Hard membrane

Abstract

To provide a hard film with sufficient hardness, light transmittance, and conductivity. [Solution] The hard film 1 of this disclosure comprises a SiAlON layer 10, which is a layer made of SiAlON, and a TiAlN layer 12, which is a layer made of TiAlN. The TiAlN layer 12 is arranged on the side opposite the substrate to the SiAlON layer 10. The hard film 1 is made of SiN x SiN is a layer made of (1 ≤ x ≤ 1.33) x The layers may be provided on both the substrate side and the non-substrate side of the TiAlN layer 12. The hard film 1 may also include an SiO2 layer, which is a layer made of SiO2, located on the non-substrate side of the SiAlON layer 10.

Description

[Technical Field]

[0001] This disclosure relates to a hard film. [Background technology]

[0002] As a surface protective film, one is known that has a hard film made of SiAlON, as described in International Publication No. 2022 / 091848 (Patent Document 1). Furthermore, a hard coating removal device is known, as described in Japanese Patent Publication No. 2024-126948 (Patent Document 2). This hard coating removal device removes titanium aluminum nitride (TiAlN) coatings formed on the surface of cemented carbide, high-speed tools, etc. [Prior art documents] [Patent Documents]

[0003] [Patent Document 1] International Publication No. 2022 / 091848 [Patent Document 2] Japanese Patent Publication No. 2024-126948 [Overview of the project] [Problems that the invention aims to solve]

[0004] SiAlON films have sufficient hardness and light transmission, but they are not conductive. TiAlN films also have sufficient hardness and conductivity, but they absorb visible light, and therefore, depending on the film thickness, they may not have sufficient light transmission.

[0005] Therefore, the main objective of this disclosure is to provide a hard film with sufficient hardness, light transmittance, and conductivity. [Means for solving the problem]

[0006] This specification discloses a hard film. This hard film may include a SiAlON layer, which is a layer made of SiAlON. The hard film may also include a TiAlN layer, which is a layer made of TiAlN. The TiAlN layer may be located on the side opposite the substrate to the SiAlON layer. [Effects of the Invention]

[0007] The main effect of this disclosure is to provide a hard film with sufficient hardness, light transmittance, and conductivity. [Brief explanation of the drawing]

[0008] [Figure 1] This is a schematic cross-sectional view of the hard film and substrate related to this disclosure. [Figure 2] This is a schematic graph illustrating the various properties of a SiAlON layer, with the atomic ratio of silicon to aluminum on the horizontal axis and the relative strength of various properties on the vertical axis. [Figure 3] This is a schematic top view of a hard film manufacturing apparatus. [Figure 4] Figure 3 is a flowchart illustrating an example of the operation when manufacturing the hard film shown in Figure 1. [Figure 5] This is a schematic surface diagram of a Ti+Al target. [Modes for carrying out the invention]

[0009] Examples of embodiments relating to this disclosure will be described below with reference to the drawings as appropriate. Furthermore, this disclosure is not limited to the following examples.

[0010] <<Structure of the hard membrane>> As shown in Figure 1, the hard film 1 according to this disclosure is formed on the film-forming surface M of a glass substrate 2. The substrate 2 with the hard film 1 is used as an optical product C. Examples of optical products C include lighting covers and windows. The substrate 2 is the base on which the hard film 1 is formed, and in particular, in the case of a plate, it is a substrate. Furthermore, the film deposition surface M may be provided in multiple locations, such as both sides of the substrate. Also, one or more interlayers may be placed between the substrate 2 and the hard film 1. When an interlayer is present, the hard film 1 is formed on the surface of the interlayer and indirectly on the film deposition surface M. The substrate 2 may be made of a material other than glass. Moreover, the hard film 1 may be formed on a variety of objects, for example, on roads, railways (tracks), monorails, and guide lights and indicators related to sidewalks.

[0011] The hard film 1 has multiple layers. The hard film 1 has one or more SiAlON layers 10 and one or more TiAlN layers 12.

[0012] The SiAlON layer 10 is a film made of SiAlON. The properties of the SiAlON layer 10 change depending on the atomic ratio of silicon to aluminum. When the number of silicon atoms is greater than the number of aluminum atoms, the properties of the SiAlON layer 10 approach those of a silicon nitride (Si3N4) film, and when the number of aluminum atoms is greater than the number of silicon atoms, the properties approach those of an aluminum oxide (Al2O3) film. The atomic ratio of bonded oxygen and nitrogen changes depending on the atomic ratio of silicon to aluminum. The properties of the SiAlON layer 10, such as the atomic ratio of silicon to aluminum, can be changed depending on the type of manufacturing method and its settings.

[0013] Figure 2 is a schematic graph of the various properties of the SiAlON layer 10, with the atomic ratio of silicon to aluminum on the horizontal axis and the relative strength of various properties, namely hardness, adhesion, and chemical resistance, on the vertical axis. On the horizontal axis, as you move to the left, the number of aluminum atoms increases relative to the number of silicon atoms, and at the far left end it becomes Al2O3. Conversely, as you move to the right, the number of silicon atoms increases relative to the number of aluminum atoms, and at the far left end it becomes Si3N4. The hardness of the SiAlON layer 10 increases as the number of silicon atoms increases (upwards on the vertical axis). The adhesion of the SiAlON layer 10 to the substrate is high in the central part of the horizontal axis where aluminum and silicon are mixed (located at the top on the vertical axis), and low on both sides of that. The chemical resistance of the SiAlON layer 10 shows a consistently high level (upper on the vertical axis) when the number of silicon atoms is above a predetermined level relative to the number of aluminum atoms, and decreases when the number of silicon atoms is below a predetermined level relative to the number of aluminum atoms. The SiAlON layer 10 according to this disclosure preferably has an atomic ratio of silicon to aluminum that provides high levels of hardness, adhesion, and chemical resistance (see the good region in Figure 2).

[0014] Furthermore, the refractive index of the SiAlON layer 10 changes depending on the atomic ratio of silicon to aluminum, and generally increases as the number of silicon atoms increases relative to the number of aluminum atoms. Preferably, the refractive index of the SiAlON layer 10 for light with a wavelength of 550 nm (nanometers) is 1.90 or more and 1.94 or less. In this case, the SiAlON layer 10 has the atomic ratio within the good range described above.

[0015] The TiAlN layer 12 is a film made of TiAlN. The properties of the TiAlN layer 12 change depending on the atomic ratio of titanium to aluminum. When the number of titanium atoms is greater than the number of aluminum atoms, the properties of the TiAlN layer 12 approach those of a titanium nitride (TiN) film, and when the number of aluminum atoms is greater than the number of titanium atoms, the properties approach those of an aluminum nitride (AlN) film. The atomic ratio of the bonded nitrogen atoms changes according to the atomic ratio of titanium to aluminum. The properties of the TiAlN layer 12, such as the atomic ratio of titanium to aluminum, can be changed depending on the type of manufacturing method and the settings of that method.

[0016] The hardness of the TiAlN layer 12 is sufficient, regardless of the atomic ratio of titanium to aluminum. The visible light transmittance, or transparency, of the TiAlN layer 12 decreases as the number of titanium atoms increases relative to the number of aluminum atoms. Visible light is light that can be seen. The wavelength range of visible light is the visible range. In this case, the visible range is between 400 nm and 700 nm. The lower limit of the visible range may be, for example, 380 nm, 390 nm, 410 nm, or 420 nm. The upper limit of the visible range may be, for example, 680 nm, 690 nm, 710 nm, 720 nm, 740 nm, 750 nm, 780 nm, or 800 nm. Furthermore, the conductivity of the TiAlN layer 12 changes depending on the atomic ratio of titanium to aluminum, and increases as the number of titanium atoms increases relative to the number of aluminum atoms. In the TiAlN layer 12, the greater the number of titanium atoms relative to the number of aluminum atoms, the less transparent the layer becomes and the greater its conductivity.

[0017] The hard film 1 may consist only of the TiAlN layer 12. Alternatively, the hard film 1 may have layers other than the SiAlON layer 10 and the TiAlN layer 12. For example, the hard film 1 may have one or more SiO2 layers. The SiO2 layer may be placed between the SiAlON layer 10 and the TiAlN layer 12, or on the anti-substrate side of the TiAlN layer 12, or it may be placed as the layer on the anti-substrate side of the hard film 1, i.e., the outermost layer. The anti-substrate side can also be called the air side. Furthermore, the hard film 1 contains 1 or more SiN x SiN x It may have layers. x is 1 ≤ x ≤ 1.33. When x = 1.33, SiN x This becomes Si3N4. x The layer may be positioned between the SiAlON layer 10 and the TiAlN layer 12, or it may be positioned on the side opposite the TiAlN layer 12, or it may be positioned as the layer on the side closest to the substrate in the hard film 1, i.e., the outermost layer.

[0018] Furthermore, the hard film 1 may also have an anti-fouling layer. The antifouling layer is disposed on the outermost layer. The antifouling layer imparts an antifouling function to the hard film 1. The antifouling function includes at least one of a water repellent function and an oil repellent function. The antifouling layer is preferably a single-layer film of a single layer. Incidentally, the antifouling layer may be a multilayer film having a plurality of layers. The antifouling layer is, for example, a polycondensate of an organosilicon compound. By polycondensation, thickening and densification of the film are possible, and the adhesion to the adjacent layer and the surface hardness are increased. Therefore, the antifouling layer exhibits both water repellency and oil repellency in addition to water repellency. Also, in the antifouling layer, a film excellent in stain wiping property is easily obtained. The organosilicon compound before polycondensation is preferably a compound having a silicon-containing functional group represented by -SiR y X 3-y (R is a monovalent organic group, X is a hydrolyzable group, and y is an integer from 0 to 2). Here, as X, for example, an alkoxy group such as -OCH3, -OCH2CH3, an acyloxy group such as -OCOCH3, -ON=CR a R b such as a ketoxime group (R a 、R b each represent a monovalent organic group), a halogen group such as -Cl, -Br, -NR c R d such as an amino group (R c 、R d each represent a monovalent organic group), etc. As such an organosilicon compound, a fluorine-containing organosilicon compound is suitable. The fluorine-containing organosilicon compound is excellent in water and oil repellency, electrical insulation, mold release property, solvent resistance, lubricity, heat resistance, and defoaming property in general. In particular, a relatively large organosilicon compound having a perfluoroalkyl group or a perfluoropolyether group in the molecule and having a molecular weight of about 1000 to 50000 is excellent in antifouling property. The antifouling layer is formed, for example, by a known vapor deposition method or ion sputtering method. Incidentally, the antifouling layer may be treated as a separate film independent of the hard film 1.

[0019] ≪Manufacturing apparatus for hard film≫ Next, an embodiment of the apparatus for manufacturing the hard film 1 described above will be explained. Furthermore, the manufacturing apparatus for the hard film 1 relating to this disclosure is not limited to the following forms.

[0020] Figure 3 is a schematic top view of the manufacturing apparatus 101 according to the said configuration. The manufacturing apparatus 101 is a drum-type sputtering apparatus (carousel-type sputtering apparatus) that deposits a hard film 1 on the film deposition surface M of one or more substrates 2. The manufacturing apparatus 101 comprises a vacuum chamber 102 as a film deposition chamber, and a cylindrical drum 104 positioned in the center of the vacuum chamber 102 so as to be rotatable around its own axis. A substrate 2, to be deposited on, is held on the outer cylindrical surface of the drum 104 with the film deposition surface M facing outwards.

[0021] A first sputtering source 110 is positioned on one side of the vacuum chamber 102. The first sputtering source 110 includes a sputtering cathode 112 for setting the first target T1, a pair of protective plates 114, and a sputtering gas inlet 116 through which sputtering gas is introduced after appropriate flow rate adjustment. The sputter cathode 112 is connected to an external DC power supply (not shown). The protective plate 114 is positioned to separate the first target T1 from the opposing portion of the drum 104 from the rest of the vacuum chamber 102. The sputtering gas inlet 116 directs the sputtering gas towards the space separated by the protective plate 114.

[0022] A second sputtering source 120 is located on another side of the vacuum chamber 102. The second sputtering source 120, like the first sputtering source 110, includes a sputtering cathode 122 for setting the second target T2, a pair of protective plates 124, and a sputtering gas inlet 126.

[0023] Furthermore, a radical source 130 is positioned on the other side of the vacuum chamber 102. The radical source 130 includes a radical gas inlet 134 into which gas can be introduced after adjusting the flow rate by a valve 132, and a gun 136 into which plasma can be generated when a voltage is applied by an acceleration voltage power supply (not shown). The gas introduced into the vacuum chamber 102 from the radical gas inlet 134 is radicalized by the plasma generated by the gun 136 and irradiated towards the substrate 2 in a beam shape.

[0024] In addition, exhaust units 140 are provided on both sides of the radical source 130. Each exhaust unit 140 is used to evacuate the vacuum chamber 102. Furthermore, the arrangement and number of at least one of the first sputtering source 110, the second sputtering source 120, the radical source 130, and each exhaust unit 140 are not limited to those described above. The current (voltage) in at least one of the first sputtering source 110, the second sputtering source 120, and the radical source 130 may be direct current, or low-frequency or high-frequency alternating current.

[0025] An example of the operation of the manufacturing apparatus 101 when manufacturing the hard film 1 shown in Figure 1 (an example of a method for manufacturing the hard film 1) will be explained mainly based on Figure 4.

[0026] First, a series of processes related to the deposition of the SiAlON layer 10 are carried out. The substrate 2 is set in the drum 104, and silicon (Si) is set as the first target T1, and aluminum (Al) is set as the second target T2 (step S1). Next, the inside of the vacuum chamber 102 is evacuated (step S2). Next, the drum 104 is rotated, and the substrate 2 held in the drum 104 passes sequentially and repeatedly at high speed inside the first sputtering source 110, the second sputtering source 120, and the radical source 130 (step S3). Next, the substrate 2 is cleaned (step S4). That is, with oxygen (O2) gas introduced from the radical gas inlet 34 of the radical source 130, a high-frequency voltage is applied to the gun 136 to generate radical oxygen, which is then irradiated onto the moving substrate 2 for a predetermined time. By such irradiation with radical oxygen, even if organic matter is attached to the surface of the substrate 2, the organic matter is decomposed and peeled off by the radical oxygen and ultraviolet light generated by the plasma, and the surface of the substrate 2 is cleaned. Such cleaning improves the adhesion of the film to be formed later.

[0027] Next, the SiAlON layer 10 is formed (step S5). Specifically, while the rotation of the drum 104 is maintained, a rare gas (in this case, Ar gas) is introduced from the sputtering gas inlet 116 of the first sputtering source 110, and a DC voltage is applied to the sputtering cathode 112, causing Si on the surface of the first target T1 to be deposited onto the surface of the substrate 2 by sputtering with Ar. Furthermore, a rare gas (in this case, Ar gas) is introduced from the sputtering gas inlet 126 of the second sputtering source 120, and a DC voltage is applied to the sputtering cathode 122, causing Al on the surface of the second target T2 to be deposited onto the surface of the substrate 2 by sputtering with Ar. Furthermore, with oxygen gas (O2 gas) and nitrogen gas (N2 gas) introduced from the radical gas inlet 134 of the radical source 130, a high-frequency voltage is applied to the gun 136 to generate radical oxygen and radical nitrogen, which are irradiated onto the moving substrate 2 on which Si and Al are deposited, thereby causing oxynitridation of Si and Al. A noble gas may also be introduced along with the O2 and N2 gases. The thickness of the hard film 1 is controlled by the length of the sputtering time, provided that the power supplied to the sputter cathodes 112 and 122 is constant and the deposition rate, which is the physical thickness deposited per unit time, is constant. Therefore, when a time corresponding to the desired film thickness has elapsed, the voltage application to the sputter cathodes 112 and 122 and the gun 136 is stopped, and the deposition of the hard film 1 is completed.

[0028] Once the formation of the SiAlON layer 10 is complete, the drum 104 is stopped (step S6), and after appropriate cooling, a series of processes for forming the TiAlN layer 12 are carried out. In other words, while the Si of the first target T1 is maintained, Al is removed as the second target T2 and a combination of aluminum and titanium (Ti+Al) is set (step S8). Next, the inside of the vacuum chamber 102 is evacuated (step S8). Next, drum 104 is rotated (step S9).

[0029] Next, the TiAlN layer 12 is formed (step S10). Specifically, while the rotation of the drum 104 is maintained, a rare gas (in this case, Ar gas) is introduced from the sputtering gas inlet 126 of the second sputtering source 120, and a DC voltage is applied to the sputtering cathode 122, causing Al and Ti on the surface of the second target T2 to be deposited onto the surface of the substrate 2 with the SiAlON layer 10 by sputtering with Ar. In contrast, the introduction of a rare gas from the sputtering gas inlet 116 of the first sputtering source 110 and the application of a DC voltage to the sputtering cathode 112 are not performed, and no Si is deposited. Furthermore, with N2 gas introduced from the radical gas inlet 134 of the radical source 130, a high-frequency voltage is applied to the gun 136 to generate radical nitrogen, which is then irradiated onto the substrate 2 with the moving SiAlON layer 10 containing deposited Al and Ti, thereby nitriding the Al and Ti. A noble gas may also be introduced along with the N2 gas. The thickness of the TiAlN layer 12 is controlled by the length of the sputtering time, provided that the power supplied to the sputter cathode 122 is constant and the deposition rate, which is the physical thickness deposited per unit time, is constant. Therefore, when a time corresponding to the desired thickness has elapsed, the voltage applied to the sputter cathode 122 and the gun 136 is stopped, and the deposition of the hard film 1, which comprises the TiAlN layer 12 on the SiAlON layer 10, is completed.

[0030] Once the formation of the TiAlN layer 12 is complete, the drum 104 is stopped (step S11), and after appropriate cooling, the substrate 2 with the hard film 1 is removed (step S12). Furthermore, a third sputtering source similar to the first sputtering source 110 and the second sputtering source 120 may be provided. The third sputtering source may be provided on one side of the vacuum chamber 102, the same side as the first sputtering source 110 or the second sputtering source 120, or on yet another side of the vacuum chamber 102. For example, by setting a Si target in the first sputtering source 110, an Al target in the second sputtering source 120, and a Ti target in the third sputtering source, the replacement of targets as in step S7 may be omitted in the formation of the SiAlON layer 10 and the TiAlN layer 12. In addition, one or more interlayer films may be further applied between the hard film 1 and the substrate 2 by the manufacturing apparatus 101 or another apparatus.

[0031] Furthermore, when an SiO2 layer is formed, the Si target is activated and radical oxygen is introduced. Furthermore, SiN x When a layer is formed, the Si target is activated and radical nitrogen is introduced. [Examples]

[0032] Next, various case studies will be explained. Furthermore, this disclosure is not limited to the following examples.

[0033] [TiAlN 12-layer monolayer film] Various examples were fabricated using the manufacturing apparatus 101 described above, in the case where the hard film 1 consists of only one TiAlN layer 12. The substrate was a plate-shaped substrate 2 made of white glass. The hard film 1 was deposited directly onto one side (film deposition surface M) of the substrate without an interlayer. The Vickers hardness (HV) of the white glass substrate was 647.57. For comparison, the Vickers hardness of the quartz substrate was 910.48. The Vickers hardness (HV) here was measured using a measuring device (NT-2100 manufactured by Elionix Co., Ltd.), and the same applies below. Furthermore, in the manufacturing apparatus 101, the inside of the vacuum chamber 102 is 2 × 10 at the start of film deposition. -4 It was assigned the unit Pa (Pascal). Furthermore, the rotational speed of drum 104 was set to 100 rpm (revolutions per minute). Note that the rotation of drum 104 may be temporarily changed or stopped. Furthermore, the high frequency of the radical source 130 was set to 13.56 MHz (megahertz).

[0034] Furthermore, the Ti+Al material used as the second target T2 during the deposition of the TiAlN layer 12 had the surface shown in Figure 5. Specifically, a Ti+Al target was used, which consisted of a Ti target section A1 and an Al target section A2 combined. The vertical lengths of the Ti target section A1 and the Al target section A2 corresponded to the vertical length of the drum 104. The Ti target section A1 was provided with a first inclined surface, and the Al target section A2 was provided with a second inclined surface corresponding to the first inclined surface, so that the first inclined surface of the Ti target section A1 was in contact with the second inclined surface of the Al target section A2. The Ti+Al target was then set to align with the drum 104 in the vertical direction. As a result, the substrate set at the upper end of the outer surface of the drum 104 passed through the inner surface of the upper end of the Ti+Al target, the substrate set in the central part of the outer surface of the drum 104 in the vertical direction passed through the inner surface of the central part of the Ti+Al target, and the substrate set at the lower end of the outer surface of the drum 104 passed through the inner surface of the lower end of the Ti+Al target. Eleven substrates were arranged at approximately equal intervals in the vertical direction of the drum 104. The uppermost substrate passed through the first section W1, which is the uppermost section of the 11 sections obtained by dividing the Ti+Al target evenly in the vertical direction. The second substrate from the top passed through the second section W2, which is the second section from the top of the 11 sections obtained by dividing the Ti+Al target evenly in the vertical direction. Then, the third to eleventh substrates from the top passed through the third section W3 to the eleventh section in sequence. Note that the number of sections may be 10 or less, or 12 or more. Ti with a purity of 99.99% was used for the Ti target section A1. Al with a purity of 99.99% was used for the Al target section A2.

[0035] In addition, O2 gas, N2 gas, and Ar gas were all used with a purity of 99.99% or higher. Furthermore, a turbomolecular pump was used in the exhaust section 140.

[0036] Then, in Study Examples 1-1 to 1-11, samples were formed in which only the TiAlN layer 12 was directly formed on each substrate using a Ti+Al target. Study Examples 1-1 to 1-11 are sometimes collectively referred to as Study Example 1, and the same applies to the other study examples. Study Example 1-1 concerned the first circuit board set from the top, corresponding to the first section W1. Study Example 1-2 concerned the second circuit board set from the top, corresponding to the second section W2. Similarly, Study Examples 1-3 to 1-11 concerned the third to eleventh circuit boards from the top, corresponding to the third to eleventh sections W3 to W11. The suffix numbers after the "-" in Study Example 1 were treated similarly in the other study examples. In Study Example 1, the physical thickness of the TiAlN layer 12 was set to 5 nm. The structure of hard film 1 in Example 1 is shown below. Substrate [TiAlN 5nm]

[0037] Furthermore, the atomic ratios of Ti and Al in the TiAlN layers 12 of the examples 1-1 to 1-11 were determined by observing each TiAlN layer 12 using X-ray fluorescence analysis (XRF). Furthermore, the surface resistivity of the TiAlN layer 12 as a single layer film on such a glass substrate was measured. For this measurement, a Hi-Lester UX MCP-HT800 manufactured by Nitto Seiko Airanatech Co., Ltd. was used, and the surface resistivity was obtained in units of Ω / □ (ohms per square). The surface resistivity measurements in other study examples were performed in the same manner as the surface resistivity measurements in Study Example 1. Furthermore, the average transmittance in the visible range for the TiAlN layer 12 in Study Examples 1-1 to 1-11 was measured. A Hitachi High-Tech U4100 spectrophotometer was used for this measurement. The incident angle of the measurement light was 0°. The measurement of the average transmittance in the visible range in the other study examples was performed in the same manner as the measurement of the average transmittance in Study Example 1.

[0038] Table 1 shows the area ratios of the Ti target portion A1 and the Al target portion A2 in the first to eleventh sections W1 to W11 of the Ti+Al target, the atomic ratios of Ti and Al in the TiAlN layer 12 in the study examples 1-1 to 1-11 for the 1st to 11th substrates corresponding to the first to eleventh sections W1 to W11, the surface resistivity (Ω / □), and the average value of the transmittance in the visible range. The atomic ratios of Ti and Al in the TiAlN layer 12 correspond to the atomic ratio of Ti to Al, i.e., Ti:Al. For example, the 16.00% Ti and 84.00% Al in Study Example 1-1 indicate a Ti:Al ratio of 16:84 in the TiAlN layer 12. In surface resistivity, the number after "E" indicates an exponent of 10. For example, 2.82E+09 is 2.82 × 10⁻⁶. 9 That is the case. In the average transmittance values, the underlined values ​​are calculated values ​​obtained using a computer. The same applies to the atomic ratio, surface resistivity, and average transmittance values ​​in other studies as well.

[0039] [Table 1]

[0040] Table 1 shows that the atomic ratio of Ti to Al in the TiAlN layer 12 is determined by the ratio of the area of ​​the Ti target portion A1 to the area of ​​the Al target portion A2 for each section on the Ti+Al target surface. Furthermore, Table 1 shows that in the TiAlN layer 12, the greater the number of Ti atoms relative to the number of Al atoms, the lower the surface resistivity and the better the conductivity. Furthermore, Table 1 shows that in the TiAlN layer 12, the greater the number of Al atoms relative to the number of Ti atoms, the higher the average transmittance and the better the visibility.

[0041] Furthermore, in Study Examples 2-1 to 2-11, structures similar to Study Examples 1-1 to 1-11 were formed, except for the physical thickness of the TiAlN layer 12. In Study Example 2, the physical thickness of the TiAlN layer 12 was set to 4 nm. Furthermore, in Study Examples 3-1 to 3-11, samples similar to Study Examples 1-1 to 1-11 were formed, except for the physical thickness of the TiAlN layer 12. In Study Example 3, the physical thickness of the TiAlN layer 12 was set to 3 nm. The structure of hard film 1 in Example 2 is shown below. Substrate [TiAlN 4nm] The structure of hard film 1 in Example 3 is shown below. Substrate [TiAlN 3nm]

[0042] Then, for examples 2 and 3, the average values ​​of surface resistivity and transmittance in the visible range were measured. Table 2 shows the average values ​​of surface resistivity and transmittance in study examples 2 and 3.

[0043] [Table 2]

[0044] Table 2 shows that, as with Example 1, even when the physical thickness of the TiAlN layer 12 changes in Examples 2 and 3, the average transmittance increases and visibility improves as the number of Al atoms in the TiAlN layer 12 increases relative to the number of Ti atoms, while a trade-off occurs where the surface resistivity increases and conductivity decreases. Furthermore, Tables 1 and 2 show that when comparing similar Ti:Al study examples, i.e., study examples 1 to 3 with the same sub-numbers, the surface resistivity increases and the average transmittance increases as the physical film thickness of the TiAlN layer 12 decreases from study example 1 to 2 to 3.

[0045] [Two layers: SiAlON layer 10 and TiAlN layer 12] Various examples were fabricated using the above-described manufacturing apparatus 101 when the hard film 1 consists of two layers: a SiAlON layer 10 on the substrate side and a TiAlN layer 12 on the non-substrate side. The TiAlN layer 12 was formed in the same manner as in Examples 1-3. On the other hand, the formation of the SiAlON layer 10 prior to the formation of the TiAlN layer 12 was carried out in the same manner as the formation of the TiAlN layer 12 in Study Examples 1 to 3, except for the following: Specifically, 99.99% pure Si doped with B (boron) was used as the Si for the first target T1. Also, 99.99% pure Al was used as the Al for the second target T2 during the formation of the SiAlON layer 10.

[0046] In study examples 4-1 to 4-11, a hard film 1 was formed on each substrate, with a SiAlON layer 10 having a physical thickness of 3 μm and a TiAlN layer 12 on top of it having a physical thickness of 5 nm. The structure of hard film 1 in Example 4 is shown below. Substrate [SiAlON / TiAlN 5nm] Furthermore, in study examples 5-1 to 5-11, a hard film 1 was formed on each substrate, with a SiAlON layer 10 having a physical thickness of 3 μm and a TiAlN layer 12 above it having a physical thickness of 4 nm. The structure of hard film 1 in Example 5 is shown below. Substrate [SiAlON / TiAlN 4nm] Furthermore, in study examples 6-1 to 6-11, a hard film 1 was formed on each substrate, with a SiAlON layer 10 having a physical thickness of 3 μm and a TiAlN layer 12 above it having a physical thickness of 3 nm. The structure of hard film 1 in study example 6 is shown below. Substrate [SiAlON / TiAlN 3nm]

[0047] Then, for examples 4-6, the average transmittance in the visible range was measured. Table 3 shows the average transmittance values ​​for examples 4 to 6.

[0048] [Table 3]

[0049] Table 3 shows that, similar to examples 1-3, in the TiAlN layer 12 on the SiAlON layer 10 related to hard film 1 in study examples 4-6, the average transmittance is higher and visibility is better as the number of Al atoms is greater than the number of Ti atoms. Furthermore, as can be seen from Tables 1 to 3, when the SiAlON layer 10 is added to study examples 1 to 3 to create study examples 4 to 6, the average transmittance decreases when comparing examples with the same sub-number. Furthermore, since the SiAlON layer 10 does not have sufficient conductivity, and the TiAlN layer 12 is positioned on the anti-substrate side of the SiAlON layer 10, it can be said that the hard film 1 in Study Examples 4-6 has the same surface resistivity as the TiAlN layer 12 in Study Examples 1-3.

[0050] [Two layers: SiO2 layer and TiAlN layer 12] Various examples were fabricated using the above-described manufacturing apparatus 101 when the hard film 1 consists of two layers: an SiO2 layer on the substrate side and a TiAlN layer 12 on the non-substrate side. The TiAlN layer 12 was formed in the same manner as in Examples 1-3. On the other hand, the formation of the SiO2 layer prior to the formation of the TiAlN layer 12 was carried out in the same manner as the formation of the SiAlON layer 10 in Study Examples 4-6, except for the following: the second target T2 was not activated, and only oxygen radicals were introduced.

[0051] In study examples 7-1 to 7-11, a hard film 1 was formed on each substrate, with a physical thickness of 90 nm for the SiO2 layer and a physical thickness of 5 nm for the TiAlN layer 12 on top of it. The structure of hard film 1 in Example 7 is shown below. Substrate [SiO2 / TiAlN 5nm]

[0052] For example 7, the average values ​​of surface resistivity and transmittance in the visible range were measured. Table 4 shows the average values ​​of surface resistivity and transmittance in Study Example 7.

[0053] [Table 4]

[0054] Table 4 shows that, similar to Examples 1-6, in Example 7, the average transmittance and surface resistivity increase as the number of Al atoms increases relative to the number of Ti atoms. Furthermore, as can be seen from Tables 1 and 4, compared to Study Example 1, which involved a single layer of TiAlN 12 with a thickness of 5 nm, Study Example 7, in which an SiO2 layer was added beneath the 5 nm thick TiAlN 12, showed a slight increase in surface resistivity. Furthermore, Tables 1 and 4 show that, compared to Study Example 1, which involved a single layer of TiAlN 12 with a thickness of 5 nm, Study Example 7, in which an SiO2 layer was added beneath the 5 nm thick TiAlN layer 12, showed an average transmittance increase of approximately 1 percentage point.

[0055] [Three layers: SiAlON layer 10, SiO2 layer, and TiAlN layer 12] Various examples were fabricated using the above-described manufacturing apparatus 101 for the case where the hard film 1 consists of three layers arranged in the order of SiAlON layer 10, SiO2 layer, and TiAlN layer 12 from the substrate side. Specifically, in study examples 8-1 to 8-11, a hard film 1 was formed on each substrate, with a physical thickness of 3 μm for the SiAlON layer 10, a physical thickness of 90 nm for the SiO2 layer above it, and a physical thickness of 5 nm for the TiAlN layer 12 above that. The hard film 1 in Study Example 8 is constructed by superimposing the structure of the hard film 1 in Study Example 7 onto the SiAlON layer 10. The structure of hard film 1 in study example 8 is shown below. Substrate [SiAlON / SiO2 / TiAlN 5nm]

[0056] Then, for example 8, the average transmittance in the visible range was measured. Table 5 shows the average transmittance values ​​in Example 8.

[0057] [Table 5]

[0058] Table 5 shows that, similar to studies 1-7, in the TiAlN layer 12 related to hard film 1 in study example 8, the average transmittance is higher and visibility is better as the number of Al atoms is greater than the number of Ti atoms. Furthermore, from Tables 4 and 5, it can be seen that when the SiAlON layer 10 is added to Study Example 7 to create Study Example 8, the average transmittance increases slightly when comparing the same sub-numbered examples. Furthermore, it is considered that the hard film 1 in Study Example 8 has the same surface resistivity as the hard film 1 in Study Example 7.

[0059] [Two layers: TiAlN layer 12 and SiO2 layer] Various examples were fabricated using the above-described manufacturing apparatus 101 when the hard film 1 consists of two layers: a TiAlN layer 12 on the substrate side and an SiO2 layer on the non-substrate side. Specifically, in study examples 9-1 to 9-11, a hard film 1 was formed on each substrate, with a TiAlN layer 12 having a physical thickness of 5 nm and an SiO2 layer on top of it having a physical thickness of 90 nm. The structure of hard film 1 in example 9 is shown below. Substrate [TiAlN 5nm / SiO2]

[0060] For example 9, the average values ​​of surface resistivity and transmittance in the visible range were measured. Table 6 shows the average values ​​of surface resistivity and transmittance in Example 9.

[0061] [Table 6]

[0062] Table 6 shows that, similar to Examples 1-8, in Example 9, the average transmittance and surface resistivity increase as the number of Al atoms increases relative to the number of Ti atoms. Furthermore, as can be seen from Tables 1 and 6, the surface resistivity increased in Study Example 9, in which an SiO2 layer was added on top of the 5nm thick TiAlN layer 12, compared to Study Example 1, which involved a single layer of 5nm thick TiAlN layer 12. Furthermore, Tables 1 and 6 show that, compared to Study Example 1, which involved a single layer of TiAlN 12 with a thickness of 5 nm, Study Example 9, in which an SiO2 layer was added on top of the 5 nm thick TiAlN layer 12, showed an average transmittance increase of approximately 3 to 5 points.

[0063] [Three layers: SiAlON layer 10, TiAlN layer 12, and SiO2 layer] Various examples were fabricated using the above-described manufacturing apparatus 101 for the case where the hard film 1 consists of three layers arranged in the order of SiAlON layer 10, TiAlN layer 12, and SiO2 layer from the substrate side. Specifically, in study examples 10-1 to 10-11, a hard film 1 was formed on each substrate, with a physical thickness of 3 μm for the SiAlON layer 10, a physical thickness of 5 nm for the TiAlN layer 12 above it, and a physical thickness of 90 nm for the SiO2 layer above that. The hard film 1 in Study Example 10 is constructed by superimposing the structure of the hard film 1 in Study Example 9 onto the SiAlON layer 10. The structure of hard film 1 in example 10 is shown below. Substrate [SiAlON / TiAlN 5nm / SiO2]

[0064] Then, for example 10, the average transmittance in the visible range was measured. Table 7 shows the average transmittance values ​​in Example 10.

[0065] [Table 7]

[0066] Table 7 shows that, similar to Examples 1-9, in the TiAlN layer 12 of hard film 1 in Study Example 10, the average transmittance is higher and visibility is better as the number of Al atoms is greater than the number of Ti atoms. Furthermore, from Tables 6 and 7, it can be seen that when the SiAlON layer 10 is added to Study Example 9 to create Study Example 10, the average transmittance increases even further when comparing examples with the same sub-number. Furthermore, it is considered that the hard film 1 in Study Example 10 has the same surface resistivity as the hard film 1 in Study Example 9.

[0067] [TiAlN layer 12 and 2 layers of SiN x [3 layers] The hard film 1 consists of SiN in order from the substrate side. x Layer, TiAlN layer 12 and SiN x Various examples of the case consisting of three layers were produced using the manufacturing apparatus 101 described above. SiN x The layer formation was carried out in the same manner as the formation of the SiO2 layer, except that radical nitrogen was introduced instead of radical oxygen. Then, as examples 11-1 to 11-11, SiN x The physical thickness of the layer is 5nm, the physical thickness of the TiAlN layer 12 above it is 5nm, and further on is SiN x A hard film 1 with a physical thickness of 5 nm was formed on each substrate. The structure of the hard film 1 in Study Example 11 is shown below. Substrate [SiN x / TiAlN5nm / SiN x ] Furthermore, as examples 12-1 to 12-11, SiN x The physical thickness of the layer is 5 nm, the physical thickness of the TiAlN layer 12 above it is 4 nm, and further on is SiN x A hard film 1 with a physical thickness of 5 nm was formed on each substrate. The structure of the hard film 1 in Study Example 12 is shown below. Substrate [SiN x / TiAlN4nm / SiN x ] Furthermore, as examples 13-1 to 13-11, SiN x The physical thickness of the layer is 5 nm, the physical thickness of the TiAlN layer 12 above it is 3 nm, and further on is SiN x A hard film 1 with a physical thickness of 5 nm was formed on each substrate. The structure of the hard film 1 in Study Example 13 is shown below. Substrate [SiN x / TiAlN3nm / SiN x ] In addition, as examples 14-1 to 14-11, SiN x The physical thickness of the layer is 5 nm, the physical thickness of the TiAlN layer 12 above it is 2 nm, and further on is SiN x A hard film 1 with a physical thickness of 5 nm was formed on each substrate. The structure of the hard film 1 in Study Example 14 is shown below. Substrate [SiN x / TiAlN2nm / SiN x ]

[0068] Then, for examples 11-14, the average values ​​of surface resistivity and transmittance in the visible range were measured. Table 8 shows the average values ​​of surface resistivity and transmittance for study examples 11 to 14.

[0069] [Table 8]

[0070] Table 8 shows that, similar to examples 1 to 10, in study examples 11 to 14, the average transmittance and surface resistivity increase as the number of Al atoms increases relative to the number of Ti atoms. Furthermore, from Tables 1 and 8, for Study Example 1 concerning a single-layer film of a 5nm thick TiAlN layer 12, SiN was placed above and below the 5nm thick TiAlN layer. x In example 11, where a layer was added, it can be seen that the surface resistivity decreased and the average transmittance dropped by about 3 points. Furthermore, from Table 8, the TiAlN layer 12 is SiN xIn the examples 11-14, which involve sandwiching layers, it can be seen that as the physical thickness of the TiAlN layer 12 decreases, the average transmittance increases and the surface resistivity decreases.

[0071] [SiAlON layer 10, TiAlN layer 12 and two layers of SiN x [Four layers] The hard film 1 consists of a SiAlON layer 10 and a SiN layer from the substrate side. x Layer, TiAlN layer 12 and SiN x Various examples were fabricated using the manufacturing apparatus 101 described above, for the case consisting of four layers arranged in a specific order. Specifically, in study examples 15-1 to 15-11, the physical thickness of the SiAlON layer 10 is 3 μm, and on top of it is SiN x The layer is 5nm, and the physical thickness of the TiAlN layer 12 above it is also 5nm, and on top of that is SiN x A hard film 1 with a physical thickness of 5 nm was formed on each substrate. The hard film 1 in Study Example 15 is formed by superimposing the structure of the hard film 1 in Study Example 11 onto the SiAlON layer 10. The structure of the hard film 1 in Study Example 15 is shown below. Substrate [SiAlON / SiN x / TiAlN5nm / SiN x ] Furthermore, in study examples 16-1 to 16-11, the physical thickness of the SiAlON layer 10 is 3 μm, and the SiN layer on top of it x The layer is 5nm, the physical thickness of the TiAlN layer 12 above it is 4nm, and on top of that is SiN x A hard film 1 with a physical thickness of 5 nm was formed on each substrate. The hard film 1 in Study Example 16 is formed by superimposing the structure of the hard film 1 in Study Example 12 onto the SiAlON layer 10. The structure of the hard film 1 in Study Example 16 is shown below. Substrate [SiAlON / SiN x / TiAlN4nm / SiN x ] Furthermore, in study examples 17-1 to 17-11, the physical thickness of the SiAlON layer 10 is 3 μm, and on top of it is SiN x The layer is 5nm thick, and the physical thickness of the TiAlN layer 12 above it is 3nm, and on top of that is SiN xA hard film 1 with a physical thickness of 5 nm was formed on each substrate. The hard film 1 in Study Example 17 is formed by superimposing the structure of the hard film 1 in Study Example 13 onto the SiAlON layer 10. The structure of the hard film 1 in Study Example 17 is shown below. Substrate [SiAlON / SiN x / TiAlN3nm / SiN x ] Furthermore, in study examples 18-1 to 18-11, the physical thickness of the SiAlON layer 10 is 3 μm, and on top of it is SiN x The layer is 5nm thick, and the physical thickness of the TiAlN layer 12 above it is 2nm, and on top of that is SiN x A hard film 1 with a physical thickness of 5 nm was formed on each substrate. The hard film 1 in Study Example 18 is constructed by superimposing the structure of the hard film 1 in Study Example 14 onto the SiAlON layer 10. The structure of the hard film 1 in Study Example 18 is shown below. Substrate [SiAlON / SiN x / TiAlN2nm / SiN x ]

[0072] Then, for examples 15-18, the average transmittance in the visible range was measured. Table 9 shows the average transmittance values ​​for study examples 15 to 18.

[0073] [Table 9]

[0074] Table 9 shows that, similar to examples 1-14, in the TiAlN layer 12 of hard film 1 in study examples 15-18, the average transmittance is higher and visibility is better as the number of Al atoms is greater than the number of Ti atoms. Furthermore, from Tables 8 and 9, it can be seen that when the SiAlON layer 10 is added to study examples 11-14 to create study examples 15-18, the average transmittance decreases when comparing examples with the same sub-number. Furthermore, Table 9 shows that in study examples 15-18, the average transmittance increases as the physical thickness of the TiAlN layer 12 decreases. Furthermore, it is considered that the hard film 1 in study examples 15-18 has the same surface resistivity as the hard film 1 in study examples 11-14.

[0075] [SiO2 layer, TiAlN layer 12 and 2 layers of SiN] x [Four layers] Hard film 1 consists of two SiO2 layers and SiN2 layers from the substrate side. x Layer, TiAlN layer 12 and SiN x Various examples were fabricated using the manufacturing apparatus 101 described above, specifically for the case consisting of four layers. Specifically, in study examples 19-1 to 19-11, the physical film thickness of the SiO2 layer is 90 nm, and on top of that is SiN x The physical thickness of the layer is 5nm, and the physical thickness of the TiAlN layer 12 above it is also 5nm, and on top of that is SiN x A hard film 1 with a physical thickness of 5 nm was formed on each substrate. The structure of hard film 1 in study example 19 is shown below. Substrate [SiO2 / SiN x / Ti AlN / SiN x ]

[0076] Then, for example 19, the average values ​​of surface resistivity and transmittance in the visible range were measured. Table 10 shows the average values ​​of surface resistivity and transmittance in Example 19.

[0077] [Table 10]

[0078] Table 10 shows that, similar to Examples 1-18, in Study Example 19, the average transmittance and surface resistivity increase as the number of Al atoms increases relative to the number of Ti atoms. Furthermore, from Tables 8 and 10, the 5nm thick TiAlN layer 12 is made of 5nm thick SiN x Compared to study example 11, where the material was sandwiched between layers, study example 19, in which an additional SiO2 layer was added to the substrate side, shows that the surface resistivity and transmittance remain largely unchanged.

[0079] [SiAlON layer 10, SiO2 layer, TiAlN layer 12 and two layers of SiN x [5 layers] The hard film 1 consists of a SiAlON layer 10, an SiO2 layer, and SiN from the substrate side. x Layer, TiAlN layer 12 and SiN x Various examples were fabricated using the manufacturing apparatus 101 described above, for the case consisting of five layers arranged in a specific order. Specifically, in study examples 20-1 to 20-11, the physical thickness of the SiAlON layer 10 is 3 μm, the physical thickness of the SiO2 layer above it is 90 nm, and further on top of that is SiN x The physical thickness of the layer is 5nm, and the physical thickness of the TiAlN layer 12 above it is also 5nm, and on top of that is SiN x A hard film 1 with a physical thickness of 5 nm was formed on each substrate. The hard film 1 in Study Example 20 is constructed by superimposing the structure of the hard film 1 in Study Example 19 onto the SiAlON layer 10. The structure of hard film 1 in example 20 is shown below. Substrate [SiAlON / SiO2 / SiN x / Ti AlN / SiN x ]

[0080] Then, for example 20, the average transmittance in the visible range was measured. Table 11 below shows the average transmittance values ​​for example 20.

[0081] [Table 11]

[0082] Table 11 shows that, similar to studies 1-19, in the TiAlN layer 12 of hard film 1 in study example 20, the average transmittance is higher and visibility is better as the number of Al atoms is greater than the number of Ti atoms. Furthermore, from Tables 10 and 11, it can be seen that when the SiAlON layer 10 is added to Study Example 19 to create Study Example 20, the average transmittance decreases slightly when comparing examples with the same sub-number. Furthermore, it is considered that hard film 1 in study example 20 has the same surface resistivity as hard film 1 in study example 19.

[0083] [TiAlN layer 12, 2 layers of SiN x [Four layers: a layer and an SiO2 layer] Hard film 1 is made up of SiN in order from the substrate side. x layer, TiAlN layer 12, SiN x Various examples were fabricated using the manufacturing apparatus 101 described above, for the case consisting of four layers: a layer and an SiO2 layer. In other words, as examples 21-1 to 19-11, SiN x The physical thickness of the layer is 5nm, the physical thickness of the TiAlN layer 12 above it is 5nm, and further on is SiN x A hard film 1 with a physical thickness of 5 nm in the layer and a physical thickness of 90 nm in the SiO2 layer above it was formed on each substrate. The structure of hard film 1 in study example 21 is shown below. Substrate [SiN x / Ti AlN / SiN x [SiO2]

[0084] Then, for example 21, the average values ​​of surface resistivity and transmittance in the visible range were measured. Table 12 shows the average values ​​of surface resistivity and transmittance in Example 21.

[0085] [Table 12]

[0086] Table 12 shows that, similar to Examples 1-20, in Study Example 21, the average transmittance and surface resistivity increase as the number of Al atoms increases relative to the number of Ti atoms. Furthermore, from Tables 8 and 12, the 5nm thick TiAlN layer 12 is made of 5nm thick SiN x In contrast to study example 11, where the material was sandwiched between layers, in study example 21, where an additional SiO2 layer was added to the non-substrate side, it can be seen that the surface resistivity increased slightly and the transmittance increased by about 4 points. Furthermore, Tables 10 and 12 show that, compared to Study Example 19 where the SiO2 layer was placed on the substrate side, Study Example 21, where the SiO2 layer was placed on the non-substrate side, showed a slight increase in surface resistivity and an increase of approximately 4 points in transmittance.

[0087] [SiAlON layer 10, TiAlN layer 12, 2 layers of SiN x [Five layers: a layer and an SiO2 layer] The hard film 1 consists of a SiAlON layer 10 and a SiN layer from the substrate side. x layer, TiAlN layer 12, SiN x Various examples were fabricated using the manufacturing apparatus 101 described above, for the case consisting of five layers arranged in the order of a layer and an SiO2 layer. Specifically, in study examples 22-1 to 22-11, the physical thickness of the SiAlON layer 10 is 3 μm, and on top of it is SiN x The physical thickness of the layer is 5nm, and the physical thickness of the TiAlN layer 12 above it is also 5nm, and on top of that is SiN x A hard film 1 with a physical thickness of 5 nm in the layer and a physical thickness of 90 nm in the SiO2 layer above it was formed on each substrate. The hard film 1 in Study Example 22 is constructed by superimposing the structure of the hard film 1 in Study Example 21 onto the SiAlON layer 10. The structure of hard film 1 in example 22 is shown below. Substrate [SiAlON / SiN x / Ti AlN / SiN x [SiO2]

[0088] Then, for example 22, the average transmittance in the visible range was measured. Table 13 below shows the average transmittance values ​​in Example 22.

[0089] [Table 13]

[0090] Table 13 shows that, similar to studies 1 to 21, in the TiAlN layer 12 of hard film 1 in study example 22, the average transmittance is higher and visibility is better as the number of Al atoms is greater than the number of Ti atoms. Furthermore, from Tables 12 and 13, it can be seen that when the SiAlON layer 10 is added to Study Example 21 to create Study Example 22, the average transmittance increases slightly when comparing examples with the same sub-number. Furthermore, it is considered that the hard film 1 in Study Example 22 has the same surface resistivity as the hard film 1 in Study Example 21.

[0091] [Various examinations] Furthermore, various tests were conducted using different hard films 1 as samples, primarily to investigate their durability. Here, constant temperature and humidity tests, vacuum heat resistance tests, and gamma ray irradiation tests were conducted. In the constant temperature and humidity test, the initial surface resistivity and transmittance of the sample were measured. Then, the sample was placed in a constant temperature and humidity chamber for a predetermined time, removed, and its surface resistivity, transmittance, indentation hardness (HIT), and Vickers hardness were measured after being left in a constant temperature and humidity environment. The temperature of the constant temperature and humidity chamber was 85°C. The humidity of the constant temperature and humidity chamber was 85%. The predetermined time was 72 hours. HIT and Vickers hardness were measured using the nanoindentation method with an ENT-2100 instrument manufactured by Eliolinics Co., Ltd. The unit of HIT was GPa (gigapascals). In the vacuum heat resistance test, the initial surface resistivity and transmittance of the sample were measured. Then, the sample was placed in a vacuum chamber and subjected to a heating and cooling process repeated for a predetermined number of cycles. After removal, the surface resistivity, transmittance, HIT (Heat Intensity Test), and Vickers hardness of the sample were measured after it had been subjected to thermal changes in a vacuum. The heating process involved maintaining the sample at 150°C for one hour. The cooling process involved maintaining the sample at -150°C for one hour. The vacuum heat resistance test consisted of seven cycles, with one set of heating and cooling processes representing one cycle. In the gamma-ray irradiation test, after the initial surface resistivity and transmittance of the sample were measured, the sample was irradiated with a predetermined amount of gamma-rays in a radiation irradiation facility, and the surface resistivity, transmittance, HIT, and Vickers hardness of the sample after gamma-ray irradiation were measured. The gamma-rays were derived from cobalt 60. The absorbed dose of gamma-rays was set to three types: 10 kGy (kilogray), 100 kGy, and 200 kGy.

[0092] The samples for the constant temperature and humidity test were the following Examination Examples 23 to 28 and Comparative Examples 1 and 2. Examination Example 23 was the same as Examination Examples 4 - 6 and had a hard film 1 in which the physical film thickness of the SiAlON layer 10 was 3 μm and the physical film thickness of the TiAlN layer 12 thereon was 5 nm. Examination Example 24 was the same as Examination Examples 8 - 6 and had a hard film 1 in which the physical film thickness of the SiAlON layer 10 was 3 μm, the physical film thickness of the SiO2 layer thereon was 90 nm, and the physical film thickness of the TiAlN layer 12 thereon was 5 nm. When various tests were conducted on Examination Example 9 in which only the arrangement of the SiO2 layer was different, test results similar to those of Examination Example 24 based on Examination Example 8 were considered to be obtained. Examination Example 25 was the same as Examination Examples 18 - 6. x The physical film thickness of the SiAlON layer 10 was 3 μm, the SiN layer thereon was 5 nm, the physical film thickness of the TiAlN layer 12 thereon was 2 nm, and the physical film thickness of the SiN layer thereon was 5 nm. x It had a hard film 1. Examination Example 26 was the same as Examination Examples 20 - 6 except for the physical film thickness of the TiAlN layer 12. The physical film thickness of the SiAlON layer 10 was 3 μm, the physical film thickness of the SiO2 layer thereon was 90 nm, the physical film thickness of the SiN layer thereon was 5 nm, the physical film thickness of the TiAlN layer 12 thereon was 2 nm, and the physical film thickness of the SiN layer thereon was 5 nm. x It had a hard film 1. x The physical film thickness of the SiAlON layer 10 was 3 μm, the physical film thickness of the SiO2 layer thereon was 90 nm, the physical film thickness of the SiN layer thereon was 5 nm, the physical film thickness of the TiAlN layer 12 thereon was 2 nm, and the physical film thickness of the SiN layer thereon was 5 nm. Examination Example 27 was the same as Examination Examples 22 - 6 except for the physical film thickness of the TiAlN layer 12. The physical film thickness of the SiAlON layer 10 was 3 μm, and the SiN layer thereon was 5 nm. xThe physical thickness of the layer is 5 nm, and the physical thickness of the TiAlN layer 12 above it is 2 nm, and on top of that is SiN x It had a hard film 1 with a physical thickness of 5 nm for the layer and a physical thickness of 90 nm for the SiO2 layer above it. Study Example 27 was an additional antifouling layer added as the outermost layer compared to Study Example 26. The surface resistivity and transmittance of the hard film 1 structure in Study Example 27 are considered to be the same as in Study Example 22, which corresponds to Study Example 26, because the influence of the antifouling layer on the surface resistivity and transmittance is considered to be very small. The antifouling layer was a polycondensate of a fluorine-containing organosilicon compound. The physical film thickness of the antifouling layer was 5 nm. The structure of hard film 1 in study example 27 is shown below. Substrate [SiAlON / SiN x / Ti AlN / SiN x [SiO2 / anti-fouling layer]

[0093] Comparative Example 1 was constructed by forming only a SiAlON layer 10 with a physical film thickness of 3 μm on the same substrate as in Study Examples 1 to 27. Comparative Example 2 involved forming a SiAlON layer 10 with a physical thickness of 3 μm on the same substrate as in Study Examples 1 to 27, and then forming an SiO2 layer with a physical thickness of 90 nm on top of it.

[0094] Vacuum heat resistance tests were conducted using samples from Examples 25-28 and Comparative Examples 1-2. Gamma-ray irradiation tests were conducted using samples 25-28 and comparative examples 1-2. For each type of test, new materials were prepared in accordance with Examples 25-28 and Comparative Examples 1-2. In other words, samples after a test were not used in any further tests.

[0095] Table 14 shows the transmittance before and after the constant temperature and humidity test and the vacuum heat resistance test. Table 15 also shows the transmittance before and after the gamma ray irradiation test.

[0096] [Table 14]

Table 15

[0097] According to Table 14, the transmittance after the constant temperature and humidity test was almost unchanged compared with that before the test in Study Examples 23 to 28 and Comparative Examples 1 to 2, and in some cases, it increased compared with that before the test. Also, according to Table 14, the transmittance after the vacuum heat resistance test was almost unchanged compared with that before the test in Study Examples 25 to 28 and Comparative Examples 1 to 2, and in some cases, it increased compared with that before the test. According to Table 15, the transmittance after the gamma-ray irradiation test was almost unchanged compared with that before the test in Study Examples 25 to 28 and Comparative Examples 1 to 2 regardless of the absorbed dose of gamma rays, and in some cases, it increased compared with that before the test.

[0098] The surface resistivity before and after the constant temperature and humidity test and the vacuum heat resistance test is shown in Table 16 below. Also, the surface resistivity before and after the gamma-ray irradiation test is shown in Table 17 below.

[0099]

Table 16

Table 17

[0100] According to Table 16, the surface resistivity after the constant temperature and humidity test was almost unchanged in Study Examples 25 to 28 compared with that before the test. However, the surface resistivity after the constant temperature and humidity test increased to about 10 times that before the test in Study Examples 23 to 24 and Comparative Examples 1 to 2. Therefore, when the TiAlN layer 12 is sandwiched between SiN x layers as in the hard film 1 of Study Examples 25 to 28, it was found that the durability against temperature and humidity is higher than when the TiAlN layer 12 is not sandwiched between SiN <00所求的翻译内容如下:

Table 15

[0101] Table 18 shows the HIT before and after the constant temperature and humidity test and the vacuum heat resistance test. Table 19 shows the HIT before and after the gamma ray irradiation test. Furthermore, while ITO (Indium Tin Oxide) films are known to be conductive films, the HIT of an ITO monolayer film having the same physical thickness as TiAlN layer 12 in study examples 23-28 is 9.08 GPa. Also, the HIT of a hard film with an SiO2 layer placed on top of a Si3N4 layer made of Si3N4 is 12.63 GPa.

[0102] [Table 18] [Table 19]

[0103] According to Table 18, the HIT after the constant temperature and humidity test remained almost unchanged from before the test in Examples 23-28 and Comparative Examples 1-2, and in some cases even increased compared to before the test. Furthermore, according to Table 18, the HIT after the vacuum heat resistance test remained almost unchanged from before the test in Study Examples 25-28 and Comparative Examples 1-2, and in some cases even increased compared to before the test. According to Table 19, regardless of the absorbed dose of gamma rays, the HIT after the gamma-ray irradiation test remained almost unchanged from before the test in Examples 25-28 and Comparative Examples 1-2, and in some cases even increased compared to before the test.

[0104] Table 20 shows the Vickers hardness before and after the constant temperature and humidity test and the vacuum heat resistance test. Table 21 also shows the Vickers hardness before and after the gamma ray irradiation test. Furthermore, the Vickers hardness of an ITO monolayer film having the same physical thickness as the TiAlN layer 12 in study examples 23-28 is 839.22. Also, the Vickers hardness of a hard film with an SiO2 layer placed on top of a Si3N4 layer is 1166.82.

[0105] [Table 20] [Table 21]

[0106] According to Table 20, the Vickers hardness after the constant temperature and humidity test remained almost unchanged from before the test in Examples 23-28 and Comparative Examples 1-2, and in some cases even increased compared to before the test. Furthermore, according to Table 20, the Vickers hardness after the vacuum heat resistance test remained almost unchanged from before the test in Examples 25-28 and Comparative Examples 1-2, and in some cases even increased compared to before the test. According to Table 21, regardless of the absorbed dose of gamma rays, the Vickers hardness after the gamma ray irradiation test remained almost unchanged from before the test in Examples 25-28 and Comparative Examples 1-2, and in some cases even increased compared to before the test.

[0107] [Considerations for Examples 1-28] For reference, the structures of hard film 1 for study examples 1 to 28 are reproduced in Table 22 below.

[0108] [Table 22]

[0109] Examples 4-6, 8, 10, 15-18, 20, and 22-28 include a SiAlON layer 10 made of SiAlON and a TiAlN layer 12 made of TiAlN, with the TiAlN layer 12 being positioned on the side opposite the substrate to the SiAlON layer 10. Therefore, the combination of the SiAlON layer 10 and the TiAlN layer 12 provides a hard film with sufficient hardness, light transmittance, and conductivity. In particular, for the SiAlON layer 10 which does not have sufficient conductivity to provide antistatic properties, the arrangement of the TiAlN layer 12 closer to the surface of the hard film 1 on the non-substrate side provides a hard film 1 with excellent conductivity.

[0110] Examples 11-22 and 25-28 are SiN x SiN x It has multiple layers, where x is 1 ≤ x ≤ 1.33, and SiN x The layers are located on the substrate side and the non-substrate side of the TiAlN layer 12. Therefore, a more durable hard film with sufficient hardness, light transmittance, and conductivity is provided. In particular, in study examples 15-18, 22, 25, and 27, SiN is used between the TiAlN layer 12 and the SiAlON layer 10 on the substrate side. x The interposed layer protects the TiAlN layer 12 from the influence of O atoms in the SiAlON layer 10, which is thought to contribute to improved durability. Furthermore, in study examples 19-20 and 26, the TiAlN layer 12 is interposed to the substrate side, x The arrangement of the layers protects against the influence of O atoms from the SiO2 layer on the substrate side. Furthermore, in study examples 21-22 and 27-28, the TiAlN layer 12 protects against SiN on the anti-substrate side. x The layer arrangement protects it from the influence of oxygen atoms in the SiO2 layer on the anti-substrate side.

[0111] Furthermore, examples 7-10, 19-22, 24, and 26-28 include an SiO2 layer, which is a layer made of SiO2, and the SiO2 layer is located on the anti-substrate side of the SiAlON layer 10. Therefore, a hard film 1 with sufficient hardness, light transmittance, and conductivity is provided. In particular, the placement of the SiO2 layer improves the transmittance in the visible range and enhances light transmittance.

[0112] Furthermore, in study examples 1 to 28, the atomic ratio of Ti to Al in the TiAlN layer 12, Ti:Al, ranges from 16:84 to 32.8:67.2. Therefore, a hard film 1 with sufficient hardness, light transmittance, and conductivity is provided.

[0113] Furthermore, in examples 1 to 28, the surface resistivity was 1.0 × 10⁻⁶. 11 It is less than or equal to Ω / □. Therefore, compared to comparative examples 1 to 2, which lack the TiAlN layer 12, such as a single-layer film of SiAlON layer 10 or a two-layer film of SiAlON layer 10 and SiO2 layer, the examples 1 to 28 exhibit superior conductivity and sufficient antistatic properties.

[0114] Furthermore, in examples 1-28, the indentation hardness was 15.9 GPa or higher. Therefore, a hard film 1 is provided that is harder than an ITO film (9.08 GPa) and a hard film (12.63 GPa) in which an SiO2 layer is placed on top of a Si3N4 layer, and has excellent conductivity and light transmittance.

[0115] Furthermore, in examples 1-28, the Vickers hardness is 1500 or higher. Therefore, a hard film 1 is provided that is harder than an ITO film (839.22) and a hard film (1166.82) having an SiO2 layer placed on top of a Si3N4 layer, and has excellent conductivity and light transmittance.

[0116] Furthermore, in examples 1-28, the average transmittance in the visible range is 76% or higher. Therefore, a hard film 1 with excellent hardness, conductivity, and light transmittance is provided. [Explanation of Symbols]

[0117] 1. Hard membrane 2. Substrate 10··SiAlON layer 12··TiAlN layers M·· Film-forming surface

Claims

1. A SiAlON layer, which is a layer made of SiAlON, A TiAlN layer, which is a layer made of TiAlN, It is equipped with, The TiAlN layer is positioned on the side opposite the substrate of the SiAlON layer. A hard membrane characterized by the following features.

2. Furthermore, SiN ｘ SiN is a layer made of SiN ｘ It has multiple layers, where x is 1 ≤ x ≤ 1.

33. The SiN ｘ The layers are arranged on the substrate side and the anti-substrate side of the TiAlN layer. The hard film according to feature 1.

3. Furthermore, SiO ２ The SiO layer is made of ２ It has layers, The SiO ２ The layer is positioned on the side opposite the substrate from the SiAlON layer. The hard film according to feature 1.

4. The atomic ratio of Ti to Al in the TiAlN layer, Ti:Al, is between 16:84 and 32.8:67.

2. The hard film according to feature 1.

5. Surface resistivity is 1.0 × 10 １１ It is less than or equal to Ω / □ The hard film according to feature 1.

6. The indentation hardness is 15.9 GPa or higher. The hard film according to feature 1.

7. The Vickers hardness is 1500 or higher. The hard film according to feature 1.

8. The average transmittance in the visible range is 76% or higher. The hard film according to feature 1.

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