Rutile titanium oxide film forming method and film forming apparatus

Abstract

To provide a technique for forming a film of rutile-type titanium oxide on the surface of a synthetic resin material without deforming or dissolving the synthetic resin material. The method for forming a rutile titanium oxide film is a method for forming a thin film of rutile titanium oxide on a target surface of an object, and includes a power supply step of supplying power at a predetermined frequency N to a target T containing Ti, wherein the instantaneous power density of the power in the power supply step is 1.1 kW / cm. 2 The average power density is 5.8 W / cm 2 The following is the result.

Description

[Technical Field]

[0001] The present invention relates to a method and apparatus for forming a rutile-type titanium oxide film. [Background technology]

[0002] Optical devices such as cameras and liquid crystal projectors use coatings made of laminated materials with different refractive indices to control the reflection and transmission of light. Materials with higher refractive indices are required for these coatings. Rutile titanium dioxide is a transparent material known to have the highest refractive index among transparent materials. For example, Patent Document 1 discloses a technique in which a precursor film is formed on the surface of a transparent substrate, a glass plate, by sputtering, and then heat-treated at temperatures between 550°C and 750°C to convert the precursor into rutile titanium dioxide. [Prior art documents] [Patent documents]

[0003] [Patent Document 1] Japanese Patent Application Laid-Open No. 2015-166287 Summary of the Invention [Problem to be solved by the invention]

[0004] When a synthetic resin material is used for the transparent substrate, there is a concern that the transparent substrate may be deformed or dissolved if the transparent substrate is subjected to heat treatment at the temperatures disclosed in Patent Document 1 in order to form a film of rutile titanium oxide on the surface of the transparent substrate. For this reason, there has been a demand for a technology that can form a film of rutile titanium oxide on the surface of a synthetic resin material without deforming or dissolving the synthetic resin material.

[0005] The present invention has been made in view of the above-mentioned conventional circumstances, and an object of the present invention is to provide a technology for forming a film of rutile-type titanium oxide on the surface of a synthetic resin material without deforming or dissolving the synthetic resin material. [Means for solving the problem]

[0006] The method for forming a rutile-type titanium oxide film of the first invention comprises the steps of: A method for forming a thin film of rutile titanium oxide on a target surface of an object, comprising: a power supply step of supplying power at a predetermined frequency to a target containing Ti, In the power supplying step, The instantaneous power density of the power is 1.1 kW / cm 2 That's all, The average power density of the power is 5.8 W / cm 2 The following is the result.

[0007] The film forming apparatus of the second invention comprises: A film-forming apparatus for carrying out the rutile titanium oxide film-forming method of the first invention, a power supply that supplies the power to the target disposed within the chamber; a temperature detection unit that detects the temperature of the object placed in the chamber; a control unit that controls the power supply unit; Equipped with The control unit controls the average power density based on the temperature of the object detected by the temperature detection unit.

[0008] According to this configuration, it is possible to form a film of rutile-type titanium oxide on the surface of the synthetic resin material without deforming or dissolving the synthetic resin material. [Brief explanation of the drawings]

[0009] [Figure 1] 1 is a schematic diagram showing the configuration of a film forming apparatus according to a first embodiment. [Figure 2] 10 is a graph showing an example of a waveform of power density in a power supply unit. [Figure 3] This is a schematic diagram showing the behavior of each atom and electron in a chamber where HiPIMS is performed. [Figure 4]10 is a graph showing an example of a pulsed power waveform supplied from a power supply unit to a target. [Figure 5] 10 is a graph showing the relationship between the potential difference and the instantaneous power density, and the relationship between the potential difference and the proportion of Ti + ions and Ar + ions, in Samples 1 to 5. [Figure 6] 1A shows the results of XRD measurements for Samples 1 to 5, and FIG. 1B is a graph showing the relationship between the substrate temperature and the average power density and the potential difference for Samples 1 to 5. [Figure 7] Graph (A) shows the relationship between the average power density and the substrate temperature and the frequency of the power supply unit for samples 6 to 9, and graph (B) shows the relationship between the frequency of the power supply unit and the instantaneous power density for samples 6 to 9. [Figure 8] 1 is a graph showing the XRD measurement results for Samples 6 to 9. [Figure 9] 10 is a graph showing the relationship between average power density and substrate temperature in Samples 10 to 18. [Figure 10] 1A is a graph showing the waveform of power density in Sample 18, and FIG. 1B is a graph showing the results of XRD measurement in Sample 18. DETAILED DESCRIPTION OF THE INVENTION

[0010] A preferred embodiment of the present invention will now be described.

[0011] In the power supply step of the method for forming a rutile titanium oxide film of the present invention, the average power density can be controlled based on the temperature of the target object, making it possible to form a rutile titanium oxide film while stably maintaining the substrate temperature at a target temperature.

[0012] Next, a first embodiment of the rutile titanium oxide film forming method and film forming apparatus of the present invention will be described with reference to the drawings.

[0013] Example 1 [Configuration of film deposition equipment] 1 is capable of performing so-called HiPIMS (High Power Impulse Magnetron Sputtering) and includes a chamber 10A, a power supply unit 10B, a temperature detection unit 10C, and a control unit 10D.

[0014] The chamber 10A is box-shaped with a storage space R formed therein. The chamber 10A is formed with an inlet 10E and an outlet 10F. Ar gas and O2 gas flow into the chamber 10A through the inlet 10E. The Ar gas and O2 gas that flow into the chamber 10A flow out through the outlet 10F. An exhaust pump (not shown) is provided at the outlet 10F. The exhaust pump evacuates the chamber 10A when in operation, thereby reducing the air pressure inside the chamber 10A to a desired low pressure. For example, a turbomolecular pump is used as the exhaust pump.

[0015] A target stage 10G and an object stage 10H are provided in the chamber 10A. The target stage 10G and the object stage 10H are arranged such that their respective mounting surfaces 10J and 10K face each other.

[0016] A disk-shaped target T made of Ti is attached to a mounting surface 10J of the target mounting table 10G. A substrate S, which is an object, is mounted on a mounting surface 10K of the object mounting table 10H. The substrate S may be made of, for example, a synthetic resin material, glass, or Si. The surface of the substrate S facing the target mounting table 10G is the object surface Ss.

[0017] A magnet (not shown) is disposed within the target mounting table 10G. This magnet has the function of confining electrons generated during HiPIMS in the vicinity of the target T. This allows the magnet to increase the plasma density in the vicinity of the target T, thereby promoting the release of titanium atoms from the target T to improve the film formation rate, and promoting the ionization of the titanium atoms released from the target T (to produce titanium ions).

[0018] The power supply unit 10B can supply concentrated power for a predetermined short period (approximately several μs to several tens of μs) to the target T placed on the target mounting table 10G in the chamber 10A. Specifically, as shown in FIG. 2, the power supply unit 10B supplies pulsed power to the target T at a predetermined cycle Pe (seconds). This allows the power supply unit 10B to increase the electron density in the plasma generated in the chamber 10A compared to conventional DCMS (direct current magnetron sputtering) and RFMS (RF magnetron sputtering). The value obtained by dividing one second by the predetermined cycle Pe is the frequency N (Hz), which indicates the number of times pulsed power is supplied to the target T per second.

[0019] 1, the temperature detection unit 10C is attached near the substrate S placed on the object placement table 10H, and has a function of detecting the temperature of the substrate S placed in the chamber 10A. For example, a known thermocouple is used as the temperature detection unit 10C. The temperature detection unit 10C outputs a temperature signal Ts indicating the temperature of the substrate S.

[0020] The control unit 10D is configured, for example, by mounting a CPU, memory, etc. on a circuit board. A temperature signal Ts is input to the control unit 10D from the temperature detection unit 10C. Based on the input temperature signal Ts, the control unit 10D outputs a control signal Sc to the power supply unit 10B, and is configured to perform feedback control of the operation of the power supply unit 10B so that the temperature of the substrate S approaches a target temperature. Examples of feedback control include PI control and PID control.

[0021] For example, when the temperature signal Ts indicates that the temperature of the substrate S is higher than the target temperature during the power supply process described below, the control unit 10D outputs a control signal Sc to the power supply unit 10B to decrease the average power density of the power supplied to the target T. Also, when the temperature signal Ts indicates that the temperature of the substrate S is lower than the target temperature during the power supply process, the control unit 10D outputs a control signal Sc to the power supply unit 10B to increase the average power density of the power supplied to the target T. That is, the control unit 10D controls the operation of the power supply unit 10B based on the temperature of the substrate S during the power supply process. The average power density will be described later. The film forming apparatus 100 is configured in this manner.

[0022] [About HiPIMS] When the electron density in the plasma P increases, the chances of electrons colliding with Ar atoms in the plasma P (see FIG. 3(A)) increase, resulting in the generation of Ar atoms in the plasma P. + The number of ions increases. + Ions collide with target T, knocking out Ti atoms from target T. Therefore, as the electron density in plasma P increases, the number of Ti atoms knocked out into plasma P also increases. The knocked-out Ti atoms behave in plasma P as shown in Figures 3(B) to (D).

[0023] Specifically, as shown in FIG. 3(B), the Ti atoms knocked out from the target T collide with the electrons in the plasma P, and the electrons in the plasma P knock out the Ti atoms, resulting in the Ti atoms being ejected. + As shown in Figure 3(C), the Ti atoms ejected from the target T collide with Ar atoms in the plasma P, and the Ar atoms eject their own electrons, turning them into Ti ions. + As shown in Figure 3(D), the Ti atoms ejected from the target T are converted into Ar ions in the plasma P. + When colliding with ions, the electrons it has are transferred to Ar + Ti is taken by ions +Among these, Ti atoms are converted into Ti ions, as shown in Figure 3(B). + The frequency of the change into ions increases as the electron density in the plasma P increases.

[0024] As shown in Figure 3(D), + The behavior of the change to ions is + It depends on the number of ions. + The number of ions depends on the frequency of collisions between Ar atoms and electrons in the plasma P (see FIG. 3(A)), and therefore increases as the electron density in the plasma P increases. + As in FIG. 3(B), the frequency of the change into ions increases as the electron density in the plasma P increases.

[0025] In this way, HiPIMS increases the electron density in the plasma P, thereby + It is known that HiPIMS ionizes Ti atoms about five times more than conventional DCMS or RFMS. + As the ions increase, the number of Ti atoms that reach the target surface Ss of the substrate S increases. + The amount of ions also increases. Then, the titanium oxide film formed on the surface of the substrate S is filled with Ti. + Ions collide with Ti + The kinetic energy imparted to the titanium oxide film by the ions also increases. As a result, the titanium oxide film formed on the substrate S + By increasing the kinetic energy imparted by the ions, the substrate S can be transformed from anatase to rutile without heat treatment using a heater or the like.

[0026] [Instantaneous power density and average power density] The power density (kW / cm) of the power supplied from the power supply unit 10B to the target T 2 ) is the current density (A / cm ) flowing between the target T and the substrate S.2 The Ti in the plasma P that reaches the target surface Ss of the substrate S can be calculated by multiplying the potential difference (V) between the target T and the substrate S by the potential difference (V) (hereinafter simply referred to as the potential difference). + The ions correspond to a current flowing between the target T and the substrate S.

[0027] As shown in FIG. 4, the maximum value Max of the pulsed power density waveform supplied from the power supply unit 10B to the target T is defined as the instantaneous power density (kW / cm 2 The larger the instantaneous power density, the greater the Ti that reaches the substrate S from the target T. + This indicates an increase in the amount of ions, and the smaller the value, the more Ti reaches the substrate S from the target T. + This indicates a decrease in the amount of ions.

[0028] For example, the power supply unit 10B supplies power with a pulsed waveform as shown in FIG. 4 to the target T at a predetermined frequency N (Hz). For example, when the frequency N is 500 Hz, the power supply unit 10B supplies power with a pulsed waveform to the target T 500 times per second. The total amount of power density supplied to the target T by the power supply unit 10B per unit time (1 second) corresponds to the value obtained by multiplying the area A of the pulsed waveform (see FIG. 4) by N, and this value divided by the unit time (1 second) is the average power density (W / cm 2 ) Specifically, as shown in Figure 2, the maximum value Max is the instantaneous power density of the pulsed power, dotted line D is the waveform obtained by multiplying the area of ​​the pulsed waveform by N and dividing it by unit time (1 second), and the magnitude Ave of dotted line D is the average power density.

[0029] To increase the average power density, it is possible to increase the frequency N without changing the area A, or to increase the area A by widening the width Pw of the power waveform without changing the frequency N and the instantaneous power density (maximum value Max).To decrease the average power density, it is possible to decrease the frequency N without changing the area A, or to decrease the area A by narrowing the width Pw of the power waveform without changing the frequency N and the instantaneous power density (maximum value Max).

[0030] The larger the average power density, the greater the temperature rise in the substrate S, and the smaller the value, the smaller the temperature rise in the substrate S. In other words, the larger the instantaneous power density and average power density, the easier it is to change the titanium oxide film formed on the substrate S from anatase to rutile, and the smaller the value, the more difficult it is to change the titanium oxide film formed on the substrate S from anatase to rutile.

[0031] [An example of a method for forming a film of rutile-type titanium oxide] Next, an example of a method for forming a rutile-type titanium oxide film on the target surface Ss of the substrate S using the film forming apparatus 100 will be described. First, a preparation step is performed. Specifically, the substrate S is immersed in acetone and ultrasonically cleaned for 10 minutes. The dried substrate S is then placed on the mounting surface 10K of the target mounting table 10H. A target T made of Ti and having a diameter of 2 inches is attached to the mounting surface 10J of the target mounting table 10G. The distance between the target T and the substrate S is 30 mm. An exhaust pump (not shown) is then operated to reduce the air pressure in the chamber 10A to 3×10 -3 Pa. Then, Ar gas and O2 gas begin to flow into chamber 10A via inlet 10E. The total inflow rate of Ar gas and O2 gas is set to 10 sccm, and the pressure inside chamber 10A is set to 3 Pa. The oxygen gas inflow ratio (O2 / O2+Ar) is set to 30%.

[0032] Then, the power supply unit 10B is started to operate, and pre-sputtering is performed. Pre-sputtering is a process for removing foreign matter and oxides adhering to the surface of the target T. In pre-sputtering, the potential difference between the target T and the substrate S is set to 600 V, and pulsed power is supplied to the target T at a frequency of 500 Hz. The width Pw of the pulsed power waveform is set to 28 μs (see FIG. 4). This completes the preparation process.

[0033] After the preparation step (pre-sputtering) is performed, a power supply step is performed in which power is supplied at a predetermined frequency N to a target T placed in a chamber 10A of the film formation apparatus 100. The control unit 10D controls the operation of the power supply unit 10B based on the temperature of the substrate S detected by the temperature detection unit 10C during the power supply step, thereby controlling the average power density. Specifically, the control unit 10D outputs a control signal Sc to the power supply unit 10B during the power supply step to adjust the frequency N and the width Pw of the power waveform in the power supply unit 10B, thereby feedback-controlling the operation of the power supply unit 10B so that the temperature of the substrate S approaches the target temperature, thereby controlling the average power density. The preparation step was performed in common in the fabrication of Samples 1 to 15 described below.

[0034] [Verification of titanium oxide thin films when the potential difference is changed] Next, using the film formation apparatus 100, the potential difference between the target T and the substrate S was varied between five levels: 550V, 570V, 640V, 650V, and 670V. The power application process was performed for approximately 180 minutes to form a titanium oxide thin film on the substrate S, producing Samples 1, 2, 3, 4, and 5. The duration of the voltage application process was fine-tuned by adjusting the potential difference between the target T and the substrate S to achieve a uniform thin film thickness. The frequency N used to prepare each sample was 500Hz, and the width Pw of the power waveform was 28μs. The substrate S was either an alkali-free glass substrate or a Si substrate.

[0035] As shown in Figure 5, the instantaneous power density of Sample 1 (potential difference 550 V) is approximately 0.55 kW / cm 2 The instantaneous power density of sample 2 (potential difference 570 V) is approximately 0.65 kW / cm 2 The instantaneous power density of sample 3 (potential difference 640 V) is approximately 0.9 kW / cm 2 The instantaneous power density of sample 4 (potential difference 650 V) is approximately 1 kW / cm 2 The instantaneous power density of sample 5 (potential difference 670 V) was approximately 1.1 kW / cm 2 Also, Ar +The ratio of ions to Ar (Ar + / Ar), and Ti + The ratio of ions to Ti (Ti + / Ti), it was found that samples 3, 4, and 5 were larger than samples 1 and 2. In Fig. 5, the instantaneous power density is shown on the vertical axis at the right end, and Ar + The ratio of ions to Ar (Ar + / Ar), and Ti + The ratio of ions to Ti (Ti + / Ti) refers to the leftmost vertical axis.

[0036] As shown in Figure 6(A), the XRD measurement results for Samples 1, 2, and 3 showed peaks indicating anatase-type titanium oxide. In contrast, the XRD measurement results for Samples 4 and 5 showed clear peaks indicating rutile-type titanium oxide.

[0037] As shown in FIG. 6(B), the temperature of the substrate S in Sample 1 was approximately 315°C, the temperature of the substrate S in Sample 2 was approximately 348°C, the temperature of the substrate S in Sample 3 was approximately 422°C, the temperature of the substrate S in Sample 4 was approximately 445°C, and the temperature of the substrate S in Sample 5 was approximately 470°C. That is, Samples 4 and 5, which clearly showed peaks indicative of rutile-type titanium oxide, indicate that a rutile-type titanium oxide film was formed at a temperature approximately 100°C lower than the temperatures (550°C to 750°C) disclosed in Patent Document 1. In FIG. 6(B), the average power density is indicated by the vertical axis on the far right, and the temperature of the substrate S is indicated by the vertical axis on the far left.

[0038] 5 and 6, when the power supply process is started by the film forming apparatus 100, a titanium oxide film is formed on the target surface Ss of the substrate S. Then, the titanium oxide film formed on the target surface Ss is replaced by the titanium oxide film formed on the target surface Ss. + The ions collide with the titanium oxide film that was previously formed, and Ti +It is believed that the kinetic energy imparted by the ions caused the titanium oxide film formed earlier to change from anatase to rutile. Here, the results shown in Figures 5 and 6 indicate that as the potential difference increases, both the instantaneous power density and the temperature of the substrate S also increase. In other words, the results of Figures 5 and 6 indicate that the factor that causes the titanium oxide film formed on the substrate S to change from anatase to rutile is Ti + It is not possible to determine whether this is due to the kinetic energy of the ions or the temperature of the substrate S. For this reason, the following experiment was conducted to explore the cause of the change in the titanium oxide film formed on the substrate S from anatase to rutile.

[0039] [Verification of titanium oxide thin films when frequency and potential difference are changed to maintain a constant average power density] Specifically, the film forming apparatus 100 was used, and the average power density was 11 W / cm 2 The power supply process was carried out for approximately 180 minutes while changing the frequency N of the power supply unit 10B that supplies pulsed power to the target T and the potential difference between the target T and the substrate S so that four types of samples 6, 7, 8, and 9 were produced. The width Pw of the power waveform when producing each sample was set to 28 μs. The substrate S was a non-alkali glass substrate or a Si substrate made of the same material as samples 1 to 5.

[0040] In sample 6, the frequency N was 500 Hz and the potential difference was 680 (V), in sample 7, the frequency N was 550 Hz and the potential difference was 660 (V), in sample 8, the frequency N was 600 Hz and the potential difference was 630 (V), and in sample 9, the frequency N was 1000 Hz and the potential difference was 580 (V).

[0041] As shown in FIG. 7(A), the temperatures of the substrate S of Samples 6, 8, and 9 all showed values ​​around 470°C, with no significant difference observed. The temperature of the substrate S of Sample 7 was not measured, but is thought to have been approximately 470°C. In FIG. 7(A), the average power density is shown on the left vertical axis, and the temperature of the substrate S is shown on the right vertical axis. Furthermore, as shown in FIG. 7(B), the instantaneous power density of Sample 6 was approximately 1.1 kW / cm. 2 The instantaneous power density in sample 7 is approximately 1 kW / cm 2 The instantaneous power density in sample 8 was approximately 0.8 kW / cm 2 The instantaneous power density in Sample 9 was approximately 0.6 kW / cm 2 It was.

[0042] As shown in Figure 8, the XRD measurement results for Sample 6 clearly showed peaks indicating rutile-type titanium oxide. In contrast, the XRD measurement results for Samples 7, 8, and 9 showed peaks indicating anatase-type titanium oxide. Note that when the frequency N was reduced to less than 500 Hz and the potential difference was increased to more than 670 V while maintaining the average power density, the instantaneous power density increased to 1.1 kW / cm. 2 It is believed that the XRD measurement results of a sample prepared under these conditions will also clearly show a peak indicating rutile-type titanium oxide.

[0043] Furthermore, the temperature of the substrate S of Samples 6, 8, and 9 was approximately 470°C (see FIG. 7(A)), and the temperature of Sample 7 was also thought to be approximately 470°C. Therefore, if the frequency N is reduced while keeping the average power density unchanged (keeping the temperature of the substrate S unchanged) and the potential difference between the target T and the substrate S is adjusted, it is possible to increase the instantaneous power density while suppressing the change in the temperature of the substrate S (i.e., the Ti in the plasma P). +It was found that the concentration of ions can be increased. It was also found that a rutile titanium oxide film can be successfully formed by increasing the instantaneous power density. Thus, the factor that causes the titanium oxide film formed on the substrate S to change from anatase to rutile is the magnitude of the instantaneous power density, and this magnitude is 1.1 W / cm 2 The above was found to be preferable.

[0044] [Verification of the case where the substrate temperature is reduced while maintaining a constant instantaneous power density] Next, the instantaneous power density is set to 1.1 kW / cm 2 Specifically, the film forming apparatus 100 was used, and the instantaneous power density was set to 1.1 kW / cm. 2 While maintaining the temperature constant, the power supply process was performed while changing the average power density to produce eight types of samples 10, 11, 12, 13, 14, 15, 16, and 17. The potential difference when producing each sample was 670 V. The substrate S was an alkali-free glass substrate or a Si substrate made of the same material as samples 1 to 9. The power supply process was performed for samples 10, 11, 12, 13, 14, 15, 16, and 17 for several tens of minutes until the temperature of the substrate S stabilized. In other words, almost no titanium oxide film was formed on the substrate S of samples 10, 11, 12, 13, 14, 15, 16, and 17.

[0045] The average power density for sample 10 was 11 W / cm 2 The average power density in sample 11 was 10.5 W / cm 2 The average power density in sample 12 is 9 W / cm 2 The average power density in sample 13 was 7 W / cm 2 The average power density in sample 14 was 5 W / cm 2 The width Pw of the power waveform when producing Samples 10, 11, 12, 13, and 14 was 28 μs, and the potential difference was 670 V. The average power density in Sample 15 was 11.6 W / cm 2, the width of the power waveform Pw was set to 28 μs, and the average power density in sample 16 was 6.0 W / cm 2 , the width of the power waveform Pw was 18 μs, and the average power density in sample 17 was 2.1 W / cm 2 The width Pw of the power waveform was set to 8 μs.

[0046] 9, the temperature of the substrate S of Sample 10 was 470°C, the temperature of the substrate S of Sample 11 was 445°C, the temperature of the substrate S of Sample 12 was 420°C, the temperature of the substrate S of Sample 13 was 345°C, the temperature of the substrate S of Sample 14 was 315°C, the temperature of the substrate S of Sample 15 was 445°C, the temperature of the substrate S of Sample 16 was 268°C, and the temperature of the substrate S of Sample 17 was 116°C. In other words, it was found that when the average power density was reduced while maintaining the magnitude of the instantaneous power density constant, the temperature of the substrate S decreased as the average power density decreased.

[0047] It was also found that the average power density and the temperature of the substrate S at this time were roughly directly proportional. In Fig. 9, the approximate line As plotted based on the results of the temperature of the substrate S versus the average power density shows that the average power density at which the temperature of the substrate S reaches 300°C is approximately 5.8 W / cm 2 It was found that...

[0048] Next, using the film forming apparatus 100, the instantaneous power density was set to 1.1 kW / cm 2 , with an average power density of 3.8 W / cm 2 Sample 18 was produced by carrying out the power supply process for approximately 11 hours under the conditions of (corresponding to a temperature of substrate S of 280°C), frequency N of 250 Hz, width of power waveform Pw of 18 μs (see FIG. 10(A)), and potential difference of 670 V. The same type of alkali-free glass substrate or Si substrate as used for Samples 1 to 17 was used for substrate S. As shown in FIG. 10(B), the XRD measurement result of Sample 18 clearly showed a peak indicating rutile-type titanium oxide. That is, the average power density was 5.8 W / cm. 2It was found that by setting the width Pw of the power waveform so that it was possible to deposit a rutile-type titanium oxide film while keeping the temperature of the substrate S at 300°C or less. The instantaneous power density of the power during the power supply process when sample 18 was produced was 1.1 kW / cm 2 and the average power density is 3.8 W / cm 2 (i.e., average power density is 5.8W / cm 2 (See below).

[0049] The instantaneous power density is 1.1kW / cm 2 and an average power density of 5.8W / cm 2 It is believed that if a sample is produced by carrying out the power supply step under the following settings, an XRD measurement result will be obtained in which a peak indicating rutile titanium oxide appears. For example, it is believed that it is possible to form a film of rutile titanium oxide by carrying out the power supply step for several hours under the conditions of the temperature and average power density of the substrate S in sample 17. Specifically, it is believed that it is possible to form a film of rutile titanium oxide by carrying out the power supply step for several hours under the conditions of the temperature and average power density of the substrate S in sample 17. 2 After fixing the frequency N, the width Pw of the power waveform is reduced, and the instantaneous power density is set to 1.1 kW / cm. 2 After fixing the above, the frequency N can be reduced while fixing the width Pw of the power waveform, or the instantaneous power density can be set to 1.1 kW / cm 2 It is believed that a rutile-type titanium oxide film can be formed by fixing the above, and then reducing both the width Pw of the power waveform and the frequency N, and running the power supply process for several hours. It is also believed that, even when the width Pw of the power waveform is fixed and the frequency N in the power supply unit 10B is changed, the average power density and the temperature of the substrate S will be roughly directly proportional to each other.

[0050] Next, the effects of the above embodiment will be described.

[0051] The method for forming a rutile-type titanium oxide film includes forming a thin film of rutile-type titanium oxide on a target surface Ss of a substrate S. The method for forming a rutile-type titanium oxide film includes a power supply step of supplying power at a predetermined frequency N to a target T placed in a chamber 10A of a film forming apparatus 100. In the power supply step, the instantaneous power density of the power is 1.1 kW / cm. 2 The average power density is 5.8 W / cm 2 According to this configuration, it is possible to form a film of rutile-type titanium oxide on the surface of a synthetic resin material without deforming or dissolving the synthetic resin material.

[0052] In the method for forming a rutile titanium oxide film, during the power supply step, the control unit 10D controls the power supply unit 10B based on a temperature signal Ts indicating the temperature of the substrate S input from the temperature detection unit 10C, thereby controlling the average power density of the power supplied to the target T. With this configuration, it is possible to form a rutile titanium oxide film while stably maintaining the temperature of the substrate S at the target temperature.

[0053] The film formation apparatus 100 performs a method for forming a rutile titanium oxide film. The film formation apparatus 100 includes a power supply unit 10B that supplies power to a target T placed in a chamber 10A, a temperature detection unit 10C that detects the temperature of a substrate S placed in the chamber 10A, and a control unit 10D that controls the power supply unit 10B. The control unit 10D controls the average power density based on the temperature of the substrate S detected by the temperature detection unit 10C. This configuration enables operation such that a film of rutile titanium oxide is formed on the surface of a synthetic resin material while maintaining the temperature of the substrate S at a target temperature and suppressing deformation or dissolution of the synthetic resin material.

[0054] The present invention is not limited to the first embodiment described above with reference to the drawings, and the following embodiments are also included within the technical scope of the present invention. (1) Unlike the above-described embodiment, the target may contain Ti. Specifically, the target may be a Ti alloy containing materials other than Ti. (2) Any film deposition apparatus capable of carrying out HIPIMS is usable, and is not limited to the film deposition apparatus used in the above embodiment. [Explanation of symbols]

[0055] 10A: Chamber 10B: Power supply section 10C: Temperature detection unit 10D: Control section 100: Film deposition equipment N: Frequency (predetermined frequency) S: Substrate (object) Ss: Target surface T: Target V: Potential difference

Claims

1. A method for forming a thin film of rutile titanium oxide on a target surface of an object, comprising: a power supplying step of supplying power at a predetermined frequency to a target containing Ti, In the power supplying step, The instantaneous power density of the power is 1.1 kW / cm 2 That's all, The average power density of the power is 5.8 W / cm 2 The following is a method for forming a film of rutile-type titanium oxide.

2. The method for forming a rutile titanium oxide film according to claim 1 , wherein the average power density is controlled based on the temperature of the object in the power supply step.

3. A film-forming apparatus for carrying out the method for forming a rutile-type titanium oxide film according to claim 1 or 2, comprising: a power supply that supplies the power to the target disposed in the chamber; a temperature detection unit that detects the temperature of the object placed in the chamber; a control unit that controls the power supply unit; Equipped with The control unit controls the average power density based on the temperature of the object detected by the temperature detection unit.

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