ”. I.“ To 0.5% by weight, the rest is composed of heart and Qin. ”The weight ratio of qualitative offenders is 仏 to ^ 1, U:;: = membrane, its characteristics Contains ― to 5.0% by weight, ..... 1 to 0.5% by weight, the remainder is composed of 0 and milk 316421 29 200523386, and the weight ratio of Cr / Nl is substantially 0.15 to 15 and the resistance A number is within the range of 25ppm / C in the soil, maintaining 1 75 ° CX 2000 hour resistance change rate is less than 0.25%. 12 A method for manufacturing a resistive film, characterized by using Sl: 0.2 to 5.0% by weight, rare earth elements: 0.01 to 0.5% by weight %, The remainder ', Tian Q and Ni, which are essentially sputtering targets with a Cr / Ni weight ratio of 0.15 to •, are formed on the insulating material substrate by the sputtering method. The resistive film is then heat-treated in the atmosphere at a temperature of 200 ° C to 500 ° C for 1 to 10 hours. 30 316421