JP2014034699A - Film manufacturing method - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a film manufacturing method that enables reducing a temperature for deposition to 100°C or less and gives an indium oxide film having low resistance.SOLUTION: The film manufacturing method of the present invention comprises: a film deposition step of forming an indium oxide film M1 on a substrate 101 by an ion plating process; and an anneal step of annealing the indium oxide film M1 after the film deposition step. In the film deposition step, the pressure in a film deposition chamber 123 is set to 0.3 Pa or less and the temperature of the substrate 101 in the film deposition chamber 123 is set to 100°C or less and in the anneal step, the annealing is carried out at the temperature of the indium oxide film of 100°C or less.

Description

  The present invention relates to a film manufacturing method for forming an indium oxide film on a film formation target.

  2. Description of the Related Art Conventionally, a technique for forming a low-resistance indium oxide film on a substrate by an ion plating method for application to a touch panel or the like is known. For example, according to the film manufacturing apparatus shown in Patent Document 1, an indium oxide film is formed on a substrate by ionizing and diffusing a film forming material at a temperature higher than 100 ° C. in the chamber.

JP-A-2005-050730

  Here, there is an increasing demand for forming a low-resistance indium oxide film on a resin substrate having low heat resistance. When forming an indium oxide film on a resin substrate or the like, it is required to form the film at a low temperature of 100 ° C. or lower. However, the conventional ion plating method has a problem that it is difficult to obtain a low-resistance indium oxide film when film formation is performed at a chamber temperature of 100 ° C. or lower.

  Accordingly, an object of the present invention is to provide a film manufacturing method for manufacturing a low-resistance indium oxide film while setting the temperature during film formation to 100 ° C. or lower.

  A film manufacturing method according to the present invention includes a film forming process for forming an indium oxide film on a film formation target by an ion plating method, and an annealing process for annealing the indium oxide film after the film forming process. In the film formation process, the pressure in the chamber is set to 0.3 Pa or less, the temperature of the film formation target is set to 100 ° C. or less, and in the annealing process, the indium oxide film is annealed at 100 ° C. or less. .

  According to the film manufacturing method of the present invention, the temperature in the film forming step is set to 100 ° C. or lower, and the annealing temperature in the annealing step is set to 100 ° C. or lower (for example, at a low temperature such as a resin substrate). An indium oxide film can be produced regardless of the heat resistance of the film-forming object (even when using a film-forming object related to the material for which the film is required). In addition, the pressure in the film formation process is set to 0.3 Pa or less, and an annealing process is performed after the film formation process, so that even if the temperature in the film formation process is 100 ° C. or less, low resistance oxidation An indium film can be produced. As described above, the temperature during film formation can be set to 100 ° C. or lower, and a low-resistance indium oxide film can be manufactured.

Moreover, in the film manufacturing method according to the present invention, the moisture partial pressure in the chamber is preferably 5.8 × 10 ⁻⁴ Pa or less. Also, the moisture partial pressure in the chamber may be 3.9 × 10 ⁻⁴ Pa or less. Thereby, a low resistance indium oxide film can be manufactured more reliably.

  According to the present invention, the temperature during film formation can be set to 100 ° C. or lower, and a low-resistance indium oxide film can be manufactured.

It is a schematic block diagram which shows the film | membrane manufacturing apparatus used for the manufacturing method of the film | membrane which concerns on embodiment of this invention. It is sectional drawing along the II-II line of FIG. 6 is a graph showing the results of Experimental Example 1. 10 is a table showing the results of Experimental Example 2.

  Hereinafter, embodiments of the present invention will be described with reference to the drawings. In the description of the drawings, the same elements are denoted by the same reference numerals, and redundant descriptions are omitted. Further, terms indicating directions such as “up” and “down” are based on the state shown in the drawings and are for convenience. 1 and 2 also show an XYZ rectangular coordinate system for ease of explanation.

  FIG. 1 is a schematic configuration diagram showing a film manufacturing apparatus 1 used in a film manufacturing method according to an embodiment of the present invention. The film manufacturing apparatus 1 is an apparatus for manufacturing an indium oxide film M1 formed on a substrate (film formation target) 101. As shown in FIG. 1, a film forming apparatus 100, an annealing apparatus 200, and the like. It is equipped with.

  In the present embodiment, a material having low heat resistance can be applied as the material of the substrate 101, and a glass substrate coated with a resin material or resin can be applied. As the resin material, for example, PET, acrylic, polycarbonate and the like can be applied. In addition, the board | substrate 101 may be a thing with the whole board | substrate comprised with the resin material, and a part of board | substrate may be comprised with the resin material. The film M1 formed on the substrate 101 is made of a film forming material containing indium oxide as a composition. As a film formation material containing indium oxide, for example, indium oxide without a doping element, indium tin oxide (ITO), indium tungsten oxide (IWO), indium zinc oxide (ISnO), or the like can be used. In the film manufacturing method according to the present embodiment, an indium oxide film M1 having a thin film thickness and a low resistance can be obtained. Specifically, the thickness of the indium oxide film M1 can be set to 100 nm or less. It can also be set to 50 nm or less, and can also be set to 20 nm or less. Note that the thickness of the indium oxide film M1 is at least 5 nm or more. Even with such a thin film thickness, the indium oxide film M1 having a low specific resistance (about 2 to 3 μΩm) can be obtained. The substrate 101 on which the indium oxide film M1 is formed is used for, for example, a touch panel and illumination.

(Deposition system)
In FIG. 1, the film forming apparatus 100 is shown from the side in the Y-axis direction, which is the transport direction (arrow A) of the substrate 101 (see FIG. 2). FIG. 2 is a cross-sectional view taken along line II-II in FIG. 1 and shows a configuration in the vicinity of the vapor deposition apparatus 140 of the film formation apparatus 100. A film forming apparatus 100 shown in FIGS. 1 and 2 is for performing a film forming process on a substrate 101. The film forming apparatus 100 is an apparatus that performs film formation by an ion plating method. The film forming apparatus 100 includes a plasma gun that generates plasma, and uses the generated plasma to ionize the film forming material and deposit the particles of the film forming material on the surface of the substrate 101. In this embodiment, the substrate 101 is described as an example of the type of film forming apparatus 100 arranged in an upright state, but the substrate 101 may be a type of film forming apparatus in which the substrate 101 is arranged horizontally.

  The film forming apparatus 100 includes a load lock chamber 121, a buffer chamber 122, a film forming chamber (chamber) 123, a buffer chamber 124, and a load lock chamber 125. These chambers 121 to 125 are arranged in this order. All the chambers 121 to 125 are constituted by vacuum containers, and open / close gates 131 to 136 are provided at the entrances and exits of the chambers 121 to 125. The film forming apparatus 100 may have a configuration in which a plurality of buffer chambers 122 and 124 and a plurality of film forming chambers 123 are arranged.

  A vacuum pump 150 is connected to each of the vacuum chambers 121 to 125 to bring the inside to an appropriate pressure. Each vacuum chamber 121 to 125 is provided with a vacuum gauge (not shown) for monitoring the pressure in the chamber. A vacuum exhaust pipe connected to the vacuum pump 150 is communicated with each of the chambers 121 to 125, and a vacuum gauge is installed in the vacuum exhaust pipe. A part of each chamber 121, 122, 124, 125 may be omitted.

  The load lock chamber 121 is a chamber in which a substrate 101 to be processed and a transfer tray (not shown) for holding the substrate 101 are introduced by opening an open / close gate 131 provided on the inlet side to open the atmosphere. is there. The outlet side of the load lock chamber 121 is connected to the inlet side of the buffer chamber 122 through an open / close gate 132.

  The buffer chamber 122 is a pressure adjusting chamber that is communicated with the load lock chamber 121 by opening the open / close gate 132 provided on the inlet side and into which the substrate 101 that has passed through the load lock chamber 121 is introduced. The outlet side of the buffer chamber 122 is connected to the inlet side of the film forming chamber 123 through an open / close gate 133. In this embodiment, since the substrate 101 is disposed in an upright state, the film formation surface is disposed along the vertical direction. The buffer chamber 122 is installed in front of the film formation chamber 123.

  The film formation chamber 123 opens the open / close gate 133 provided on the entrance side, thereby communicating with the buffer chamber 122. The substrate 101 and the transfer tray that have passed through the buffer chamber 122 are introduced, and the indium oxide layer M1 is formed on the substrate 101. Is a processing chamber for forming a film. The outlet side of the film forming chamber 123 is connected to the inlet side of the buffer chamber 124 via an open / close gate 134. As shown in FIG. 2, the deposition chamber 123 is provided with a vapor deposition apparatus 140 for depositing the indium oxide layer M1 on the substrate 101. The vapor deposition apparatus 140 includes a main hearth holding a film forming material, a plasma gun for irradiating the main hearth with a plasma beam, and the like (detailed description will be described later).

  The buffer chamber 124 shown in FIG. 1 is connected to the film forming chamber 123 by opening an open / close gate 134 provided on the inlet side, and the substrate 101 on which the indium oxide film M1 is formed by the film forming chamber 123 and the substrate 101 are connected. It is a pressure adjusting chamber into which a transport tray to be held is introduced. The outlet side of the buffer chamber 124 is connected to the inlet side of the load lock chamber 125 via an open / close gate 135. The buffer chamber 124 may be installed after the film formation chamber 123 and function as a cooling chamber for cooling the substrate 101. The substrate 101 may be cooled (air cooled) with the atmosphere in an atmospheric pressure environment after exiting the vacuum chamber. Note that a cooling plate for cooling the substrate 101 may be provided in the buffer chamber 124. The cooling plate may be disposed to face the film formation surface of the substrate 101 in order to cool the film formation surface of the substrate 101. A configuration including a cooling plate for cooling the substrate 101 from the back side of the substrate 101 may be employed.

  The load lock chamber 125 is a chamber that communicates with the buffer chamber 124 by opening the open / close gate 135 provided on the inlet side, and into which the substrate 101 that has passed through the buffer chamber 124 is introduced. On the outlet side of the load lock chamber 125, an open / close gate 136 is provided. By opening the open / close gate 136, the load lock chamber 125 is opened to the atmosphere. In the load lock chamber 125, when the temperature of the substrate 101 is higher than the atmospheric temperature, the substrate is cooled by air release.

  Next, the structure around the vapor deposition apparatus 140 will be described in detail.

  The vapor deposition apparatus 140 of the film forming apparatus 100 of this embodiment includes a main anode 2, a plasma source 5 (plasma gun), and an auxiliary anode 6.

  As shown in FIG. 2, the film forming chamber 123 in which the vapor deposition apparatus 140 is provided is a transfer chamber in which a transfer mechanism 3 (see FIG. 1) for transferring the substrate 101 while exposing the substrate 101 to the ionized film forming material particles Mb. 10a, a film forming chamber 10b for ionizing and diffusing the film forming material Ma, a plasma port 10g for receiving the plasma P irradiated from the plasma source 5 into the film forming chamber 10b, and an atmospheric gas such as oxygen are formed. It has gas supply ports 10d and 10e for introducing into the film chamber 10b, and an exhaust port 10f for exhausting the residual gas in the film formation chamber 10b. The transfer chamber 10a extends in the transfer direction (arrow A in the drawing) which is a predetermined direction in the present embodiment, and is disposed at a position adjacent to the film forming chamber 10b. In the present embodiment, the transport direction (arrow A) is set to the positive direction of the Y axis. The film forming chamber 123 is made of a conductive material and connected to the ground potential.

  The film forming chamber 10b includes a pair of side walls 10h and 10i along the transport direction (arrow A) and a pair of side walls (not shown) along the direction (Z-axis direction) intersecting the transport direction (arrow A). Have.

  The transport mechanism 3 transports the transport tray that holds the substrate 101 in the transport direction (arrow A) while facing the exposed surface of the film forming material Ma. The transport mechanism 3 includes a plurality of transport rollers 31 installed in the transport chamber 10a and a drive unit 32 that drives the transport rollers 31 (see FIG. 1). The transport mechanism that transports the substrate 101 is not limited to a transport mechanism that includes transport rollers. In the case of a film forming apparatus of a type in which the substrate 101 is horizontally disposed, the film forming chamber 10b is disposed on the lower side, the transfer chamber 10a is disposed on the upper side, and the lower surface side of the substrate 101 is supported by the transfer roller 31. It becomes.

  The main body of the plasma source 5 is provided on the side wall (plasma port 10g) of the film forming chamber 10b. The plasma P generated in the plasma source 5 is emitted from the plasma port 10g into the film forming chamber 10b. The emission direction of the plasma P is controlled by a steering coil 51 provided in the plasma port 10g.

  The film forming apparatus 100 is provided with a hearth part 20 (the main anode 2 and the auxiliary anode 6). The hearth unit 20 is disposed corresponding to the plasma source 5. The main anode 2 of the hearth part 20 is a part for holding the film forming material Ma. The main anode 2 is provided in the film forming chamber 10 b of the film forming chamber 123, and is disposed in the negative direction of the X axis direction with respect to the transport mechanism 3. The main anode 2 has a main hearth 21 that guides the plasma P emitted from the plasma source 5 to the film forming material Ma. The main hearth 21 is kept at a positive potential with respect to the film forming chamber 123 which is a ground potential, and sucks the plasma P. A through-hole for loading the film forming material Ma is formed in the central portion of the main hearth 21 where the plasma P is incident. And the front-end | tip part of film-forming material Ma is exposed from this through-hole.

  When the film forming material Ma is made of a conductive substance, when the main hearth 21 is irradiated with the plasma P, the plasma P directly enters the film forming material Ma, and the tip portion of the film forming material Ma is heated and evaporated. The evaporated film forming material Ma is ionized by the plasma P to become ionized film forming material particles Mb. The ionized film forming material particles Mb move to the transfer chamber 10a side (X-axis positive direction) while diffusing into the film forming chamber 10b, and adhere to the surface of the substrate 101 in the transfer chamber 10a. The film forming material Ma is pushed out from below the main anode 2 so that the tip portion always maintains a predetermined position. When the film forming material Ma is made of an insulating material, when the main hearth 21 is irradiated with the plasma P, the main hearth 21 is heated by the current from the plasma P, and the tip portion of the film forming material Ma evaporates. The ionized film forming material particles Mb ionized by the plasma P diffuse into the film forming chamber 10b.

  The auxiliary anode 6 is an electromagnet for inducing the plasma P. The auxiliary anode 6 is disposed around the main hearth 21 that holds the film forming material Ma, and includes an annular container, and a coil 6a and a permanent magnet 6b accommodated in the container. The coil 6a and the permanent magnet 6b control the direction of the plasma P incident on the main hearth 21 according to the amount of current flowing through the coil 6a.

(Annealing equipment)
The annealing apparatus 200 is an apparatus for annealing the indium oxide film M1 formed on the substrate 101 by the film forming apparatus 100. The annealing apparatus 200 is provided on the downstream side of the production line with respect to the film forming apparatus 100 (see FIG. 1). The annealing apparatus 200 includes an annealing furnace 201. The indium oxide film M1 on the substrate 101 can be annealed by housing the substrate 101 in the annealing furnace 201 and heating it at a predetermined set temperature for a predetermined time.

(Indium oxide film manufacturing method)
First, a film forming process for forming the indium oxide film M1 on the substrate 101 by an ion plating method using the film forming apparatus 100 is executed. In the film forming process, the pressure in the film forming chamber 123 is set to 0.3 Pa or less. Note that the pressure in the film formation chamber 123 may be 0.01 Pa or more as a pressure capable of maintaining plasma. Further, the pressure in the film forming chamber 123 may be 0.05 to 0.2 Pa. The pressure in the film forming chamber 123 is adjusted by controlling the vacuum pump 150.

In the film forming process, the moisture partial pressure in the film forming chamber 123 is set to 5.8 × 10 ⁻⁴ Pa or less. In the film formation process, the lower the moisture partial pressure in the film formation chamber 123, the better. Therefore, the lower limit value is not particularly limited, and may be 0 Pa or more. The moisture partial pressure in the film forming chamber 123 may be 1 × 10 ^{−4 to} 6 × 10 ⁻⁴ Pa. Adjustment of the water partial pressure in the film forming chamber 123 is performed by placing the substrate 101 in the film forming chamber 123 and operating the vacuum pump 150 and waiting until the water partial pressure drops to a desired value. Alternatively, the transport tray may be preheated to reduce water vapor evaporated from the transport tray.

  In the film forming process, the temperature of the substrate 101 in the film forming chamber 123 is set to be 100 ° C. or lower. In the film forming step, the temperature is set to 20 ° C. or higher. Further, the temperature of the substrate 101 in the film formation chamber 123 may be set to 30 to 60 ° C. No heater or the like is provided in the film formation chamber 123 (or the heater 160 as shown in FIG. 2 is turned off), and no heating (that is, the room temperature at which the film formation apparatus 100 is installed) Film formation may be performed. Alternatively, when the heater 160 is provided, the temperature of the substrate 101 in the deposition chamber 123 is controlled so as not to be higher than 100 ° C.

  After the film forming process, an annealing process for annealing the indium oxide film M1 on the substrate 101 is performed by the annealing apparatus 200. In the annealing step, the indium oxide film M1 is annealed at 100 ° C. or lower (that is, the temperature in the annealing furnace 201 is set to 100 ° C. or lower). The annealing temperature in the annealing process is 30 ° C. or higher. The annealing temperature may be 50 to 90 ° C. Note that the pressure during annealing is atmospheric pressure. The annealing time is about 15 minutes to 12 hours.

(Action / Effect)
Next, the operation and effect of the method for manufacturing the indium oxide film M1 according to the embodiment of the present invention will be described.

  First, a conventional film manufacturing method will be described. For example, when an indium oxide film (for example, an ITO film) is formed using a resin substrate, it is required to form the film at a low temperature. Here, an ion plating method (RPD) can produce a low-resistance indium oxide film at a lower temperature than other film formation methods such as sputtering, but it can be formed under a low temperature condition of 100 ° C. or lower. When the film is formed, there is a problem that it is difficult to manufacture an indium oxide film having a thin film thickness and a low resistance.

  In general, the crystallization temperature of the ITO film is 180 ° C. or higher. When the ITO film is formed at a low temperature, the ITO film becomes an amorphous film. The amorphous film has a higher resistance than the crystallized film. For example, the specific resistance of the crystallized ITO film is about 2 μΩ · m, whereas the amorphous ITO film has a specific resistance that is twice or more higher.

  Further, in the case of forming a thin indium oxide film, the thinner the film thickness, the more difficult the crystallization of the film proceeds and the higher the specific resistance. Specifically, when the film thickness is 100 nm or less, the specific resistance increases as the film thickness decreases.

  As described above, in the conventional method for producing an indium oxide film, when the film formation temperature is set to 100 ° C. or less and the film thickness is reduced, the crystallization of the film is difficult to proceed and the specific resistance is increased. was there.

  In contrast, in the film manufacturing method according to the present embodiment, a film forming process for forming the indium oxide film M1 on the substrate 101 by the ion plating method, and an annealing process for annealing the indium oxide film M1 after the film forming process. And. In the film formation process, the pressure in the film formation chamber 123 is set to 0.3 Pa or less, the temperature in the film formation chamber 123 is set to 100 ° C. or less, and in the annealing process, the indium oxide film is annealed at 100 ° C. or less. .

  In the film manufacturing method according to the present embodiment, the temperature in the film forming step is set to 100 ° C. or lower, and the annealing temperature in the annealing step is set to 100 ° C. or lower (for example, film formation at a low temperature such as a resin substrate). The indium oxide film M1 can be manufactured regardless of the heat resistance of the substrate 101 (even when using the substrate 101 related to a material that requires the same). In addition, the pressure in the film formation process is set to 0.3 Pa or less, and the annealing process is performed after the film formation process, so that the film thickness is thin even if the temperature in the film formation process is 100 ° C. or less. In addition, the low resistance indium oxide film M1 can be manufactured.

  Note that the annealing process is conventionally performed at a high temperature after the film forming process. However, under normal temperature conditions of 100 ° C. or lower, the film does not crystallize and the resistance is not lowered. Therefore, the annealing process is not performed at a temperature of 100 ° C. or lower as in this embodiment.

In the film forming step, the moisture partial pressure in the film forming chamber 123 is set to 5.8 × 10 ⁻⁴ Pa or less, and further set to 3 × 10 ⁻⁴ Pa or less. Thereby, the low resistance indium oxide film M1 can be manufactured more reliably.

  Note that the reason why crystallization of the indium oxide film proceeds by lowering the pressure in the deposition chamber and the partial pressure of moisture will be described. When the pressure in the film formation chamber is low, the indium oxide film is easily formed with high film formation energy. On the other hand, since hydrogen atoms contained in water have an action of inhibiting crystallization, crystallization is likely to proceed by lowering the water partial pressure. As described above, by performing the film forming process with the pressure reduced and the moisture partial pressure lowered, the film is easily crystallized even under low temperature conditions, and the crystallization proceeds by annealing at a low temperature. It is estimated to be.

  EXAMPLES Hereinafter, although an Example demonstrates this invention in detail, this invention is not limited to these Examples.

(Experimental example 1)
With reference to FIG. 3, Experimental Example 1 for confirming that the indium oxide film is crystallized by the film manufacturing method according to the present invention will be described.

In the example according to Experimental Example 1, the ITO film on the substrate was manufactured by executing the film forming process and the annealing process under predetermined conditions using the film manufacturing apparatus according to the configuration shown in FIG. Each condition in each condition in the film forming process was set as follows. In the annealing process, the substrate on which the ITO film was formed in the film forming process was placed in an annealing furnace and annealed at 90 ° C. for 1 hour.
Pressure in the deposition chamber: 0.2Pa
Moisture partial pressure in the deposition chamber: 4 × 10 ⁻⁴ Pa
Temperature condition: No heating (specifically, 30 ° C)
Substrate material: Glass Film-forming material: ITO
Film thickness: 20nm

In the comparative example according to Experimental Example 1, the conditions were the same as in the example except that the pressure in the film formation chamber was 0.33 Pa and the water partial pressure in the film formation chamber was 4 × 10 ⁻⁴ Pa. An ITO film on the substrate was manufactured.

  The X-ray analysis result of the ITO film manufactured by the film manufacturing method according to the comparative example is shown in FIG. As shown in FIG. 3A, since a peak indicating crystallinity does not appear in the graph of the X-ray analysis result, it is understood that the ITO film is not crystallized in the film manufacturing method according to the comparative example.

  The X-ray analysis result of the ITO film manufactured by the film manufacturing method according to the example is shown in FIG. As shown in FIG. 3B, since a peak indicating crystallinity appears in the graph of the X-ray analysis result, in the film manufacturing method according to the example, the ITO film has a thin film thickness of 20 nm. It is understood that it has crystallized.

  FIG. 3C shows the relationship between the time course of the annealing process and the change in sheet resistance of the ITO film in the example. As shown in FIG. 3C, the ITO film has a sheet resistance of 300Ω / □ (specific resistance 6.0 μΩ · m) immediately after the film forming step, and 100 Ω / □ (ratio) after the annealing treatment for 1 hour. Resistance is 2.0 μΩ · m).

  From the result of FIG. 3 (c), a substrate on which the ITO film crystallizes in the film forming process by adjusting the pressure in the film forming chamber and the water partial pressure to a predetermined condition. It is understood that crystallization is progressing. Note that the progress of crystallization includes not only the case where the entire film is crystallized, but also the state where the amorphous state and the crystalline state are mixed and the ratio of the crystalline state is large.

(Experimental example 2)
With reference to FIG. 4, Experimental Example 2 for confirming the conditions of the pressure and moisture partial pressure in the film forming process of the film manufacturing method according to the present invention will be described.

In Example 1 according to Experimental Example 2, an ITO film on a substrate was manufactured by executing a film forming process and an annealing process under predetermined conditions using the film manufacturing apparatus according to the configuration shown in FIG. . Each condition in each condition in the film forming process was set as follows. In the annealing process, the substrate on which the ITO film was formed in the film forming process was placed in an annealing furnace and annealed at 90 ° C. for 1 hour.

Pressure in the deposition chamber: 0.2Pa
Moisture partial pressure in the deposition chamber: 3.9 × 10 ⁻⁴ Pa
Temperature condition: No heating (specifically, 30 ° C)
Substrate material: Glass Film-forming material: ITO
Film thickness: 20nm

Example 2 according to Experimental Example 2 is the same as Example 1 except that the pressure in the film forming chamber was set to 0.25 Pa and the moisture partial pressure in the film forming chamber was set to 3.5 × 10 ⁻⁴ Pa. An ITO film on the substrate was manufactured under the same conditions.

In Example 3 according to Experimental Example 2, an ITO film on the substrate was manufactured under the same conditions as in Example 1 except that the moisture partial pressure in the film forming chamber was 5.8 × 10 ⁻⁴ Pa. did.

Comparative Example 1 according to Experimental Example 2 is the same as Example 1 except that the pressure in the film forming chamber was 0.33 Pa and the water partial pressure in the film forming chamber was 4.1 × 10 ⁻⁴ Pa. An ITO film on the substrate was manufactured under the same conditions.

Comparative Example 2 according to Experimental Example 2 is the same as Example 1 except that the pressure in the film forming chamber was 0.6 Pa and the water partial pressure in the film forming chamber was 3.3 × 10 ⁻⁴ Pa. An ITO film on the substrate was manufactured under the same conditions.

In Comparative Example 3 according to Experimental Example 2, an ITO film on the substrate was manufactured under the same conditions as in Example 1 except that the moisture partial pressure in the film forming chamber was 7.0 × 10 ⁻⁴ Pa. did.

  About Examples 1-3 and Comparative Examples 1-3, while measuring the sheet resistance before performing an annealing process, the sheet resistance after performing an annealing process was measured. Further, from the measurement results, it was evaluated whether or not there was an effect of low-temperature annealing treatment (whether the resistance of the ITO film was lowered by the annealing treatment). In addition, when the sheet resistance decreased by 20% or more, it was evaluated that “there was an annealing effect”. The evaluation results are shown in FIG.

FIG. 4A is a table in which the evaluation results of Example 1, Example 2, Comparative Example 1, and Comparative Example 2 are arranged. Although Example 1, Example 2, Comparative Example 1, and Comparative Example 2 all satisfy the condition of a moisture partial pressure of 5.8 × 10 ⁻⁴ Pa or less, Comparative Examples 1 and 2 have a pressure of 0.3 Pa or less. This condition is not met. Examples 1 and 2 were evaluated as having an annealing effect, and Comparative Examples 1 and 2 were evaluated as having no annealing effect. From the evaluation result of FIG. 4A, it is understood that the effect of low-temperature annealing occurs when the pressure is 0.3 Pa.

FIG. 4B is a table in which the evaluation results of Example 1, Example 3, and Comparative Example 3 are arranged. In Example 1, Example 3, and Comparative Example 3, the pressure is 2.0 Pa, and the condition of 0.3 Pa or less is satisfied. However, Comparative Example 3 has a moisture partial pressure of 5.8 × 10 ⁻⁴ Pa or less. This condition is not met. Examples 1 and 3 were evaluated as having an annealing effect, and Comparative Example 3 was evaluated as having no annealing effect. From the evaluation result of FIG. 4B, it is understood that the effect of low-temperature annealing is more reliably generated by setting the moisture partial pressure to 5.8 × 10 ⁻⁴ Pa or less. In Experimental Examples 1 and 2, glass is used as the material of the substrate, but the same result can be obtained by using a resin material.

  DESCRIPTION OF SYMBOLS 1 ... Film manufacturing apparatus, 100 ... Film-forming apparatus, 101 ... Board | substrate (film-forming object), 123 ... Film-forming chamber, 140 ... Deposition apparatus, 200 ... Annealing apparatus, M1 ... Indium oxide film.

In this embodiment, a material having low heat resistance can be applied as the material of the substrate 101, and a glass substrate coated with a resin material or resin can be applied. As the resin material, for example, PET, acrylic, polycarbonate and the like can be applied. In addition, the board | substrate 101 may be a thing with the whole board | substrate comprised with the resin material, and a part of board | substrate may be comprised with the resin material. The film M1 formed on the substrate 101 is made of a film forming material containing indium oxide as a composition. As a film formation material containing indium oxide, for example, indium oxide without a doping element, indium tin oxide (ITO), indium tungsten oxide (IWO), indium zinc oxide (ISnO), or the like can be used. In the film manufacturing method according to the present embodiment, an indium oxide film M1 having a thin film thickness and a low resistance can be obtained. Specifically, the thickness of the indium oxide film M1 can be set to 100 nm or less. It can also be set to 50 nm or less, and can also be set to 20 nm or less. Note that the thickness of the indium oxide film M1 is at least 5 nm or more. Even with such a thin film thickness, the indium oxide film M1 having a low specific resistance (about 2 to 3 μΩm ) can be obtained. The substrate 101 on which the indium oxide film M1 is formed is used for, for example, a touch panel and illumination.

The transport mechanism 3 transports the transport tray that holds the substrate 101 in the transport direction (arrow A) in a state of facing the exposed surface of the film forming material Ma. The transport mechanism 3 includes a plurality of transport rollers 31 installed in the transport chamber 10a and a drive unit 32 that drives the transport rollers 31 (see FIG. 1). The transport mechanism that transports the substrate 101 is not limited to a transport mechanism that includes transport rollers. In the case of a film forming apparatus of a type in which the substrate 101 is horizontally disposed, the film forming chamber 10b is disposed on the lower side, the transfer chamber 10a is disposed on the upper side, and the lower surface side of the substrate 101 is supported by the transfer roller 31. It becomes.

In Example 1 according to Experimental Example 2, an ITO film on a substrate was manufactured by executing a film forming process and an annealing process under predetermined conditions using the film manufacturing apparatus according to the configuration shown in FIG. . Each condition in the deposition process, were set as follows. In the annealing process, the substrate on which the ITO film was formed in the film forming process was placed in an annealing furnace and annealed at 90 ° C. for 1 hour.

FIG. 4A is a table in which the evaluation results of Example 1, Example 2, Comparative Example 1, and Comparative Example 2 are arranged. Although Example 1, Example 2, Comparative Example 1, and Comparative Example 2 all satisfy the condition of a moisture partial pressure of 5.8 × 10 ⁻⁴ Pa or less, Comparative Examples 1 and 2 have a pressure of 0.3 Pa or less. This condition is not met. Examples 1 and 2 were evaluated as having an annealing effect, and Comparative Examples 1 and 2 were evaluated as having no annealing effect. From the evaluation result of FIG. 4A, it is understood that the effect of low-temperature annealing occurs when the pressure is 0.3 Pa.

Claims (3)

A film forming step of forming an indium oxide film on an object to be formed by an ion plating method;
An annealing step for annealing the indium oxide film after the film-forming step,
In the film formation step, the pressure in the chamber is 0.3 Pa or less, the temperature of the film formation target is 100 ° C. or less,
In the annealing step, the indium oxide film is annealed at 100 ° C. or less. 2. The film manufacturing method according to claim 1, wherein in the film forming step, a partial pressure of water in the chamber is set to 5.8 × 10 ⁻⁴ Pa or less. 3. The film manufacturing method according to claim 2, wherein, in the film forming step, a moisture partial pressure in the chamber is set to 3.9 × 10 ⁻⁴ Pa or less.

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