TWI496919B - Film manufacturing method and film manufacturing apparatus - Google Patents

Description

Film manufacturing method and film manufacturing device

The present invention relates to a film production method and a film production apparatus for forming an indium oxide film on a film formation object.

Conventionally, in order to apply to a touch panel or the like, a technique of forming a low-resistance indium oxide film on a substrate by ion plating has been known. For example, according to the apparatus for manufacturing a film disclosed in Patent Document 1, the film forming material is ionized and diffused at a temperature higher than 100 ° C in the chamber, and an indium oxide film is formed on the substrate.

(previous technical literature) (Patent Literature)

Patent Document 1: Japanese Patent Laid-Open Publication No. 2005-050730

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

Therefore, an object of the present invention is to provide a film production method and a film production apparatus which produce a low-resistance indium oxide film by setting the temperature at the time of film formation to 100 ° C or lower.

The film production method of the present invention comprises: a film formation process of forming an indium oxide film on a film formation object by an ion plating method; and an annealing process of annealing the indium oxide film after the film formation process; In the film forming process, the pressure in the chamber is set to 0.3 Pa or less, and the temperature of the film formation object is set to 100 ° C or less. In the annealing process, the indium oxide film is annealed at 100 ° C or lower.

According to the film production method of the present invention, the temperature in the film formation process is set to 100 ° C or lower, and the annealing temperature in the annealing process is set to 100 ° C or less, whereby (even if, for example, a resin substrate or the like is used, it is required to be at a low temperature. In the case of the film formation target of the material to be formed into a film, the indium oxide film can be produced irrespective of the heat resistance of the film formation object. Further, the pressure in the film forming process is set to 0.3 Pa or less, and an annealing process is performed after the film forming process, whereby a low-resistance indium oxide film can be manufactured even if the temperature in the film forming process is a low temperature of 100 ° C or lower. . As described above, the temperature at the time of film formation can be set to 100 ° C or lower, and a low-resistance indium oxide film can be produced.

Further, in the film production method of the present invention, it is preferred that the partial pressure of moisture in the chamber be 5.8 × 10 ^-4 Pa or less. Further, the partial pressure of moisture in the chamber may be set to 3.9 × 10 ^-4 Pa or less. Thereby, the low-resistance indium oxide film can be manufactured more reliably.

The film production apparatus of the present invention includes: a film formation apparatus that forms an indium oxide film on a film formation object by an ion plating method; and an annealing device that is formed on the film formation object by a film formation apparatus The indium oxide film is annealed; the film forming apparatus has a vacuum chamber; a pressure maintaining means for maintaining a pressure in the vacuum chamber at a time of film formation of 0.3 Pa or less; and a temperature maintaining means for forming a film The temperature of the film object is maintained at 100 ° C or lower; the annealing apparatus has an annealing furnace for heating the indium oxide film at 100 ° C or lower.

According to the film production apparatus of the present invention, the temperature at the time of film formation is set to 100 ° C or lower, and the annealing temperature at the time of annealing is set to 100 ° C or less, whereby (if necessary, for example, a film substrate or the like is required to form a film at a low temperature. In the case of the film formation target of the material, the indium oxide film can be produced regardless of the heat resistance of the film formation object. In addition, the pressure at the time of film formation is set to 0.3 Pa or less, and the indium oxide film formed on the film formation object by the film formation apparatus is annealed, whereby the temperature at the time of film formation is 100 ° C or less. Low temperature can also produce a low-resistance indium oxide film. As described above, the temperature at the time of film formation can be set to 100 ° C or lower, and a low-resistance indium oxide film can be produced.

Further, in the film production apparatus of the present invention, the film formation apparatus has a moisture partial pressure maintaining means for maintaining the partial pressure of moisture in the chamber at the time of film formation at 5.8 × 10 ^-4 Pa or less. Further, the moisture partial pressure maintaining means can maintain the partial pressure of moisture in the chamber at the time of film formation at 3.9 × 10 ^-4 Pa or less. Thereby, the low-resistance indium oxide film can be manufactured more reliably.

According to the invention, the temperature at the time of film formation can be set to 100 ° C or lower, and a low-resistance indium oxide film can be produced.

1‧‧‧ film manufacturing equipment

100‧‧‧ film forming device

101‧‧‧Substrate (film formation object)

123‧‧‧filming chamber

140‧‧‧Vapor deposition unit

150‧‧‧Vacuum pump (pressure maintenance means, moisture partial pressure maintenance means)

160‧‧‧heater (temperature maintenance means)

200‧‧‧ Annealing device

201‧‧‧ Annealing furnace

M1‧‧‧ indium oxide film

Fig. 1 is a schematic configuration view showing a film production apparatus used in a film production method according to an embodiment of the present invention.

Fig. 2 is a cross-sectional view taken along line II-II of Fig. 1.

Fig. 3 is a graph showing the results of Example 1.

Fig. 4 is a table showing the results of Example 2.

Hereinafter, embodiments of the present invention will be described with reference to the accompanying drawings. In the description of the drawings, the same reference numerals will be given to the same elements, and the repeated description will be omitted. Further, the words "upper", "lower", etc., indicating the directions are based on the state shown in the drawings, and are for ease of understanding. Further, in the first and second drawings, an XYZ rectangular coordinate system is also shown for convenience of explanation.

Fig. 1 is a schematic block diagram showing a film production apparatus 1 according to an embodiment of the present invention. The film manufacturing apparatus 1 is used for manufacturing a substrate (formed) As shown in Fig. 1, the apparatus for indium oxide film M1 on the film object 101 includes a film forming apparatus 100 and an annealing apparatus 200.

Fig. 1 is a schematic block diagram showing a film production apparatus 1 according to an embodiment of the present invention. The film manufacturing apparatus 1 is a device for forming an indium oxide film M1 on a substrate (film formation target) 101, and as shown in Fig. 1, a film forming apparatus 100 and an annealing apparatus 200 are provided.

In the present embodiment, a material having a lower heat resistance can be applied as the material of the substrate 101, and a resin material or a glass substrate coated with a resin can be applied. As the resin material, for example, PET, acrylic, polycarbonate, or the like can be applied. Further, the substrate 101 may be formed of a resin material as a whole of the substrate, or may be formed of a resin material as a part of the substrate. The indium oxide film M1 formed on the substrate 101 is composed of a film forming material containing indium oxide as a composition. As the film-forming material including indium oxide as a composition, for example, indium oxide, indium tin oxide (ITO), indium tungsten oxide (IWO), indium zinc oxide (IZnO), or the like, which is an undoped element, can be used. In the film production method of the present embodiment, the indium oxide film M1 having a small film thickness and low electrical resistance can be obtained. Specifically, the film thickness of the indium oxide film M1 can be set to 100 nm or less. Further, it can be set to 50 nm or less, and can be set to 20 nm or less. Further, the film thickness of the indium oxide film M1 is at least 5 nm or more. Even in such a thin film thickness, an indium oxide film M1 having a lower 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 example, for a touch panel or illumination.

(film forming device)

In the first drawing, the film forming apparatus 100 is shown on the side in the Y-axis direction from the transport direction (arrow A) of the substrate 101 (see FIG. 2). Fig. 2 is a cross-sectional view taken along line II-II of Fig. 1 showing the structure in the vicinity of the vapor deposition device 140 of the film forming apparatus 100. The film forming apparatus 100 shown in Figs. 1 and 2 is for performing a film forming process on the substrate 101. The film forming apparatus 100 is a device for forming a film by an ion plating method. The film forming apparatus 100 includes a plasma gun that generates plasma, and ionizes the film forming material by using the generated plasma, and deposits particles of the film forming material on the surface of the substrate 101 to form a film. In the present embodiment, the film forming apparatus 100 of the type in which the substrate 101 is placed in an upright state will be described as an example. However, a film forming apparatus of a type in which the substrate 101 is horizontally disposed may be used.

The film forming apparatus 100 is provided with 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. The chambers 121 to 125 are arranged side by side in this order. All of the chambers 121 to 125 are constituted by vacuum vessels, and opening and closing 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 structure in which a plurality of buffer chambers 122 and 124 and a film forming chamber 123 are arranged side by side.

A vacuum pump 150 for setting the inside to an appropriate pressure is connected to each of the vacuum chambers 121 to 125. The vacuum pump 150 is controlled by a control device (not shown). The pressure maintenance means in the present application is constituted by a vacuum pump and a control device. Further, a vacuum gauge (not shown) for monitoring the pressure in the chamber is provided in each of the vacuum chambers 121 to 125. Each chamber 121 ~125 is in communication with a vacuum exhaust pipe connected to the vacuum pump 150, and a vacuum gauge is disposed on the vacuum exhaust pipe. In addition, each of the chambers 121, 122, 124, 125 may be omitted.

The load lock chamber 121 is a chamber that opens and closes the opening and closing gate 131 provided on the inlet side, thereby opening the atmosphere, and introducing the substrate 101 to be processed and the transport tray 102 holding the substrate 101 (see FIG. 2). ). The outlet side of the load lock chamber 121 is connected to the inlet side of the buffer chamber 122 via the opening and closing gate 132.

The buffer chamber 122 is a pressure adjustment chamber that opens and closes the opening and closing gate 132 on the inlet side, thereby communicating with the load lock chamber 121 and introducing the substrate 101 and the transport tray 102 that have passed through the load lock chamber 121. . The outlet side of the buffer chamber 122 is connected to the inlet side of the film forming chamber 123 via the opening and closing gate 133. In the present embodiment, since the substrate 101 is placed in an upright state, the film formation surface is arranged in the vertical direction. The buffer chamber 122 is disposed at a front portion of the film forming chamber 123.

The film forming chamber 123 is a processing chamber that opens and closes the opening and closing gate 133 provided on the inlet side, thereby communicating with the buffer chamber 122, introducing the substrate 101 and the transport tray 102 that have passed through the buffer chamber 122, and is on the substrate 101. Forming an indium oxide layer M1. The outlet side of the film forming chamber 123 is connected to the inlet side of the buffer chamber 124 via the opening and closing gate 134. As shown in FIG. 2, a vapor deposition device 140 for forming an indium oxide layer M1 on the substrate 101 is provided in the film formation chamber 123. The vapor deposition device 140 is composed of a main hearth that holds a film forming material, a plasma gun that irradiates a plasma jet to the main hearth, and the like (details will be described later).

The buffer chamber 124 shown in Fig. 1 is a pressure adjusting chamber that opens and closes the opening and closing gate 134 provided on the inlet side, thereby communicating with the film forming chamber 123, and introducing indium oxide formed by the film forming chamber 123. The substrate 101 of the film M1 and the transport tray 102 holding the substrate. The outlet side of the buffer chamber 124 is connected to the inlet side of the load lock chamber 125 via an opening and closing gate 135. The buffer chamber 124 may be disposed in the rear portion of the film forming chamber 123 to function as a cooling chamber for cooling the substrate 101. In the atmospheric pressure environment after being carried out from the vacuum chamber, the substrate 101 may be cooled (air-cooled) by the atmosphere. In addition, a cooling plate for cooling the substrate 101 may be provided in the buffer chamber 124. In order to cool the film formation surface of the substrate 101, the cooling plate can be disposed to face the film formation of the substrate 101. It may be configured to include a cooling plate that cools the substrate 101 from the back side of the substrate 101.

The load lock chamber 125 is a chamber that communicates with the buffer chamber 124 so as to be open to the opening and closing gate 135 provided on the inlet side, and is introduced into the substrate 101 and the transport tray 102 that have passed through the buffer chamber 124. An opening and closing gate 136 is provided on the outlet side of the load lock chamber 125, and the load lock chamber 125 is opened in the atmosphere by opening the opening and closing gate 136. In the load lock chamber 125, when the temperature of the substrate 101 is higher than the atmospheric temperature, it is air-cooled by being opened in the atmosphere.

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

The vapor deposition device 140 of the film formation apparatus 100 of the present 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 provided with the vapor deposition device 140 has a transfer chamber 10a provided with a transport mechanism 3 for transporting the substrate 101 while being exposed to the ionized film-forming material particles Mb. (Refer to Fig. 1); a film forming chamber 10b for ionizing and diffusing the film forming material Ma; a plasma port 10g for introducing the plasma P irradiated from the plasma source 5 into the film forming chamber 10b; gas supply ports 10d, 10e for introducing an environmental gas such as oxygen into the inside of the film forming chamber 10b; and an exhaust port 10f for discharging the remaining gas in the film forming chamber 10b. The transport chamber 10a extends in a predetermined direction, that is, a transport direction (arrow A in the drawing) 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. Further, the film forming chamber 123 is made of a conductive material and connected to a ground potential.

The film forming chamber 10b has a pair of side walls 10h and 10i opposed to each other in the transport direction (arrow A) and a pair of side walls (not shown) opposed to each other in the direction intersecting the transport direction (arrow A) (Z-axis direction). ).

The transport mechanism 3 transports the transport tray 102 holding the substrate 101 in the transport direction (arrow A) in a state of being opposed to the exposed surface of the film forming material Ma. The transport mechanism 3 is configured by a plurality of transport rollers 31 that are disposed in the transport chamber 10a, and a drive unit 32 that drives the transport roller 31 (see FIG. 1). Further, the transport mechanism of the transport substrate 101 is not limited to the transport mechanism including the transport roller. Further, when the film forming apparatus of the type of the substrate 101 is horizontally disposed, the film forming chamber 10b is disposed on the lower side, and the transport chamber 10a is disposed on the upper side, and is transported. The roller 31 supports the structure of the lower surface side of the substrate 101.

The main body portion of the plasma source 5 is disposed on the side wall (the 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 direction in which the plasma P is emitted is controlled by the steering coil 51 provided at the plasma port 10g.

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

When the film forming material Ma is made of a conductive material, when the plasma P is irradiated to the main hearth 21, the plasma P is directly incident on the film forming material Ma, and the tip end portion of the film forming material Ma is heated and evaporated. The vaporized 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 toward the transport chamber 10a side (the positive X-axis direction) while diffusing into the film forming chamber 10b, and adhere to the surface of the substrate 101 in the transport chamber 10a. Further, the film forming material Ma is pushed out from the lower side of the main anode 2 so that the front end portion thereof is always maintained at a predetermined position. In addition, when the film forming material Ma is composed of an insulating material, if the main hearth is When the plasma P is irradiated, the main hearth 21 is heated by the current from the plasma P, and the front end portion of the film forming material Ma is evaporated, and the ionized film forming material particles Mb are ionized by the plasma P to the film forming chamber. Diffusion within 10b.

The auxiliary anode 6 is an electromagnet for inducing the plasma P. The auxiliary anode 6 is disposed around the main hearth 21 holding the film forming material Ma, and has an annular container and a coil 6a and a permanent magnet 6b housed in the container. The coil 6a and the permanent magnet 6b control the direction of the plasma P incident on the main hearth 21 in accordance with the amount of current flowing through the coil 6a.

Further, a heater 160 is disposed in the film forming chamber 123. The heater 160 is used to adjust the temperature of the substrate 101 and the transport tray 102 in the film forming chamber 123. The heater 160 can use a well-known heating means, for example, a lamp heater or the like can be used. The heater 160 is controlled by a control device (not shown). The heater 160 and the control device constitute the temperature maintenance means in the present application.

(annealing device)

The annealing device 200 is a device for annealing the indium oxide film M1 formed on the substrate 101 by the film forming apparatus 100. The annealing device 200 is disposed on the downstream side of the production line from the film forming apparatus 100 (see FIG. 1). That is, the annealing device 200 is disposed in the rear stage of the film forming apparatus 100. The annealing device 200 is provided with an annealing furnace 201. The substrate 101 is placed in the annealing furnace 201 and heated at a predetermined set temperature for a predetermined time, whereby the indium oxide film M1 on the substrate 101 can be annealed. In addition, the annealing device 200 is provided with a temperature for controlling the temperature in the annealing furnace 201. Control device (not shown).

(Method for Producing Indium Oxide Film)

First, a film forming process for forming an indium oxide film M1 on the substrate 101 by ion plating is performed by the film forming apparatus 100. In the film forming process, the pressure in the film forming chamber 123 is set to 0.3 Pa or less. Further, the pressure of the film forming chamber 123 may be 0.01 Pa or more as a pressure capable of maintaining the plasma. Further, the pressure of the film forming chamber 123 may be set to 0.05 to 0.2 Pa. The adjustment of the pressure of the film forming chamber 123 is performed by controlling the vacuum pump 150 by a control device (not shown). In other words, the pressure in the film forming chamber 123 at the time of film formation is maintained at 0.3 Pa or less by the pressure maintaining means constituted by the vacuum pump 150 and the control device.

In the deposition process, the moisture in the deposition chamber 123 is set to a partial pressure of less 5.8 × 10 ^-4 Pa. In the film forming process, the lower the partial pressure of moisture of the film forming chamber 123 is, the lower the limit is not particularly limited, and may be 0 Pa or more. Further, the partial pressure of moisture in the film forming chamber 123 can be set to 1 × 10 ^-4 to 6 × 10 ^-4 Pa. The adjustment of the partial pressure of moisture in the film forming chamber 123 is performed by arranging the substrate 101 in the film forming chamber 123, and operating the vacuum pump 150 until the partial pressure of moisture drops to a desired value. At this time, the vacuum pump 150 and the control device for controlling the same constitute the moisture partial pressure maintaining means in the present application. By the moisture partial pressure maintaining means, the partial pressure of moisture in the film forming chamber 123 at the time of film formation is maintained at 5.8 × 10 ^-4 Pa or less (preferably 3.9 × 10 ^-4 Pa). Further, it is also possible to reduce the evaporation of the water vapor from the transport tray 102 by preheating the transport tray 102 in advance. At this time, the pre-heating means for preheating the transport tray 102 before film formation constitutes the moisture partial pressure maintaining means in the present application.

In the film forming process, the heater 160 heats the substrate 101 so that the temperature of the substrate 101 in the film forming chamber 123 becomes 100 ° C or lower. In the film forming process, the temperature is set to 20 ° C or higher. Further, the temperature of the substrate 101 in the film forming chamber 123 can be set to 30 to 60 °C. The heater 160 is not provided in the film forming chamber 123 (or even if the heater 160 is provided as turned off as shown in FIG. 2), and there is no heating (that is, the temperature of the room temperature in which the film forming apparatus 100 has been set). It is also possible to form a film. At this time, the temperature of the substrate 101 is adjusted by the temperature (room temperature) inside the film forming chamber 123. Therefore, at this time, the film forming chamber 123 constitutes the temperature maintaining means in the present application.

After the film forming process, an annealing process for annealing the indium oxide film M1 on the substrate 101 is performed by the annealing device 200. In the annealing process, 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 set to 30 ° C or higher. Further, the annealing temperature can be set to 50 to 90 °C. Further, the pressure at the time of annealing is atmospheric pressure. The annealing time is set to be about 15 minutes to 12 hours.

(Effect)

Next, the action and effect of the film production method and the film production apparatus of the indium oxide film M1 according to the embodiment of the present invention will be described.

First, a conventional film production method and a film production apparatus will be described. For example, when a film of an indium oxide film (for example, an ITO film) is formed using a resin substrate, film formation at a low temperature is required. Here, in comparison with other film forming methods such as a sputtering method, a low-resistance indium oxide film can be produced at a low temperature by an ion plating method (RPD), but when a film is formed under a low temperature condition of 100 ° C or lower, There is a problem that it is difficult to produce an indium oxide film having a thin film thickness and low electrical resistance.

Usually, the crystallization temperature of the ITO film is set to 180 ° C or higher, and when the film is formed at a low temperature, the ITO film becomes an amorphous film. The amorphous film has a higher electrical resistance than the crystallized film. For example, the specific resistance of the crystallized ITO film is 2 μΩ. On the other hand, the specific resistance of the amorphous ITO film is increased by a factor of two or more.

Further, when an indium oxide film having a small film thickness is formed, the thinner the film thickness, the more difficult the film crystallizes and the higher the specific resistance. Specifically, when the film thickness is 100 nm or less, the film thickness is reduced and the specific resistance is increased.

As described above, in the conventional method for producing an indium oxide film and a film production apparatus, when the film formation temperature is 100° C. or less and the film thickness is made thin, the film crystal is hard to be formed, and the specific resistance is high. The problem.

On the other hand, in the film production method and the film production apparatus of the present embodiment, annealing is performed by forming an indium oxide film M1 on the substrate 101 by ion plating, and forming an indium oxide film M1 formed on the substrate 101. Annealing is performed. Further, at the time of film formation, the pressure in the film forming chamber 123 is set to 0.3 Pa or less, and the temperature in the film forming chamber 123 is set to 100 ° C or lower, and at the time of annealing, the indium oxide film is formed at 100 ° C or lower. get on Annealing treatment.

In the film production method and the film production apparatus of the present embodiment, the temperature at the time of film formation is set to 100 ° C or lower, and the annealing temperature at the time of annealing is set to 100 ° C or less, whereby (for example, a resin substrate or the like is used. The indium oxide film M1 can also be manufactured irrespective of the heat resistance of the substrate 101 in the case of the substrate 101 of the material formed at a low temperature. Further, the pressure at the time of film formation is set to 0.3 Pa or less, and an annealing process is performed after film formation, whereby even if the temperature at the time of film formation is a low temperature of 100 ° C or lower, it is possible to produce a film having a small film thickness and low resistance. Indium film M1.

In addition, it has been known to perform annealing at a relatively high temperature after film formation. However, in general, under the temperature conditions of 100 ° C or lower, the crystallization of the film does not progress and does not become low resistance. Therefore, the annealing treatment is not completed at a temperature of 100 ° C or lower as in the present embodiment.

In addition, the partial pressure of moisture in the film forming chamber 123 at the time of film formation is 5.8 × 10 ^-4 Pa or less, and further, 3 × 10 ^-4 Pa or less. Thereby, the low-resistance indium oxide film M1 can be manufactured more reliably.

In addition, the reason why the crystallization of the indium oxide film M1 is promoted by lowering the pressure of the film forming chamber 123 and the partial pressure of moisture will be described. In the state where the pressure of the film forming chamber 123 is low, the indium oxide film M1 is easily formed in a state where the film forming energy is high. On the other hand, since the hydrogen atom containing water has an effect of inhibiting crystallization, it is a state in which crystallization is easily promoted by lowering the partial pressure of water. As described above, it can be inferred that the film formation is performed by lowering the pressure and lowering the partial pressure of moisture, thereby making it easier to crystallize even at a lower temperature condition, by annealing treatment at a lower temperature. crystallization.

[Examples]

Hereinafter, the present invention will be described in detail by way of examples, but the invention is not limited thereto.

(Experimental Example 1)

Referring to Fig. 3, an experimental example 1 for confirming that the indium oxide film is crystallized by the film production method of the present invention will be described.

In the embodiment of Experimental Example 1, the film forming apparatus of the structure shown in Fig. 1 was used, and the film forming process and the annealing process were performed under predetermined conditions, whereby the ITO film on the substrate was produced. 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 formation process was housed in an annealing furnace, and annealed at 90 ° C for 1 hour.

Pressure in the film forming chamber: 0.2Pa

Moisture partial pressure in the film forming 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 of the experimental example 1, the same conditions as in the examples were carried out except that the pressure in the film forming chamber was 0.33 Pa and the partial pressure of moisture in the film forming chamber was set to 4 × 10 ^-4 Pa. An ITO film on the substrate was fabricated.

The X-ray analysis results of the ITO film produced by the film production method of the comparative example are shown in Fig. 3(a). As shown in Fig. 3(a), the peak of the crystallinity was not shown in the graph of the X-ray analysis result. Therefore, in the film production method of the comparative example, the ITO film was not crystallized.

The X-ray analysis results of the ITO film produced by the film production method of the example are shown in Fig. 3(b). As shown in Fig. 3(b), the peak of the crystallinity is shown in the graph of the X-ray analysis result. Therefore, in the film production method of the example, even if the film thickness is 20 nm, the ITO film is also thin. crystallization.

Further, the correlation between the time of the annealing process in the examples and the change in sheet resistance of the ITO film is shown in Fig. 3(c). As shown in Fig. 3(c), the sheet resistance of the ITO film is 300 Ω/□ (specific resistance 6.0 μΩ·m) immediately after the film formation process, and becomes 100 Ω/□ after one hour of annealing (specific resistance). 2.0 μΩ.m).

As is clear from the results of Fig. 3(c), by adjusting the pressure of the film forming chamber and the partial pressure of water to predetermined conditions, a matrix of ITO film crystals is formed in the film forming process, and annealing is performed to advance the film. Crystallization of the ITO film. In addition, the promotion of the crystal includes not only the entire crystal of the entire film but also a state in which the amorphous state and the crystalline state are mixed and the ratio of the crystalline state is large.

(Experimental Example 2)

Referring to Fig. 4, Experimental Example 2 for confirming the conditions of pressure and moisture partial pressure in the film forming process of the film production method of the present invention is described. Bright.

In the first embodiment of the experimental example 2, the film forming apparatus of the structure shown in Fig. 1 was used, and the film forming process and the annealing process were performed under predetermined conditions, whereby the ITO film on the substrate was produced. Each condition in the film forming process was set as follows. In the annealing process, the substrate on which the ITO film was formed by the film formation process was housed in an annealing furnace, and annealed at 90 ° C for 1 hour.

Pressure in the film forming chamber: 0.2Pa

Moisture partial pressure in the film forming chamber: 3.9 × 10 ^-4 Pa

Temperature condition: no heating (specifically 30 ° C)

Substrate material: glass

Film forming material: ITO

Film thickness: 20nm

In the second embodiment of the experimental example 2, the same as in the first embodiment except that the pressure in the film forming chamber was set to 0.25 Pa and the partial pressure of moisture in the film forming chamber was set to 3.5 × 10 ^-4 Pa. The ITO film on the substrate was fabricated under the conditions.

In Example 3 of Experimental Example 2, an ITO film on a substrate was produced under the same conditions as in Example 1 except that the partial pressure of moisture in the film forming chamber was set to 5.8 × 10 ^-4 Pa.

In Comparative Example 1 of Experimental Example 2, the same as in Example 1, except that the pressure in the film forming chamber was 0.33 Pa and the partial pressure of moisture in the film forming chamber was set to 4.1 × 10 ^-4 Pa. The ITO film on the substrate was fabricated under the conditions.

In Comparative Example 2 of Experimental Example 2, the same as in Example 1, except that the pressure in the film forming chamber was 0.6 Pa, and the partial pressure of moisture in the film forming chamber was set to 3.3 × 10 ^-4 Pa. The ITO film on the substrate was fabricated under the conditions.

In Comparative Example 3 of Experimental Example 2, an ITO film on a substrate was produced under the same conditions as in Example 1 except that the partial pressure of moisture in the film forming chamber was set to 7.0 × 10 ^-4 Pa.

With respect to Examples 1 to 3 and Comparative Examples 1 to 3, the sheet resistance before the annealing process was performed was measured, and the sheet resistance after the annealing process was performed was measured. Further, from the measurement results, the effect of whether or not the annealing treatment at a low temperature was performed (whether or not the annealing of the ITO film was promoted by the annealing treatment) was evaluated. Further, when the sheet resistance was decreased by 20% or more, it was evaluated as "the annealing effect". The evaluation results are shown in Fig. 4.

Fig. 4(a) is a table showing the evaluation results of Example 1, Example 2, Comparative Example 1, and Comparative Example 2. In Example 1, Example 2, Comparative Example 1, and Comparative Example 2, the conditions of the partial pressure of water of 5.8 × 10 ^-4 Pa or less were satisfied, but Comparative Examples 1 and 2 did not satisfy the condition that the pressure was 0.3 Pa or less. Each of Examples 1 and 2 was evaluated as having an annealing effect, and Comparative Examples 1 and 2 were evaluated as having no annealing effect. From the evaluation results of Fig. 4(a), it is understood that the effect of low-temperature annealing can be produced by setting the pressure to 0.3 Pa.

Fig. 4(b) is a table in which the evaluation results of Example 1, Example 3, and Comparative Example 3 are arranged. Example 1, Example 3 Pressure embodiment and Comparative Example 3 are 2.0Pa, 0.3Pa following condition, but does not satisfy the Comparative Example 3 Water partial pressure conditions of 10 ^-4 Pa or less 5.8 ×. 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 results of Fig. 4(b), it is understood that the effect of low-temperature annealing can be more reliably produced by setting the partial pressure of water to 5.8 × 10 ^-4 Pa or less. Further, in Experimental Examples 1 and 2, glass was used as a material of the substrate, but the same result was obtained by using a resin material.

1‧‧‧ film manufacturing equipment

3‧‧‧Transportation agencies

31‧‧‧Conveying roller

32‧‧‧ Drive Department

51‧‧‧ steering coil

100‧‧‧ film forming device

101‧‧‧Substrate (film formation object)

121‧‧‧Load lock chamber

122‧‧‧buffer chamber

123‧‧‧filming chamber

124‧‧‧buffer chamber

125‧‧‧Loading interlocking chamber

131‧‧‧Opening and closing valve

132‧‧‧Opening and closing valve

133‧‧‧Opening and closing valve

134‧‧‧Opening and closing valve

135‧‧‧Opening and closing valve

136‧‧‧Opening and closing valve

140‧‧‧Vapor deposition unit

150‧‧‧Vacuum pump (pressure maintenance means, moisture partial pressure maintenance means)

200‧‧‧ Annealing device

201‧‧‧ Annealing furnace

M1‧‧‧ indium oxide film

P‧‧‧Plastic

Claims (6)

A film manufacturing method comprising: a film forming process of forming an indium oxide film on a film formation object by an ion plating method; and an annealing process of annealing the indium oxide film after the film forming process; In the film forming process, the pressure in the chamber is set to 0.3 Pa or less, and the temperature of the film formation object is set to 100 ° C or lower. In the annealing process, the indium oxide film is annealed at 100 ° C or lower. The film manufacturing method according to claim 1, wherein in the film forming process, the partial pressure of moisture in the chamber is set to 5.8 × 10 ^-4 Pa or less. The film production method according to claim 2, wherein in the film forming process, the partial pressure of moisture in the chamber is set to 3.9 × 10 ^-4 Pa or less. A film manufacturing apparatus comprising: a film forming apparatus that forms an indium oxide film on a film formation object by an ion plating method; and an annealing device that forms the aforementioned film formation object on the film formation object The indium oxide film is annealed; the foregoing film forming device has: a vacuum chamber; a pressure maintaining means for maintaining a pressure in the vacuum chamber at a time of film formation of 0.3 Pa or less; and a temperature maintaining means for maintaining a temperature of the film formation object at a time of film formation at 100 ° C or lower; An annealing furnace for heating the aforementioned indium oxide film at 100 ° C or lower. The film manufacturing apparatus of the requested item 4, wherein the film forming apparatus having the film forming chamber when the moisture partial pressure was maintained at 5.8 × 10 ^-4 Pa or less means to maintain the partial pressure of water. The membrane manufacturing apparatus according to claim 5, wherein the moisture partial pressure maintaining means maintains a partial pressure of moisture in the chamber at the time of film formation at 3.9 × 10 ^-4 Pa or less.