JP6608537B2 - Film forming apparatus and film forming method - Google Patents

Description

  The present invention relates to a film forming apparatus and a film forming method.

  In film formation of a transparent conductive film used for a touch panel or the like, generally, a sputtering method excellent in large area film formation, film film quality control and the like is employed. In the sputtering method, oxygen gas may be introduced into the vacuum vessel in order to suppress oxygen deficiency in the transparent conductive film (see, for example, Patent Document 1).

  However, in an actual film forming process, gases other than the introduced gas are also present in the vacuum vessel. An example of such a gas is water vapor. For example, water vapor is released from components installed in the inner wall of the processing chamber or the vacuum chamber. The water vapor is sufficiently degassed by baking while evacuating the vacuum container in advance or by performing preliminary discharge before film formation.

  However, in the film forming apparatus, the substrate is periodically carried into a processing chamber from another vacuum chamber, or the substrate after film forming processing is again carried out from the processing chamber to another vacuum chamber. There is something. In such an apparatus, a new substrate carried in from another vacuum chamber and a carrier for holding the substrate may become a water vapor source again. Furthermore, when the processing chamber is opened by loading and unloading the substrate and the carrier, the water vapor may move between another vacuum chamber and the processing chamber.

  Therefore, in the actual film forming process, the water vapor partial pressure in the processing chamber is not stable, and the film quality of the transparent conductive film may vary from film to film.

International Publication No. 2010/004937

  In view of the circumstances as described above, an object of the present invention is to provide a film forming apparatus and a film forming method in which the water vapor partial pressure in the processing chamber is stabilized and the film quality of the transparent conductive film is more stable.

In order to achieve the above object, a film forming apparatus according to one embodiment of the present invention includes a first vacuum chamber, a gas supply source, a film forming source, and a control device. In the first vacuum chamber, the reduced pressure state is maintained, and the carrier for holding the substrate can be carried in and out. The gas supply source can supply water vapor gas to the first vacuum chamber. The film formation source is disposed in the first vacuum chamber and can generate a material for the transparent conductive film formed on the substrate. In the control device, when the transparent conductive film is formed on the substrate, a water vapor partial pressure in the first vacuum chamber is in a range not lower than a first partial pressure and not higher than a second partial pressure higher than the first partial pressure. To control.
According to such a film forming apparatus, even if water vapor is released from other than the gas supply source in the first vacuum chamber, the water vapor partial pressure in the first vacuum chamber is not less than the first partial pressure and not more than the second partial pressure. Controlled to range. Thereby, the film quality of a transparent conductive film becomes more stable.

In the film forming apparatus, the partial pressure of the water vapor in the first vacuum chamber includes a partial pressure of the water vapor gas supplied from the gas supply source, an inner wall of the first vacuum chamber, the substrate, the carrier, and And a partial pressure of water vapor gas discharged from at least one of the film forming sources.
According to such a film forming apparatus, the partial pressure of the water vapor gas supplied from the gas supply source is the partial pressure of the water vapor in the first vacuum chamber, the inner wall of the first vacuum chamber, the substrate, and the carrier. And the partial pressure of the water vapor gas discharged from at least one of the film forming sources, the water vapor partial pressure in the first vacuum chamber is controlled to be in a range from the first partial pressure to the second partial pressure, and transparent. The film quality of the conductive film is more stable.

In the film forming apparatus, when the water vapor partial pressure in the first vacuum chamber is equal to or lower than a third partial pressure lower than the second partial pressure and higher than the first partial pressure, Control is performed to supply the water vapor gas at a first flow rate to the first vacuum chamber by the gas supply source. When the water vapor partial pressure in the first vacuum chamber is lower than the third partial pressure and lower than a fourth partial pressure higher than the first partial pressure, the control device causes the gas to enter the first vacuum chamber. Control is performed to supply the water vapor gas at a second flow rate larger than the first flow rate by a supply source. When the water vapor partial pressure in the first vacuum chamber becomes larger than the third partial pressure, the control device reduces the water vapor gas to be smaller than the first flow rate by the gas supply source in the first vacuum chamber. Control to supply at the third flow rate is performed.
According to such a film forming apparatus, even when water vapor is released from the substrate or the carrier, the water vapor partial pressure in the first vacuum chamber is kept within a range between the first partial pressure and the second partial pressure. Water vapor is introduced into one vacuum chamber, and the film quality of the transparent conductive film becomes more stable.

In the film forming apparatus, a second vacuum chamber connectable to the first vacuum chamber in a reduced pressure state, an opening through which the carrier is transferred between the second vacuum chamber and the first vacuum chamber, You may further provide the valve which opens and closes the said opening.
According to such a film forming apparatus, even if the water vapor moves between the second vacuum chamber and the first vacuum chamber, the water vapor partial pressure in the first vacuum chamber is equal to or higher than the first partial pressure and the second partial pressure. Water vapor is introduced into the first vacuum chamber so as to be within the range below the pressure, and the film quality of the transparent conductive film is further stabilized.

In the film forming apparatus, the second flow rate is greater than 100% of the first flow rate and 110% or less, and the third flow rate is 90% or more and less than 100% of the first flow rate. May be.
According to such a film forming apparatus, even when water vapor is released from the substrate or the carrier, the first water vapor partial pressure in the first vacuum chamber is kept within the range of the first partial pressure to the second partial pressure. Water vapor is introduced into one vacuum chamber, and the film quality of the transparent conductive film becomes more stable.

In order to achieve the above object, a film forming method according to an embodiment of the present invention includes supplying water vapor gas to a first vacuum chamber in which a reduced pressure state is maintained and a carrier holding a substrate can be carried in and out. A transparent conductive film material is generated from a film forming source disposed in the first vacuum chamber. The transparent conductive film is formed on the substrate by controlling the partial pressure of water vapor in the first vacuum chamber to a range not lower than the first partial pressure and not higher than the second partial pressure higher than the first partial pressure.
According to such a film forming method, the partial pressure of water vapor in the first vacuum chamber is controlled in the range of the first partial pressure to the second partial pressure, and the film quality of the transparent conductive film is further stabilized.

In the film forming method, the water vapor gas supplied from a gas supply source, the inner wall of the first vacuum chamber, the substrate, the carrier, and the film forming source are used as the water vapor gas in the first vacuum chamber. You may use the water vapor | steam gas discharge | released from either.
According to such a film formation method, the water vapor partial pressure of the first vacuum chamber is supplied from the gas supply source, the inner wall of the first vacuum chamber, the substrate, the carrier, and the component. The water vapor partial pressure in the first vacuum chamber is controlled to be in the range from the first partial pressure to the second partial pressure, and the film quality of the transparent conductive film is further improved. Stabilize.

In the film forming method, when the water vapor partial pressure in the first vacuum chamber is lower than the second partial pressure and lower than or equal to a third partial pressure higher than the first partial pressure, the first vacuum chamber The gas supply source may supply the water vapor gas at a first flow rate, and the water vapor partial pressure in the first vacuum chamber is lower than the third partial pressure and higher than the first partial pressure. When the pressure is lower than the pressure, the water vapor gas may be supplied to the first vacuum chamber by the gas supply source at a second flow rate larger than the first flow rate, and the partial pressure of the water vapor in the first vacuum chamber is When it becomes larger than the third partial pressure, the water vapor gas may be supplied to the first vacuum chamber by the gas supply source at a third flow rate smaller than the first flow rate.
According to such a film forming method, even when water vapor is released from the substrate or the carrier, the water vapor partial pressure in the first vacuum chamber is kept within the range of the first partial pressure to the second partial pressure. Water vapor is introduced into one vacuum chamber, and the film quality of the transparent conductive film becomes more stable.

In the film forming method, a second vacuum chamber that can be connected to the first vacuum chamber in a reduced pressure state may be used, and the substrate and the above-described substrate are placed in the first vacuum chamber through an opening from the second vacuum chamber. A carrier may be carried in, and sputtering deposition may be performed on the substrate in the first vacuum chamber.
According to such a film forming method, even if water vapor moves between the second vacuum chamber and the first vacuum chamber, the water vapor partial pressure in the first vacuum chamber is equal to or higher than the first partial pressure and the second partial pressure. Water vapor is introduced into the first vacuum chamber so as to be within the range below the pressure, and the film quality of the transparent conductive film is further stabilized.

In the film forming method, the second flow rate is greater than 100% of the first flow rate and 120% or less, and the third flow rate is 80% or more and less than 100% of the first flow rate. May be.
According to such a film forming method, even when water vapor is released from the substrate or the carrier, the water vapor partial pressure in the first vacuum chamber is kept within the range of the first partial pressure to the second partial pressure. Water vapor is introduced into one vacuum chamber, and the film quality of the transparent conductive film becomes more stable.

  As described above, according to the present invention, there is provided a film forming apparatus and a film forming method in which the water vapor partial pressure in the processing chamber is stabilized and the film quality of the transparent conductive film is more stable.

It is a schematic sectional drawing of the film-forming apparatus which concerns on this embodiment. It is a graph which shows an example of the relationship between water vapor partial pressure and the resistivity of a transparent conductive film. It is a time chart figure by which the water vapor partial pressure in the 1st vacuum chamber is controlled. It is a graph which shows an example of the relationship between oxygen partial pressure and the resistivity of an ITO film.

  Hereinafter, embodiments of the present invention will be described with reference to the drawings. In each drawing, XYZ axis coordinates may be introduced.

  FIG. 1 is a schematic cross-sectional view of a film forming apparatus according to this embodiment.

  A film forming apparatus 101 shown in FIG. 1 includes a vacuum vessel 10, a substrate transport mechanism 20, a film forming source 30, a gas supply source 70, a pressure gauge 75, and a control device 80.

  The vacuum container 10 includes a first vacuum chamber 11, a second vacuum chamber 12, and a third vacuum chamber 13. In FIG. 1, a part of each of the second vacuum chamber 12 and the third vacuum chamber 13 is shown. The number of vacuum chambers is not limited to three, and may be two or less, or four or more.

  Each of the first vacuum chamber 11, the second vacuum chamber 12, and the third vacuum chamber 13 can maintain a reduced pressure state. For example, the gas in the first vacuum chamber 11 is exhausted to the outside through an exhaust port 10d by an exhaust mechanism such as a turbo molecular pump. Each of the second vacuum chamber 12 and the third vacuum chamber 13 is also maintained in a reduced pressure state by the exhaust mechanism. The exhaust mechanism may be provided with a cryotrap upstream of the turbo molecular pump.

  In the example of FIG. 1, a continuous (for example, in-line) film forming apparatus 101 is shown. For example, the second vacuum chamber 12 can be connected to the first vacuum chamber 11 in a reduced pressure state. The third vacuum chamber 13 can be connected to the first vacuum chamber 11 in a reduced pressure state. In the vacuum vessel 10, a valve 15 is provided on the side wall 10wa, and a valve 16 is provided on the side wall 10wb.

  For example, when the valve 15 is opened, an opening is formed between the second vacuum chamber 12 and the first vacuum chamber 11, and when the valve 15 is closed, the second vacuum chamber 12 and the first vacuum chamber 11 are The opening between is closed. When the valve 16 is in an open state, an opening is formed between the first vacuum chamber 11 and the third vacuum chamber 13, and when the valve 16 is in a closed state, it is between the first vacuum chamber 11 and the third vacuum chamber 13. The opening of is closed.

  The first vacuum chamber 11 functions as a processing chamber capable of forming a film in the film forming apparatus 101. For example, the valve 15 is opened, the substrate 21 and the carrier (substrate holder) 22 that supports the substrate 21 are carried into the first vacuum chamber 11 from the second vacuum chamber 12 through the opening, and the valve 15 is closed. Then, sputtering film formation is performed on the substrate 21 in the first vacuum chamber 11. When the sputtering film formation is completed, the valve 16 is opened, and the substrate 21 and the carrier 22 are carried out from the first vacuum chamber 11 to the third vacuum chamber 13 through the opening.

  The substrate 21 includes, for example, a glass substrate having a rectangular planar shape. The surface on which the substrate 21 faces the film forming source 30 is a film forming surface 21d.

  The substrate transport mechanism 20 carries the substrate 21 into the first vacuum chamber 11 and carries it out of the first vacuum chamber 11. For example, the substrate transport mechanism 20 includes a roller rotation mechanism 20r and a frame portion 20f. The roller rotation mechanism 20r is supported by the frame portion 20f. When the substrate 21 and the carrier 22 are placed on the roller rotation mechanism 20r, the roller rotation mechanism 20r rotates and the substrate 21 and the carrier 22 are slid and transferred from the valve 15 toward the valve 16.

  The loading / unloading of the substrate 21 in the first vacuum chamber 11 is automatically performed, for example. Further, the number of substrates on which film formation processing is performed by the film formation apparatus 101 is not limited to one. For example, a plurality of substrates 21 charged in the film forming apparatus 101 are periodically subjected to film formation one by one in the first vacuum chamber 11. Thereby, one of the valves 15 and 16 is opened and closed periodically.

  The film formation source 30 includes a first film formation source 31 and a second film formation source 32. The first film formation source 31 includes a first target 31T, a first backing tube 31B, a first magnetic circuit 31M, and a first power source 35P. The second film formation source 32 includes a second target 32T, a second backing tube 32B, a second magnetic circuit 32M, and a second power source 36P. The first target 31T and the second target 32T are so-called rotary targets.

  The first target 31T is supported by the first backing tube 31B. The first magnetic circuit 31M is disposed in the first target 31T and is disposed in the first backing tube 31B. The second target 32T is supported by the second backing tube 32B. The second magnetic circuit 32M is disposed in the second target 32T and is disposed in the second backing tube 32B. A flow path (not shown) through which a cooling medium flows may be provided inside each of the first backing tube 31B and the second backing tube 32B.

  The first target 31T and the second target 32T are opposed to the substrate 21. The first target 31T and the second target 32T are disposed along the transport direction (arrow T (Y-axis direction)) of the substrate 21. The central axis 31c of the first target 31T is parallel to the longitudinal direction (X-axis direction) of the first target 31T. The central axis 32c of the second target 32T is parallel to the longitudinal direction (X-axis direction) of the second target 32T.

  Each of the first target 31T, the first backing tube 31B, the second target 32T, and the second backing tube 32B has a cylindrical shape. However, each of the first target 31T, the first backing tube 31B, the second target 32T, and the second backing tube 32B is not limited to a cylindrical type, and may be a disk type.

  The central axis 31c of the first target 31T intersects the transport direction T of the substrate 21. The center axis 32c of the second target 32T intersects the transport direction of the substrate 21. For example, each of the central axes 31c and 32c is orthogonal to the Y-axis direction and parallel to the X-axis direction. The first target 31T is configured to be rotatable about the central axis 31c. The second target 32T is configured to be rotatable about the central axis 32c.

  The material of the first target 31T may be the same as or different from the material of the second target 32T. For example, each of the first target 31T and the second target 32T includes ITO (indium tin oxide (tin oxide content: 1 wt% or more and 15 wt% or less)). The content of tin oxide in ITO is an example and is not limited to this value. Note that a deposition preventing plate 10 p is provided between the substrate transport mechanism 20 and the film forming source 30.

  In the film forming apparatus 101, the first magnetic circuit 31M may be configured to be rotatable about the central axis 31c, and the second magnetic circuit 32M may be configured to be rotatable about the central axis 32c. Accordingly, the position of magnetic lines of force (magnetic field formed along the surface of the first target 31T) leaking from the first magnetic circuit 31M to the surface of the first target 31T is configured to be variable. Further, the position of magnetic lines of force (magnetic field formed along the surface of the second target 32T) leaking from the second magnetic circuit 32M to the surface of the second target 32T is configured to be variable.

  In the example of FIG. 1, for example, each of the first magnetic circuit 31M and the second magnetic circuit 32M is disposed so as to face the substrate 21 via the target. Thereby, the magnetic flux density on the surface of the first target 31 </ b> T is increased between the first target 31 </ b> T and the substrate 21. Furthermore, the magnetic flux density on the surface of the second target 32T increases between the second target 32T and the substrate 21.

  In the film forming apparatus 101, when a discharge gas is introduced into the vacuum vessel 10 and a voltage is applied to the first target 31T from the first power supply 35P, the first target 31T and the ground portion (the vacuum vessel 10, the substrate transfer mechanism). 20, the carrier 22, the deposition plate 10 p, and the like), and the discharge gas is ionized, and plasma is generated between the first target 31 </ b> T and the ground portion. Further, when a voltage is applied to the second target 32T from the second power source 36P, the discharge gas is ionized between the second target 32T and the ground portion, and plasma is generated between the second target 32T and the ground portion. Occur.

  The voltage supplied to each target is a DC voltage or an AC voltage. The frequency of the AC voltage is 10 kHz or more and 300 MHz or less (for example, 13.56 MHz).

  Sputtered particles emitted from each of the first target 31T and the second target 32T reach the film formation surface 21d of the substrate 21. Thereby, a layer (for example, a transparent conductive film) in which the sputtered particles S1 sputtered from the first target 31T and the sputtered particles S2 sputtered from the second target 32T are mixed is formed on the film forming surface 21d. .

  The gas supply source 70 includes a flow rate regulator 71 and a gas nozzle 72. The flow rate regulator 71 includes a first flow rate regulator 71a, a second flow rate regulator 71b, and a third flow rate regulator 71c. The gas nozzle 72 includes a first gas nozzle 72a, a second gas nozzle 72b, and a third gas nozzle 72c. Each of the first flow rate regulator 71a, the second flow rate regulator 71b, and the third flow rate regulator 71c is controlled by the control device 80. The numbers of the flow rate adjusters 71 and the gas nozzles 72 are not limited to the illustrated numbers.

The first vacuum chamber 11 is supplied with discharge gas into the vacuum vessel 10 by a gas supply source 70. The discharge gas is, for example, a rare gas such as argon or helium, oxygen (O ₂ ), water vapor (H ₂ 0), or the like. For example, the rare gas is supplied to the first vacuum chamber 11 by the first flow rate regulator 71a and the first gas nozzle 72a. Oxygen is supplied to the first vacuum chamber 11 by the second flow rate regulator 71b and the second gas nozzle 72b. The water vapor is supplied to the first vacuum chamber 11 by the third flow rate regulator 71c and the third gas nozzle 72c.

  The pressure gauge 75 includes a first pressure gauge 75a and a second pressure gauge 75b. For example, the total pressure in the first vacuum chamber 11 is measured by the first pressure gauge 75a, and the water vapor partial pressure in the first vacuum chamber 11 is measured by the second pressure gauge 75b. For example, the first pressure gauge 75a is an ionization vacuum gauge, and the second pressure gauge 75b is a mass spectrometer. The measurement values measured by the first pressure gauge 75a and the second pressure gauge 75b are sent to the control device 80.

  A film forming method (operation) of the film forming apparatus 101 will be described.

  In the film forming apparatus 101, the gas supply source 70 is a water vapor gas supply source that supplies water vapor gas to the first vacuum chamber 11. However, in the film forming apparatus 101, a portion other than the gas supply source 70 may be a water vapor source.

  For example, in the film forming apparatus 101, a very small amount of water vapor gas is released from the surface of at least one of the vacuum vessel 10, the deposition plate 10p, the substrate transport mechanism 20, the substrate 21, the carrier 22, and the film forming source 30. There is a case.

  For example, in the film forming apparatus 101, new substrates 21 and carriers 22 are periodically carried into the first vacuum chamber 11. Thereby, the substrate 21 and the carrier 22 newly carried in may be a water vapor source for each film forming process.

  Further, even if a baking process (degassing process) is previously performed on the vacuum vessel 10, the deposition plate 10p, the substrate transport mechanism 20, and the like before the start of film formation, the vacuum vessel 10, the deposition plate 10p, and the When the substrate transport mechanism 20 or the like is reheated by the plasma, water vapor may be released from the respective surfaces of the vacuum container 10, the deposition preventing plate 10p, the substrate transport mechanism 20 and the like.

  In particular, when the substrate 21 is a large substrate (for example, planar size: 1500 mm × 1850 mm or more), the carrier 22 that supports the substrate 21, the substrate transport mechanism 20 that transports the carrier 22, and the deposition preventing plate 10 p are also large. Thereby, the water vapor gas emitted from the respective surfaces of the substrate 21, the carrier 22, the substrate transport mechanism 20 and the deposition preventing plate 10p cannot be ignored. Further, when the valves 15 and 16 are opened by the substrate transfer, water vapor moves between the second vacuum chamber 12 and the first vacuum chamber 11, or between the third vacuum chamber 12 and the first vacuum chamber 11. In some cases, water vapor may move.

  Therefore, even when a constant flow rate of water vapor gas is supplied to the first vacuum chamber 11 by the gas supply source 70, the water vapor gas discharged from other than the gas supply source 70 is added, and the water vapor partial pressure in the first vacuum chamber 11 may vary. is there. When the water vapor partial pressure in the first vacuum chamber 11 varies, the degree of oxygen deficiency in the transparent conductive film varies, and the film quality (for example, resistivity) of the transparent conductive film may vary.

  For example, FIG. 2 is a graph showing an example of the relationship between the water vapor partial pressure and the resistivity of the transparent conductive film.

The film forming conditions are as follows.
Target material: indium oxide (95 wt%) / tin oxide (5 wt%)
Power: 6W / ^cm 2 (DC power supply)
Discharge gas: Argon / water vapor Total pressure: 0.4 Pa
Water vapor flow rate / (Argon flow rate + Water vapor flow rate): 0% or more and 4% or less Water vapor partial pressure: 0 Pa or more and 0.018 Pa or less Substrate temperature: 37 ° C.
Film annealing: 120 ° C, 60 minutes

  FIG. 2 shows the result of the ITO film formed on the glass substrate (ITO Layer / Glass) and the result of the ITO film formed on the glass substrate through the IM (Index Matched) film (ITO Layer / IM Layer / Glass). As shown in FIG. 2, it can be seen that the resistivity of the ITO film changes according to the water vapor partial pressure.

In order to suppress this variation, the water vapor partial pressure (P _H20 ) in the first vacuum chamber 11 is _divided by the water vapor gas supplied from the gas supply source 70 and the water vapor gas released from other than the gas supply source 70. It is necessary to control the total amount of water vapor present in the first vacuum chamber 11 on the assumption that the pressure is included.

A method for controlling the water vapor partial pressure (P _H20 ) in the present embodiment will be described.

  FIG. 3 is a time chart for controlling the water vapor partial pressure in the first vacuum chamber. The horizontal axis represents time (standard value), the left vertical axis represents water vapor partial pressure (standard value), and the right vertical axis represents water vapor flow rate (standard value) from the gas supply source 70.

In the film forming apparatus 101, when a transparent conductive film is formed on the substrate 21 in the first vacuum chamber 11, the control device 80 corresponds to the water vapor partial pressure (P _H20 ) measured by the second pressure gauge 75 b. The flow rate of water vapor supplied from the gas supply source 70 to the first vacuum chamber 11 is controlled. For example, during film formation of the transparent conductive film, the control device 80 controls the water vapor partial pressure in the first vacuum chamber 11 to be in the range of the first partial pressure (P1) to the second partial pressure (P2). Here, it is assumed that the second partial pressure (P2) is higher than the first partial pressure (P1).

For example, it is assumed that the substrate 21 and the carrier 22 are transferred from the other vacuum chamber to the first vacuum chamber 11 of the film forming apparatus 101. Subsequently, the first vacuum chamber 11 is evacuated by the exhaust mechanism. As a result, the water vapor partial pressure (P _H20 ) in the first vacuum chamber 11 gradually decreases (FIG. 3: section A). At this stage, water vapor is not supplied to the first vacuum chamber 11 by the gas supply source 70.

Next, when the water vapor partial pressure (P _H20 ) in the first vacuum chamber 11 becomes equal to or lower than the third partial pressure (P 3), the control device 80 supplies water vapor gas to the first vacuum chamber 11 by the gas supply source 70. Control to supply at one flow rate (F1) is performed. Here, the third partial pressure (P3) is lower than the second partial pressure (P2) and higher than the first partial pressure (P1).

Next, when the water vapor partial pressure (P _H20 ) in the first vacuum chamber 11 becomes equal to or lower than the fourth partial pressure (P 4), the control device 80 supplies water vapor gas to the first vacuum chamber 11 by the gas supply source 70. Control is performed to supply a second flow rate (F2) larger than the first flow rate (F1). Here, the fourth partial pressure (P4) is a partial pressure lower than the third partial pressure (P3) and higher than the first partial pressure (P1).

Next, when the water vapor partial pressure (P _H20 ) in the first vacuum chamber 11 becomes higher than the third partial pressure (P3), the control device 80 supplies water vapor to the first vacuum chamber 11 by the gas supply source 70. Control is performed to supply a third flow rate (F3) smaller than one flow rate (F1).

As an example, the first partial pressure (P1) is 8 × 10 ⁻⁴ Pa to 1 × 10 ⁻³ Pa and the fourth partial pressure (P4) is 1 × 10 ⁻³ Pa to 5 × 10 ^−3. The third partial pressure (P3) is 5 × 10 ⁻³ Pa or more and 1 × 10 ⁻² Pa or less, and the second partial pressure (P2) is 1 × 10 ⁻² Pa or more and 2 × 10. ^-2 it is Pa or less. The second flow rate (F2) is a flow rate that is greater than 100% and less than or equal to 120% of the first flow rate (F1). For example, the second flow rate (F2) is 110% of the first flow rate (F1). The third flow rate (F3) is a flow rate that is 80% or more and less than 100% of the first flow rate (F1). For example, the third flow rate (F3) is 90% of the first flow rate (F1).

  The film formation of the transparent conductive film is performed in a state where the water vapor partial pressure is within the range of the first partial pressure (P1) to the second partial pressure (P2) (FIG. 3: B section). If such control is performed, the water vapor partial pressure in the first vacuum chamber 11 is reliably controlled in the range of the first partial pressure (P1) or more and the second partial pressure (P2) or less, and the film quality of the transparent conductive film (for example, , Resistivity) variation is suppressed.

As described above, in the present embodiment, water vapor gas is supplied to the first vacuum chamber 11 in which the substrate 21 and the carrier 22 can be carried in and out, and the transparent conductive material is supplied from the film forming source 30 disposed in the first vacuum chamber 11. Generate membrane material. Then, the transparent conductive film is formed on the substrate 21 by controlling the water vapor partial pressure (P _H20 ) in the first vacuum chamber 11 to be in the range from the first partial pressure (P 1) to the second partial pressure (P 2).

According to the deposition apparatus 101, in the first vacuum chamber 11, again, even if release water vapor from the non-gas supply source 70, water vapor partial pressure in the first vacuum chamber 11 (P _H20) is first minute The pressure is controlled in the range from the pressure (P1) to the second partial pressure (P2), and the film quality of the transparent conductive film becomes more stable.

  Furthermore, when the water vapor partial pressure was appropriately controlled, further effects were obtained as the characteristics of the transparent conductive film.

  4A and 4B are graphs showing an example of the relationship between the oxygen partial pressure and the resistivity of the ITO film. However, FIG. 4B shows an example in which water vapor gas is added during the ITO film formation.

The film forming conditions are as follows. Note that the white triangle marks in the figure are subjected to film annealing at 120 ° C. for 60 minutes after film formation.
Target material: indium oxide (95 wt%) / tin oxide (5 wt%)
Electric power: 6kW / m (DC power supply)
Discharge gas: argon / oxygen (FIG. 4 (a)), argon / oxygen / water vapor (FIG. 4 (b))
Total pressure: 0.4Pa
Oxygen partial pressure: 0.004 Pa or more and 0.023 Pa or less Water vapor partial pressure: 0.009 Pa (FIG. 4B)
Substrate temperature: 37 ° C

  As shown in FIG. 4A, the resistivity of the ITO film changes according to the oxygen partial pressure. For example, in FIG. 4A, when the oxygen partial pressure increases from 0.004 Pa to 0.018 Pa, the resistivity of the ITO film decreases. However, when the oxygen partial pressure exceeds 0.018 Pa, the resistivity of the ITO film tends to increase again. Such a change in resistivity is caused by, for example, one factor that the electron mobility decreases due to oxygen vacancies, or conversely the carriers increase due to oxygen vacancies. In addition, when the annealed ITO film is annealed, the resistivity of the ITO film tends to further decrease. This is thought to be due to the fact that the crystallization of the ITO film progressed due to the annealing treatment, and the resistivity of the ITO film further decreased.

  On the other hand, when water vapor was added together with oxygen as an additive gas during film formation, the resistivity of the ITO film further decreased as shown in FIG. As one of the factors, it is presumed that when water vapor is added during film formation, microcrystallization in the ITO film is suppressed. To confirm this, when the ITO film to which water vapor was added was annealed, the resistivity was further lowered. This is presumed that the crystallization of the ITO film further progressed by the annealing treatment because the microcrystallization of the ITO film was previously suppressed by the addition of water vapor.

  As described above, it was found that the selection range of the resistivity of the ITO film is widened by adjusting the water vapor partial pressure in forming the ITO film.

  As mentioned above, although embodiment of this invention was described, this invention is not limited only to the above-mentioned embodiment, Of course, a various change can be added.

DESCRIPTION OF SYMBOLS 10 ... Vacuum container 10wa, 10wb ... Side wall 10p ... Deposit board 10d ... Exhaust port 11 ... 1st vacuum chamber 12 ... 2nd vacuum chamber 13 ... 3rd vacuum chamber 15, 16 ... Valve 20 ... Substrate conveyance mechanism 20r ... Roller rotation Mechanism 20f ... Frame portion 21 ... Substrate 21d ... Film formation surface 22 ... Carrier 30 ... Film formation source 31 ... First film formation source 31M ... First magnetic circuit 31T ... First target 31B ... First backing tube 32 ... Second composition Film source 32M ... second magnetic circuit 32B ... second backing tube 32T ... second target 31c, 32c ... center axis 35P ... first power source 36P ... second power source 70 ... gas supply source 71 ... flow rate regulator 71b ... first flow rate Adjuster 71a ... second flow rate adjuster 71c ... third flow rate adjuster 72 ... gas nozzle 72a ... first gas nozzle 72b ... second gas nozzle 72c ... third gas Nozzle 75 ... Pressure gauge 75a ... First pressure gauge 75b ... Second pressure gauge 80 ... Control device 101 ... Film forming device

Claims (8)

A first vacuum chamber in which a reduced pressure state is maintained and a carrier for holding a substrate can be carried in and out;
A gas supply source capable of supplying water vapor gas to the first vacuum chamber;
A film forming source disposed in the first vacuum chamber and capable of generating a material of a transparent conductive film formed on the substrate;
When the transparent conductive film is formed on the substrate, the water vapor partial pressure of the first vacuum chamber is controlled to a range of the first partial pressure or higher and the second partial pressure higher than the first partial pressure , When the water vapor partial pressure in the first vacuum chamber is lower than the third partial pressure lower than the second partial pressure and higher than the first partial pressure, the water vapor gas is supplied to the first vacuum chamber by the gas supply source. Is supplied at a first flow rate, and when the water vapor partial pressure in the first vacuum chamber is lower than the third partial pressure and lower than the fourth partial pressure higher than the first partial pressure, the first vacuum chamber When the water vapor gas is supplied at a second flow rate larger than the first flow rate by the gas supply source, and the water vapor partial pressure in the first vacuum chamber becomes larger than the third partial pressure, the first Supplying the water vapor gas to the vacuum chamber at a third flow rate smaller than the first flow rate by the gas supply source Film forming apparatus and a control device for controlling that. The film forming apparatus according to claim 1,
The partial pressure of water vapor in the first vacuum chamber is at least one of a partial pressure of the water vapor gas supplied from the gas supply source, an inner wall of the first vacuum chamber, the substrate, the carrier, and the film formation source. A film forming apparatus including a partial pressure of water vapor gas discharged from the apparatus. The film forming apparatus according to claim 1 or 2 ,
A second vacuum chamber connectable to the first vacuum chamber in a reduced pressure state;
An opening through which the carrier is transferred between the second vacuum chamber and the first vacuum chamber;
A film forming apparatus further comprising a valve for opening and closing the opening. The film forming apparatus according to any one of claims 1 to 3 ,
The second flow rate is greater than 100% and less than or equal to 120% of the first flow rate,
The third flow rate is 80% or more of the first flow rate and smaller than 100%. Supplying water vapor gas to the first vacuum chamber in which the reduced pressure state is maintained and the carrier holding the substrate can be carried in and out;
Generating a transparent conductive film material from a film forming source disposed in the first vacuum chamber;
The water vapor partial pressure in the first vacuum chamber is controlled to be in a range not less than a first partial pressure and not higher than a second partial pressure higher than the first partial pressure, and the water vapor partial pressure in the first vacuum chamber is set to the second partial pressure. When the pressure is lower than the third partial pressure lower than the first partial pressure and lower than the first partial pressure, the water vapor gas is supplied to the first vacuum chamber by a gas supply source at a first flow rate, and the first vacuum chamber When the water vapor partial pressure becomes lower than the fourth partial pressure lower than the third partial pressure and higher than the first partial pressure, the water vapor gas is supplied to the first vacuum chamber from the first flow rate by the gas supply source. When the water vapor partial pressure in the first vacuum chamber becomes larger than the third partial pressure, the water vapor gas is supplied to the first vacuum chamber by the gas supply source. A film forming method of forming a transparent conductive film on the substrate by supplying a third flow rate smaller than the flow rate . The film forming method according to claim 5 ,
As the vapor gas of the first vacuum chamber, and steam gas supplied from the gas supply source, an inner wall of the first vacuum chamber, said substrate, water vapor gas discharged from at least one of the carrier and the film forming source And a film forming method. The film forming method according to claim 5 or 6 ,
Using a second vacuum chamber connectable to the first vacuum chamber in a reduced pressure state;
Carrying the substrate and the carrier from the second vacuum chamber into the first vacuum chamber through an opening;
A film forming method of performing sputtering film formation on the substrate in the first vacuum chamber. A film forming method according to any one of claims 5-7,
The second flow rate is greater than 100% and less than or equal to 120% of the first flow rate,
The third flow rate is 80% or more of the first flow rate and smaller than 100%.