Cr-Si film

Abstract

A Cr-Si film, according to the present invention, includes chromium (Cr) and silicon (Si). The compositional range of the Cr-Si film is Cr / (Cr+Si)=0.25-0.75, and the TCR absolute value, in increments of 10℃ in a temperature range of 40℃-150℃, is from 0 ppm / ℃ to 100 ppm / ℃ inclusive.

Description

[Technical field]

[0001] The present invention relates to a Cr--Si based film having a small absolute value of TCR and a small change in TCR at each temperature. [Background technology]

[0002] In recent years, CrSi 2 Due to their characteristics, Cr-Si-based materials (silicides) such as the above are used as films (Cr-Si-based films) in semiconductors and solar cells. Cr-Si-based materials can have semiconducting and metallic characteristics depending on the state of the crystal phase, so they have a small temperature coefficient of resistivity (TCR) and are used in various sensors. These various sensors are used in environments where the temperature varies from room temperature to high temperatures (150°C or lower), such as electrical appliances and automobiles. Therefore, in terms of improving detection accuracy, it is desirable for the Cr-Si-based film to have the same resistivity at all temperatures from room temperature to high temperatures (i.e., it is desirable for the variation in resistivity value to be small in the temperature range from room temperature to high temperatures).

[0003] For example, Patent Document 1 discloses that the characteristics (trends) of the change in sheet resistance after heat treatment change depending on the composition ratio of Cr and Si. Specifically, a Cr-Si film formed using a target containing 40 wt% or more of Cr has a high N 2 In addition to the high thermal stability of the resistance without the addition of N, the Cr-Si film formed using a target with Cr of 30 wt% or less has a high thermal stability of the resistance without the addition of N. 2 When no N was added, the resistance fluctuation was large. 2 It has been reported that this fluctuation can be improved by adding an elemental ferroelectric. However, Patent Document 1 does not identify the composition range in which the TCR can be brought closer to 0 (i.e., the absolute value of the TCR can be reduced).

[0004] Furthermore, in Patent Document 2, the physical properties of a film formed from a Cr-Si sputtering target containing 30 wt% Cr are measured, but the TCR only measures the resistivity at 20° C. and 120° C. However, it is known that typical Cr-Si films have a curved change in resistivity with respect to temperature, and TCR at only two points, 20° C. and 120° C., is insufficient for evaluation as an actual sensor, and the change behavior of the TCR with temperature change cannot be understood. [Prior art documents] [Patent documents]

[0005] [Patent Document 1] JP 2010-278479 A [Patent Document 2] JP 2002-367803 A Summary of the Invention [Problem to be solved by the invention]

[0006] An object of the present invention is to provide a Cr--Si based film which contains chromium (Cr) and silicon (Si), has a small absolute value of TCR, and exhibits small change in TCR at each temperature. [Means for solving the problem]

[0007] The present inventors have investigated Cr-Si based films containing chromium (Cr) and silicon (Si) and have discovered a Cr-Si based film with an optimal composition ratio that has a small TCR and small change in TCR at each temperature, thereby completing the present invention.

[0008] That is, the present invention is as described in the claims, and the gist of the present invention is as follows. (1) A Cr-Si-based film containing chromium (Cr) and silicon (Si), characterized in that the composition range of the film is Cr / (Cr+Si)=0.25-0.75, and the absolute values ​​of TCR at 10°C intervals in the temperature range of 40°C to 150°C are all 0 ppm / °C or more and 100 ppm / °C or less. (2) The Cr-Si-based film according to (1), wherein the difference between the maximum and minimum values ​​of TCR in 10°C increments in the temperature range is 100 ppm / °C or less. (3) The Cr-Si-based film according to (1) or (2), wherein the absolute values ​​of TCR at 10°C intervals in the temperature range are all 0 ppm / °C or more and 50 ppm / °C or less. (4) The Cr-Si-based film according to any one of (1) to (3), wherein the absolute value of the average TCR in 10° C. increments in the temperature range is 0 ppm / ° C. or more and 50 ppm / ° C. or less. (5) A Cr-Si based film according to any one of (1) to (4), wherein the composition range of the film is Cr / (Cr+Si)=0.3 to 0.5. (6) The Cr-Si based film according to any one of (1) to (5), further containing nitrogen (N). (7) The Cr-Si based film according to (6), characterized in that Si-N=25 to 75 wt %. (8) A method for producing a Cr-Si based film according to any one of (1) to (7), characterized in that a sputtering target containing chromium and silicon as main components is used to form a film by a sputtering method. (9) The method for producing a Cr-Si based film according to (8), further comprising heat-treating the Cr-Si based film formed by sputtering at 800° C. or less in a non-oxygen atmosphere. Effect of the Invention

[0009] Since the absolute value of the TCR of the Cr-Si-based film of the present invention is small in the temperature range of 40°C to 150°C, when used as a resistor, it exhibits stable resistivity at any temperature within the above temperature range, making it possible to provide a highly accurate sensor. [Brief description of the drawings]

[0010] [Figure 1]1 is a graph showing the relationship between resistivity and temperature of the Cr—Si based film of Example 1. [Diagram 2] 1 is a graph showing the relationship between resistivity and temperature of the Cr—Si based film of Comparative Example 1. DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS

[0011] The present invention will be described in detail below. In this specification, "to" between two numerical values ​​represents a range with the two numerical values ​​as upper and lower limits, for example, "30°C to 150°C" or "30 to 150°C" means "30°C or higher and 150°C or lower". In addition, in this specification, "wt%" means "mass%".

[0012] The present invention is a Cr-Si-based film containing chromium (Cr) and silicon (Si), characterized in that the composition range of the film is Cr / (Cr+Si)=0.25 to 0.75, and the absolute values ​​of TCR at 10°C intervals in the temperature range of 40°C to 150°C are all 0 ppm / °C or more and 100 ppm / °C or less.

[0013] The present invention relates to a Cr-Si based film, that is, a silicide film having a matrix (parent phase, main phase) of chromium silicide, and further a chromium silicide film. The Cr-Si based film of the present invention may contain elements other than Cr and Si, so long as it has a matrix of chromium silicide.

[0014] The composition range of the Cr-Si based film of the present invention is Cr / (Cr+Si)=0.25-0.75. Cr / (Cr+Si) is preferably 0.3-0.7, and particularly preferably 0.3-0.5. When the Cr ratio (i.e., Cr / (Cr+Si)) is more than 0.75, the TCR becomes large, and when the Cr ratio is less than 0.25, the TCR becomes small. In Cr / (Cr+Si), "Cr" means the Cr content (wt%), and "Si" means the Si content (wt%).

[0015] The absolute value of the TCR in 10° C. increments in the temperature range of 40° C. to 150° C. of the Cr—Si-based film of the present invention is 0 ppm / ° C. or more and 100 ppm / ° C. or less. t " TCR at 100℃ t ", etc., respectively, "TCR 100 "TCR" refers to the absolute value of TCR at each of the following temperatures: 40°C, 50°C, 60°C, 70°C, 80°C, 90°C, 100°C, 110°C, 120°C, 130°C, 140°C, or 150°C.

[0016] TCR (ppm / ℃) is the resistivity R (Ω cm) of the Cr-Si film at each temperature, and the resistivity R at 30℃ 30 The value is calculated using the following formula from the electrical conductivity (Ω cm) and the measurement temperature T (°C). TCR=(RR 30 ) / (R 30 ×(T-30))×10 6

[0017] "Resistivity R at each temperature" refers to the resistivity at each measurement temperature of 30°C, 40°C, 50°C, 60°C, 70°C, 80°C, 90°C, 100°C, 110°C, 120°C, 130°C, 140°C, or 150°C. The resistivity R at 30°C, etc. is referred to as "R 30 " etc.

[0018] TCR t and TCR are preferably in the range of 0 ppm / ° C. to 50 ppm / ° C. t If the resistance falls within this range, the resistance value is unlikely to vary significantly depending on the temperature, making it easier to obtain a sensor with high detection accuracy.

[0019] The difference between the maximum and minimum values ​​of the TCR of the Cr-Si-based film of the present invention at 10°C intervals in the range of 40°C to 150°C is preferably 100 ppm / °C or less, more preferably 50 ppm / °C or less, and even more preferably 20 ppm / °C or less. The smaller the difference between the maximum and minimum values, the smaller the change in resistivity in the range of 30°C to 150°C, and therefore the resistor can exhibit high performance in all temperature ranges within this range. The difference between the maximum and minimum values ​​of the TCR (=maximum value-minimum value) can be, for example, 0 ppm / °C or more, 1 ppm / °C or more, or 5 ppm / °C or more. "The difference between the maximum and minimum TCR values" is the TCR 40 ~TCR 150 This refers to the difference between the maximum and minimum values.

[0020] The average TCR of the Cr-Si based film of the present invention is preferably within ±50 ppm / °C (i.e., the absolute value of the average TCR is 0 ppm / °C or more and 50 ppm / °C or less). The average TCR is more preferably within ±30 ppm / °C (i.e., the absolute value of the average TCR is 0 ppm / °C or more and 30 ppm / °C or less), and even more preferably within ±10 ppm / °C (i.e., the absolute value of the average TCR is 0 ppm / °C or more and 10 ppm / °C or less). A smaller absolute value of the average TCR indicates that the range of resistance is less likely to change with temperature (i.e., the change in resistivity with temperature is small). Therefore, a Cr-Si based film with a small absolute value of the average TCR exhibits high performance as a resistor. The "average TCR" refers to the above-mentioned TCR 40 ~TCR 150 The arithmetic mean value of

[0021] The resistivity (R 30 ; Ω cm) is, for example, 1.0×10 -6 Ω cm or more, 1.0×10 -5 Ω cm or more, 1.0×10 -4 Ω cm or more, or 1.0×10 -3 Ω·cm or more and 10 Ω·cm or less, 1.0 Ω·cm or less, or 1.0×10 -1The resistivity of the film can be measured, for example, by using an 8403 AC / DC Hall measurement system (manufactured by Toyo Corporation).

[0022] The thickness of the Cr-Si-based film of the present invention is preferably small. Since the Cr-Si-based film is used as a resistor in a high resistance portion, the smaller the thickness, the higher the sheet resistance. However, if the thickness is too small, the film will not have continuity and will become an insulating film. Therefore, the thickness is preferably 1 to 500 nm, more preferably 1 to 300 nm, and even more preferably 1 to 150 nm. Since it is likely to become a thin film suitable for resistors, etc., the thickness is preferably 50 nm or more or 80 nm or more, and 150 nm or less or 120 nm or less.

[0023] The Cr-Si-based film of the present invention preferably further contains nitrogen (N). The difference between the nitrogen content (wt%) and the silicon (Si) content (wt%) is preferably Si-N (=(Si content)-(N content))=25-75wt%, more preferably 25-45wt%, and particularly preferably 25-40wt%. When Si-N is 75wt% or less, the difference between the maximum and minimum values ​​of TCR is unlikely to become large. When Si-N is more than 25wt%, the Cr-Si-based film becomes a nitride film, so the absolute value of TCR is unlikely to become large.

[0024] The Cr-Si-based film of the present invention may contain metal impurities such as Fe and Al, and the lower the content (wt%) of the metal impurities, the better. The metal impurities are metal elements other than Cr contained in the Cr-Si-based film of the present invention. When the amount of metal impurities is small, the variation in TCR tends to be small, and the TCR tends to be small. The total amount of the metal impurities is preferably 1 wt% or less, more preferably 0.5 wt% or less, and even more preferably 0.1 wt% or less. The total amount of the metal impurities is, for example, 0 wt% or more, 0.001 wt% or more, 0.005 wt% or more, or 0.01 wt% or more.

[0025] Next, the method for producing the Cr-Si based film of the present invention will be described.

[0026] The method for producing a Cr-Si-based film of the present invention is a method for forming a film from a sputtering target mainly composed of chromium and silicon by a sputtering method, and further, the film can be produced by a method in which a sputtering target mainly composed of chromium and silicon is formed by a sputtering method, and then heat-treated at 800°C or less in a non-oxygen atmosphere. Alternatively, the Cr-Si-based film of the present invention can also be produced by a method for simultaneously forming a film from each of the sputtering targets of chromium and silicon by a sputtering method. Preferably, the method for producing a Cr-Si-based film includes a step of forming a film by a sputtering method using a sputtering target mainly composed of chromium and silicon. In addition, the term "main component" refers to a component whose content is 99 wt% or more. More specifically, "mainly composed of chromium and silicon" refers to a total of the mass of chromium and the mass of silicon in the total mass of the sputtering target being 99 wt% or more. More preferably, 99 wt% or more of the sputtering target is an alloy of chromium and silicon.

[0027] The sputtering target used in the manufacturing method of the present invention has a purity of 99% or more, preferably 99.5% or more, and preferably has a low oxygen content. Purity refers to the content of the main component in the sputtering target, and the unit of purity, "%", means "wt%". The manufacturing method of such a sputtering target is not limited, but an example is shown below.

[0028] <Sputtering target manufacturing process> The sputtering target can be produced by preparing (i.e., mixing) a Cr powder and a Si powder to have a specific composition range, such as the same composition as the desired Cr-Si film, to obtain a mixed powder, and using the mixed powder by a method such as powder metallurgy or melting. Specifically, the sputtering target can be obtained by a manufacturing method including an alloy powder preparation step in which the alloy powder is prepared by, for example, an alloy powder, a gas atomization method, a quenched ribbon (strip casting) method, or an arc melting method, and a sintering step in which the alloy powder is sintered. The alloy powder is preferably a powder produced by a gas atomization method.

[0029] (Alloy powder preparation process) Pure chromium (metallic chromium) and pure silicon (metallic silicon) are used as raw materials for the alloy powder preparation process. The purity of the pure chromium and pure silicon is preferably 99.9 mass% or more (3N or more), more preferably 99.99 mass% or more (4N or more), and even more preferably 99.999 mass% or more (5N or more).

[0030] In the raw material preparation step, the raw material powder is preferably treated by a gas atomization method, in which pure chromium and pure silicon are melted at their melting temperatures by high-frequency induction melting to obtain a molten metal, and the molten metal is dripped while being sprayed with high-pressure gas to obtain an alloy powder containing a fine crystal structure.

[0031] The temperature of the molten metal in the gas atomization method is preferably from the melting temperature + 50° C. to the melting temperature + 300° C., more preferably from the melting temperature + 100° C. to the melting temperature + 250° C. Here, the "melting temperature" means the temperature at which both pure chromium and pure silicon melt, and can be 1300° C. to 1500° C.

[0032] (Sintering process) The alloy powder is sintered to obtain a sputtering target. The sintering is preferably performed by pressure sintering such as hot pressing. The pressure (sintering pressure) applied to the alloy powder in the pressure sintering may be 1 MPa or more, and is 50 MPa or less, preferably 20 MPa or less, and more preferably 10 MPa or less.

[0033] The sintering temperature in the sintering step is, for example, 1100° C. or more and 1400° C. or less. The time for which the above sintering pressure and sintering temperature are maintained (sintering time) is, for example, 1 hour or more and 5 hours or less.

[0034] The sintering atmosphere is not particularly limited as long as it is an atmosphere that suppresses oxidation of the Cr-Si sintered body. In order to further suppress oxidation of the Cr-Si sintered body, the sintering atmosphere is preferably a vacuum or inert atmosphere, and more preferably a vacuum atmosphere or a reduced pressure atmosphere.

[0035] A sputtering target is obtained by the above process. If the obtained sputtering target contains a large amount of impurities, it will have a negative effect on the physical properties of the film, so it is preferable to obtain a sputtering target with a purity of 99.5% or more. In addition, it is preferable that the amount of oxygen in the sputtering target is small. If the amount of oxygen is large, it will cause particles to be generated and the production yield will decrease.

[0036] Hereinafter, an example of the method for producing a Cr-Si based film according to the present invention will be described step by step. (2) Sputtering process The above sputtering target is used to form a film by a sputtering method, that is, a film is formed by a sputtering method using the above sputtering target, thereby obtaining a film. The sputtering method (sputtering method) can be appropriately selected from at least one selected from the group consisting of DC sputtering method, RF sputtering method, AC sputtering method, DC magnetron sputtering method, RF magnetron sputtering method, and ion beam sputtering method. The sputtering method is preferably DC magnetron sputtering method or RF magnetron sputtering method, in that it can form a film uniformly and quickly over a large area.

[0037] The sputtering power was 0.6 W / cm 2 More than 10W / cm 2 Less than 0.6W / cm is preferable. 2 At a sputtering power of 10 W / cm or more, the deposition rate is high and the productivity is not likely to decrease. 2 If it is less than this, the load on the target is small and the possibility of it cracking is reduced.

[0038] During sputtering, argon gas and nitrogen gas are used as the introduced gas for film formation, but oxygen gas, hydrogen gas, etc. may also be used as necessary.

[0039] (3) Heat treatment process The obtained film may be subjected to a heat treatment under appropriate temperature conditions. This can further reduce the absolute value of TCR. The temperature of the heat treatment step is preferably 800°C or less, or 700°C or less, and is preferably 150°C or more, 200°C or more, 300°C or more, or 500°C or more. When the temperature of the heat treatment step is 800°C or less, the production efficiency of the film is less likely to decrease. On the other hand, when the temperature of the heat treatment step is 150°C or more, the absolute value of TCR is likely to be small. The heat treatment time can be, for example, 0.5 hours or more and 10 hours or less.

[0040] The heat treatment is preferably performed in a non-oxygen atmosphere. In addition, in an oxygen-containing atmosphere, oxidation proceeds due to heating, and the film properties deteriorate, so the heat treatment is preferably performed in a non-oxygen atmosphere. The non-oxygen atmosphere is an atmosphere that does not contain oxygen, and specifically, for example, at least one selected from the group consisting of a vacuum atmosphere, an argon atmosphere, and a nitrogen atmosphere is included, with a vacuum atmosphere being preferred, and a vacuum atmosphere of 10 Pa or less being particularly preferred.

[0041] Further embodiments of the present invention include the following. (1) A Cr-Si-based film containing chromium (Cr) and silicon (Si), characterized in that the composition range of the film is Cr / (Cr+Si)=0.25-0.75 and the absolute value of the average TCR is ±50 ppm or less. (2) The Cr-Si based film according to (1), further comprising nitrogen (N), Si-N=25 to 75 wt %. (3) The Cr-Si-based film according to (1) or (2), characterized in that the difference between the maximum and minimum values ​​of TCR at 10°C intervals in the range of 30°C to 150°C is 100 ppm or less. (4) A method for producing a Cr-Si-based film according to any one of (1) to (3), characterized in that a sputtering target containing chromium and silicon as main components is formed into a film by a sputtering method, and then heat-treated at 800°C or less in a non-oxygen atmosphere. EXAMPLES

[0042] The present invention will be described in more detail below with reference to examples, but the present invention is not limited thereto. , reference example The measurements in the comparative examples were carried out as follows.

[0043] (1) Cr-Si film formation conditions <Preparation of sputtering targets> Cr powder with a purity of 4N and Si powder with a purity of 5N were mixed to obtain the composition of the sputtering target shown in Table 1, and melted in a carbon crucible at a melting temperature of 1600°C to obtain a molten metal at 1600°C. The target composition shown in Table 1 is the same as the charged composition of the powder. This was made into Cr-Si alloy powder by a gas atomization method. The obtained Cr-Si alloy powder was placed in a carbon crucible and pressure sintered by hot pressing under the following conditions to produce a Cr-Si sintered body having the desired composition. (Sintering conditions) Sintering furnace: Hot press furnace Heating rate: 200℃ / hour Heating atmosphere: vacuum (5 Pa or less) Sintering temperature: 1250℃ Sintering pressure: 20MPa Sintering time: 3 hours The obtained sintered body was processed into a sputtering target having a diameter of 4 inches.

[0044] <Sputtering process> The resulting sputtering target is used to form a film having a desired composition. , reference example A Cr-Si based film was also prepared as a comparative example. , reference example The Cr-Si based films of the comparative example and the comparative example were formed under the conditions shown in Table 1. The detailed film formation conditions are shown below. (Sputtering conditions) Equipment: DC magnetron sputtering equipment (ULVAC) Magnetic field strength: 1000 Gauss (directly above the target, horizontal component) Distance between target boards: 90mm ·Board temperature: Room temperature (approx. 25°C) Type of gas introduced (sputtering atmosphere): Argon (Ar), or Argon and Nitrogen (N 2 ) Introduced gas partial pressure: Nitrogen partial pressure (N 2 / (Ar+N 2 )) was carried out. Substrate used: Glass substrate (Corning EagleXG) 0.8mm thick Sputtering power: 200W (2.5W / cm 2 ) ·Target film thickness: 100nm In Table 1, the nitrogen partial pressure (N 2 / (Ar+N 2 )) is Ar+N 2 N when the total amount is 100% 2 The results are expressed as a percentage (%).

[0045] (Post-treatment conditions after film formation) The Cr-Si based film formed on the substrate was heat-treated in vacuum for 60 minutes at the heat treatment temperature shown in Table 2.

[0046] The composition, crystallinity, and electrical properties of the film were measured by the following methods. (Film composition) The composition of the film was quantified by the RBS method (Rutherford backscattering spectroscopy) using a common measuring device (Eurofins EAG RBS-400 analytical end station).

[0047] (resistivity) The resistivity of the film was measured using an 8403-type AC / DC Hall measurement system (manufactured by Toyo Corporation). Figures 1 and 2 show the relationship between resistivity and temperature in Example 1 and Comparative Example 1 described below.

[0048] (2) Calculation method of TCR and average TCR The resistivity (Ω cm) of the film was measured at 10°C intervals from 30°C to 150°C using an 8403 AC / DC Hall measurement system (manufactured by Toyo Corporation). 30 ~R 150 ) was measured, and the resistivity R (Ω cm) at each temperature and the resistivity R at 30°C were 30 The TCR was calculated from the resistance (Ω·cm) and each temperature T (℃) using the following formula in the range from 40℃ to 150℃. TCR(ppm / ℃)=(RR 30 ) / (R 30 ×(T-30))×10 6 The average TCR was calculated as the arithmetic mean of the TCR values ​​determined in the range of 40°C to 150°C.

[0049] (3) How to calculate the difference between the maximum and minimum TCR values The difference between the maximum and minimum values ​​of TCR in the range from 40°C to 150°C obtained in (2) was calculated.

[0050] Example 1 Using a sputtering target having the Cr-Si composition (target composition) shown in Table 1, a Cr-Si film was formed by sputtering under the film formation conditions shown in Table 1. The obtained Cr-Si film was subjected to a heat treatment in vacuum (5 Pa or less) at the treatment temperature shown in Table 2. The obtained Cr-Si film was measured for average TCR, maximum TCR value at each temperature, minimum TCR value at each temperature, maximum-minimum TCR value, and resistivity at 30°C. The results are shown in Table 2.

[0051] ( Reference Examples 1 to 2, 4, 6 and Examples 9) Composition of the sputtering target and deposition conditions (atmospheric gas during deposition (introduced gas), N 2 / (Ar+N 2 A Cr-Si-based film was produced under the same conditions as in Example 1, except that the composition and film formation conditions of the sputtering target (Tc) and film thickness) were set to those shown in Table 1, and the heat treatment temperature of the Cr-Si-based film was changed to the heat treatment temperature of the Cr-Si-based film (treatment temperature shown in Table 2). The average TCR, maximum TCR value at each temperature, minimum TCR value at each temperature, maximum-minimum TCR value, and resistivity at 30°C were measured for the obtained Cr-Si-based film. The results are shown in Table 2.

[0052] ( Reference example 3 ) A Cr-Si-based film was obtained under the same conditions as in Example 1, except that when preparing the sputtering target, the temperature of the molten metal in the gas atomization method was changed to 1700°C, the sintering temperature when preparing the sintered body was changed to 1350°C, the composition of the sputtering target and the film formation conditions were changed to those shown in Table 1, and no heat treatment was performed after film formation.

[0053] Example 5 A Cr-Si-based film was obtained under the same conditions as in Example 1, except that, when preparing the sputtering target, the temperature of the molten metal in the gas atomization method was changed to 1700°C, the sintering temperature when preparing the sintered body was changed to 1350°C, the composition of the sputtering target and the film formation conditions were changed to the composition of the sputtering target and the film formation conditions shown in Table 1, and the heat treatment temperature of the Cr-Si-based film was changed to the heat treatment temperature of the Cr-Si-based film (the treatment temperature shown in Table 2).

[0054] ( Reference example 4 ) A Cr-Si based film was obtained in the same manner as in Example 1, except that the film was formed by sputtering under the film formation conditions shown in Table 1, and that the heat treatment after film formation was not performed.

[0055] (Comparative Examples 1, 2, and 4) The sputtering target composition and film formation conditions were changed to those shown in Table 1, and the heat treatment temperature of the formed Cr-Si-based film was changed to the treatment temperature shown in Table 2, but the conditions were the same as in Example 1. The obtained Cr-Si-based film was measured for average TCR, maximum TCR value at each temperature, minimum TCR value at each temperature, maximum-minimum TCR value, and resistivity at 30°C. The results are shown in Table 2.

[0056] Comparative Example 3 In preparing the sputtering target, the temperature of the molten metal in the gas atomization method was changed to 1730°C, the sintering temperature in preparing the sintered body was changed to 1350°C, the composition of the sputtering target and the film formation conditions were changed to those shown in Table 1, and the heat treatment temperature of the Cr-Si-based film after film formation was changed to the treatment temperature shown in Table 2. The sputtering target was prepared under the same conditions as in Example 1. The average TCR, the maximum TCR value at each temperature, the minimum TCR value at each temperature, the maximum-minimum TCR value, and the resistivity at 30°C were measured for the obtained Cr-Si-based film. The results are shown in Table 2.

[0057] [Table 1]

[0058] [Table 2]

[0059] In the above table, the "-" in the treatment temperature column indicates that no heat treatment was performed. Also, in the above table and in Figures 1 and 2, the resistivity "○○E-××" indicates ○○ multiplied by 10 to the power of -××. For example, "1.3E-03" indicates 1.3×10^(-3), which means 1.3 multiplied by 10 to the power of -3. The Cr-Si based film of the present invention has small absolute values ​​of TCR, small absolute values ​​of average TCR, and small differences between maximum and minimum TCR values, and has excellent characteristics as a resistor.

Claims

1. A Cr-Si-based film containing chromium (Cr) and silicon (Si), the film has a composition range of Cr / (Cr+Si)=0.25 to 0.75, and the absolute values ​​of TCR at 10°C intervals in a temperature range of 40°C to 150°C are all 0 ppm / °C or more and 100 ppm / °C or less; the absolute value of the average TCR in 10°C increments in the temperature range is 0 ppm / °C or more and 30 ppm / °C or less; A Cr--Si based film containing nitrogen (N).

2. 2. The Cr--Si based film according to claim 1, wherein the difference between the maximum and minimum values ​​of TCR in increments of 10° C. within said temperature range is 100 ppm / ° C. or less.

3. 3. The Cr--Si based film according to claim 1, wherein the absolute values ​​of TCR at intervals of 10° C. in said temperature range are all 0 ppm / ° C. or more and 50 ppm / ° C. or less.

4. 4. The Cr--Si based film according to claim 1, wherein the absolute value of the average TCR in 10° C. increments in the temperature range is 0 ppm / ° C. or more and 10 ppm / ° C. or less.

5. 5. The Cr--Si based film according to claim 1, wherein the composition range of the film is Cr / (Cr+Si)=0.3 to 0.

5.

6. The Cr--Si based film according to claim 1, characterized in that the resistivity at 30° C. is 1.0×10 −4 Ω·cm or more.

7. 7. The Cr--Si based film according to claim 6, wherein Si--N is 25 to 75 wt %.

8. 8. The method for producing a Cr--Si based film according to claim 1, wherein a sputtering target containing chromium and silicon as main components is used to form the film by a sputtering method.

9. 9. The method for producing a Cr--Si based film according to claim 8, further comprising heat-treating the Cr--Si based film formed by sputtering in an oxygen-free atmosphere at 500° C. or more and 800° C. or less.

Images