JP5014243B2 - Functional film manufacturing method and functional film manufacturing apparatus - Google Patents

Description

  The present invention relates to the production of a functional film for forming a film on a substrate surface by a vacuum film forming method, and more specifically, a functional film having a good quality by greatly reducing the adverse effect of outgas released in the film forming chamber. The present invention relates to a functional film manufacturing method and a functional film manufacturing apparatus that can stably manufacture a film.

Various functional films such as gas barrier films, protective films, optical films such as optical filters and antireflection films, etc. in various devices such as optical elements, display devices such as liquid crystal displays and organic EL displays, semiconductor devices, thin film solar cells (Functional sheet) is used.
In addition, film formation (thin film formation) by a vacuum film formation method such as sputtering or plasma CVD is used for manufacturing these functional films.

In order to perform film formation efficiently and with high productivity by the vacuum film formation method, it is preferable to perform film formation continuously on a long substrate.
As equipment for carrying out such a film forming method, a supply roll formed by winding a long substrate (web-shaped substrate) in a roll shape, and a winding roll for winding a film-formed substrate in a roll shape, There is known a so-called roll-to-roll film-forming apparatus using a film. This roll-to-roll film forming apparatus inserts a long substrate from a supply roll to a take-up roll through a predetermined path passing through a film formation chamber for film formation on a substrate by plasma CVD. The film is continuously formed on the transported substrate in the film forming chamber while the substrate is fed out and the film-formed substrate is taken up by the take-up roll in synchronization.

By the way, in such continuous film formation on a long substrate by the vacuum film forming method, a gas such as moisture (outgas) released from the substrate or the inner wall of the vacuum chamber has a great influence on the film forming process.
For example, when an oxide film is formed by reactive sputtering, moisture (H ₂ O), which is the main outgas, decomposes into oxygen and also acts as a reaction gas. For this reason, the progress of oxidation of the film (degree of oxidation) varies depending on the amount of outgas. The influence of outgas becomes a serious problem particularly when the film composition and the color of the film are greatly changed by a slight change in the degree of oxidation, such as an aluminum oxide (Al ₂ O ₃ ) film.

In order to avoid such inconvenience, the substrate is generally heat-treated before film formation for the purpose of degassing the substrate. That is, prior to film formation, the substrate is heated to remove components that become outgas such as moisture contained in the substrate. In the case of a roll-to-roll apparatus, for example, a heat treatment chamber is provided upstream of the film formation chamber, and degassing is performed by heat treatment while transporting the substrate in the longitudinal direction.
However, the amount of outgas is not constant. For example, the type and storage state of the substrate, the air release time of the film forming apparatus, the state of the deposition plate placed in the film forming apparatus, the installation environment of the film forming apparatus Fluctuates greatly depending on etc. Further, in a roll-to-roll apparatus using a long substrate, the state of the substrate is often different in the longitudinal direction, that is, the amount of outgas emitted is distributed in the longitudinal direction of the substrate.

Therefore, there are many cases where the degassing process is insufficient under certain processing conditions.
On the contrary, in order to always perform sufficient degassing processing, it is necessary to lengthen the time of degassing processing, which causes a decrease in productivity. In particular, in the roll-to-roll apparatus, it is necessary to slow down the substrate transport speed in accordance with the degassing process rather than the film formation, and the problem of a decrease in productivity is great.

Various methods for solving such problems have been proposed.
For example, in Patent Document 1, in reactive sputtering, during film formation, the amounts of argon gas and oxygen gas (reactive gas) in a vacuum chamber are detected by a mass analyzer or the like, and argon gas in the vacuum chamber: A method of controlling the supply amount of oxygen gas so that the ratio of oxygen gas is constant is disclosed.
Patent Document 2 discloses a method for controlling the discharge power supply by controlling the discharge power supply in low-power control in reactive sputtering and feeding back the discharge voltage so that the discharge voltage of sputtering is constant. Is disclosed. Further, Patent Document 3 also discloses that oxygen gas in a vacuum chamber is detected by measuring the intensity of oxygen emission lines in plasma in reactive sputtering, and oxygen gas is set so that the oxygen ratio is constant. A method for controlling the amount of introduction is disclosed.

JP 2000-109973 A JP 2002-322561 A JP 2007-123701 A

According to the methods disclosed in the above-mentioned patent documents, in reactive sputtering, film formation on a substrate can be performed while controlling the influence of the reaction gas caused by outgas.
However, even if the control of the reaction gas corresponding to such outgas is performed, depending on the type and state of the substrate and the generation status of the plasma, the outgas is greatly adversely affected, and an appropriate product cannot be obtained. There are also many. In particular, in applications where high density such as a gas barrier film is required, since the film is formed with a low discharge pressure, the influence of outgas is large and improvement is desired.

  An object of the present invention is to solve the above-mentioned problems of the prior art, and in the production of a functional film that forms a film on the surface of a substrate using a vacuum film formation method involving generation of plasma such as reactive sputtering. Regardless of the state of the plasma, such as the type, state, and strength of the substrate, the functional film manufacturing method and manufacturing that can greatly reduce the adverse effects of outgas and enable stable production of appropriate products To provide an apparatus.

  In order to achieve the above object, the functional film manufacturing method of the present invention, when performing film formation on the surface of a substrate by a vacuum film formation method accompanied by generation of plasma, prior to film formation by the vacuum film formation method, A degassing process for performing a heat treatment and a plasma treatment after the heat treatment is performed, and a hydrogen gas amount is detected in a processing chamber for performing the plasma treatment, so that the detected hydrogen gas amount becomes a predetermined amount or less. The functional film manufacturing method is characterized by controlling the conditions of the heat treatment.

  In such a functional film manufacturing method of the present invention, the heat treatment condition is such that the ratio of hydrogen gas partial pressure / plasma gas partial pressure detected in the treatment chamber for performing the plasma treatment is 0.01 or less. In addition, it is preferable that the vacuum film-forming method is reactive sputtering. Further, in the processing chamber for performing the plasma processing, the amount of the hydrogen gas can be controlled by mass spectrometry or plasma emission spectrometry. Detection is preferably performed.

  The functional film manufacturing apparatus of the present invention includes a film forming chamber for forming a film on a surface of the substrate by a vacuum film forming method accompanied by generation of plasma while conveying a long substrate in the longitudinal direction, and the film forming method. A degassing unit disposed upstream of the chamber and degassing the substrate while transporting the substrate in the longitudinal direction, and the degassing unit heats the substrate. A plasma processing chamber disposed downstream of the heat processing chamber and performing plasma processing on the substrate; and the plasma processing chamber further includes detection means for detecting an amount of hydrogen gas in the processing chamber. And the said heat processing chamber provides the functional film manufacturing apparatus characterized by controlling the heat processing conditions of the said board | substrate so that the amount of hydrogen gas by this detection means may be below predetermined amount.

  In such a functional film manufacturing apparatus of the present invention, the detection means detects a hydrogen gas partial pressure and a plasma gas partial pressure in the plasma processing chamber, and the heat processing chamber has the hydrogen gas partial pressure / It is preferable to control the heat treatment conditions of the substrate so that the plasma gas partial pressure ratio is 0.01 or less, and the film formation chamber forms a film on the surface of the substrate by reactive sputtering. Preferably, the detection means detects the amount of hydrogen gas released from the plasma processing chamber by mass spectrometry or plasma emission analysis.

In the present invention having the above structure, in order to reduce outgas released from the substrate during film formation, plasma treatment is performed after the heat treatment in the degassing treatment performed prior to the film formation, and then released by the plasma treatment. The amount of hydrogen gas to be detected is detected, and the heat treatment conditions are feedback-controlled according to the amount of hydrogen gas so that the amount of hydrogen gas becomes a predetermined amount or less.
According to the study by the present inventors, hydrogen gas as an outgas is damaged by attacking the substrate as hydrogen atoms or radicals, and is taken into the film to be formed to reduce the film density or reduce the film density. Cause defects. Therefore, according to the present invention, the amount of hydrogen gas released as outgas during film formation can be reduced to a predetermined amount or less by the degassing process, so that the adverse effect caused by the hydrogen gas can be greatly reduced and an appropriate function can be achieved. Can be produced stably.

  Hereinafter, the functional film manufacturing method and the functional film manufacturing apparatus of the present invention will be described in detail on the basis of preferred examples shown in the accompanying drawings.

  In FIG. 1, an example of the functional film manufacturing apparatus of this invention which implements the functional film manufacturing method of this invention is shown notionally.

A functional film manufacturing apparatus 10 (hereinafter referred to as a manufacturing apparatus 10) shown in FIG. 1 forms (forms) a film that expresses a target function on the surface of the substrate Z by reactive sputtering, thereby forming a functional film. And has a supply chamber 12, a degassing section 14, a film forming chamber 16, and a winding chamber 18.
Such a manufacturing apparatus 10 sends out the substrate Z from a substrate roll 20 formed by winding a long substrate Z (raw film) into a roll shape, and forms a film while transporting it in the longitudinal direction. This is an apparatus for forming a film by the aforementioned so-called roll-to-roll, in which Z is wound into a roll.

The supply chamber 12 includes a rotating shaft 24, a guide roller 26, and a vacuum exhaust unit 28.
In the manufacturing apparatus 10, a substrate roll 20 formed by winding a long substrate Z is loaded on the rotation shaft 24 of the supply chamber 12.
When the substrate roll 20 is loaded on the rotating shaft 24, the substrate Z passes through a predetermined transport path from the supply chamber 12 through the degassing unit 14 and the film forming chamber 16 to the winding shaft 25 of the winding chamber 18. Threaded (sent). In the manufacturing apparatus 10, the feeding of the substrate Z from the substrate roll 20 and the winding of the functional film 10 on the winding shaft 25 are performed in synchronization, and the long substrate Z is moved in the longitudinal direction along a predetermined transport path. The substrate Z is continuously degassed while being conveyed, and the film formation by reactive sputtering is continuously performed.

In the present invention, the substrate Z on which the film is formed is not particularly limited, and various types of resin films such as PET films, various metal sheets such as aluminum sheets, and the like are used for vacuum film formation methods (vapor phase deposition) accompanied by plasma generation. Any substrate that can be used for various functional films such as a gas barrier film, an optical film, and a protective film (base film) can be used.
In addition, the substrate Z has various functions such as a protective layer, an adhesive layer, a light reflection layer, a light shielding layer, a planarization layer, a buffer layer, and a stress relaxation layer on the surface of a resin film or a metal sheet as a base material. Various layers made of an inorganic material, an organic material, or the like may be formed.

In the supply chamber 12, the rotating shaft 24 is rotated clockwise in the drawing by a driving source (not shown), the substrate Z is sent out from the substrate roll 20, a predetermined path is guided by the guide roller 26, and the substrate Z is separated from the partition wall. The gas is sent from the slit 74 a provided in 74 to the degassing unit 14 (heat treatment chamber 30).
Further, in the manufacturing apparatus 10 shown in the drawing, as a preferred embodiment, the supply chamber 12 is also provided with a vacuum exhaust means 28. The supply chamber 12 is provided with a vacuum evacuation means 28, and during film formation, the supply chamber 12 is reduced in pressure (that is, heat treatment) in the heat treatment chamber 30 by setting the same degree of vacuum as that of the heat treatment chamber 30 described later. It has been prevented from affecting.

  The vacuum evacuation means 28 is not particularly limited, and a vacuum pump such as a turbo pump, a mechanical booster pump, and a rotary pump, an auxiliary means such as a cryocoil, an ultimate vacuum degree and an exhaust amount adjustment means, etc. are utilized. Various known (vacuum) evacuation means used in vacuum film forming apparatuses can be used. In this regard, the same applies to other vacuum exhaust means described later.

In the present invention, it is not limited to providing the evacuation means in all the chambers, but the supply chamber 12 and the winding chamber 18 (or further, the heat treatment chamber 30 when the pressure is not reduced by the heat treatment), etc. A chamber that does not require evacuation as a treatment need not be provided with a evacuation unit. However, when the adjacent chambers are evacuated, in order to reduce the influence on the degree of vacuum of the adjacent chambers, the portion through which the substrate Z passes, such as the slit 74a, is made as small as possible, A sub chamber may be provided between the chamber and the inside of the sub chamber.
In the illustrated manufacturing apparatus 10 having the vacuum exhaust means in all the chambers, it is preferable to make the portion through which the substrate Z passes, such as the slit 74a, as small as possible.

The degassing unit 14 is a part that performs a so-called degassing process for removing a substance that becomes an outgas (released gas) released from the substrate Z during film formation from the substrate Z prior to film formation in the film formation chamber 16. is there.
In the present invention, the degassing unit 14 includes a heat treatment chamber 30 and a plasma treatment chamber 32.

As described above, the substrate Z is transferred to the heat treatment chamber 30 from the slit 74 a formed in the partition wall 74 that separates the supply chamber 12 and the heat treatment chamber 30.
The heat treatment chamber 30 is a part that removes (degass) a substance (mainly moisture) that becomes an outgas contained in the substrate Z by heating the substrate Z while being transported. In the illustrated example, the heat treatment chamber 30 includes a vacuum exhaust unit 34, guide rollers 36 a, 36 b and 36 c, heating units 38 a and 38 b, and a degassing control unit 40.

The heat treatment chamber 30 is decompressed to a predetermined degree of vacuum by the vacuum exhaust means 34.
In the heat treatment chamber 30, the substrate Z transported from the supply chamber 12 is first guided downward by the guide roller 36a, then guided upward by the guide roller 36b, and further guided to the plasma processing chamber 32 by the guide roller 36c. It is conveyed by a substantially U-shaped conveyance path.
In the downward path of the U-shaped transport path, the heating means 38a heats, and in the upward path, the heating means 38b heats to perform degassing processing.

The heating means 38a and 38b are not particularly limited, and any heating means used for degassing in the vacuum film method, such as a non-contact heating means such as an infrared heater, can be used. In addition to the non-contact type heating means, a contact type heating that heats the substrate Z by providing a heating means such as a heater or a heating medium circulation means on a member that contacts the substrate Z (for example, the guide roller 36b). Means can also be suitably used.
Further, the degree of vacuum and the heating temperature (temperature range for performing the heat treatment) in the heat treatment are not particularly limited, and may be appropriately set according to the heat resistance of the substrate Z and the like.

The heating by the heating means 38a and 38b and the evacuation by the evacuation means 34 are controlled (controlled) by the degassing control means 40.
The degassing control means 40 is heated by the heating means 38a and 38b and evacuated by the evacuation means 34 (heating process) according to the detection result of the hydrogen gas amount by the hydrogen gas detection means 54 of the plasma processing chamber 32 described later. The degree of decompression in the chamber 30 is controlled. This will be described in detail later.
The degassing control means 40 is not limited to controlling both heating and evacuation according to the detection result of the hydrogen gas amount by the hydrogen gas detecting means 54, and either one of the conditions is fixed. Only the other may be controlled according to the amount of hydrogen gas.

The substrate Z that has been heat-treated in the heat treatment chamber 30 is transferred to the plasma treatment chamber 32 from a slit 76 a formed in a partition wall 76 that separates the heat treatment chamber 30 and the plasma treatment chamber 32.
The plasma processing chamber 32 is a portion that performs plasma processing on the substrate Z degassed by the heat processing and detects the amount of hydrogen gas in the plasma processing chamber 32.
In the illustrated example, the plasma processing chamber 32 includes transport roller pairs 42a and 42b, a cathode 46, a high-frequency power source 48, a gas supply means 50, a vacuum exhaust means 52, and the hydrogen gas detection means 54. Composed.

The plasma processing in the plasma processing chamber 32 may be basically the same as the normal plasma processing performed in the manufacture of various functional films that are formed by vacuum film formation.
That is, the inside of the plasma processing chamber 32 is evacuated by the vacuum evacuation means 52, and a plasma gas (discharge gas) such as argon gas is introduced into the plasma processing chamber 32 by the gas supply means 50. And a predetermined power is supplied to the cathode 46 from the high-frequency power supply 48 and discharged to generate plasma in the plasma processing chamber 32, and the pair of transport rollers 42 a and 42 b (supply chamber 12). Plasma treatment is performed on the substrate Z transported by (toward the winding chamber 18).

As the cathode 46, the high frequency power supply 48, and the gas supply means 50, all of known ones used in various plasma processing apparatuses may be used.
Furthermore, the plasma processing conditions are not particularly limited, and may be set as appropriate according to the type of the substrate Z, the transfer speed, and the like. However, preferably, the plasma state in the plasma processing chamber 32 is close to the plasma state in the film formation chamber 16 according to the plasma state during film formation in the subsequent film formation chamber 16. More preferably, the plasma processing conditions are set to be substantially equal.

Here, the plasma processing chamber 32 has a hydrogen gas detection means 54. The hydrogen gas detection means 54 detects the amount of hydrogen gas in the plasma processing chamber 32.
In the manufacturing apparatus 10 of the present invention, the heat treatment conditions in the upstream heat treatment chamber 30 are controlled (feedback) so that the amount of hydrogen gas detected by the hydrogen gas detection means 54 is not more than a predetermined amount set in advance. Control.
By having such a configuration, the present invention can more appropriately eliminate the adverse effects caused by outgas released during film formation and stably manufacture an appropriate functional film.

As described above, in the production of a functional film using the vacuum film formation method, outgas such as moisture released from the substrate, the inner wall of the vacuum chamber, the adhesion preventing plate, etc. during the film formation adversely affects the film formation. give. In particular, when a dense film such as a gas barrier film is formed, the influence of outgas is large because the film is formed at a low pressure.
In order to reduce outgas emission, degassing is performed prior to film formation. However, the outgas emission varies depending on the type and storage state of the substrate, the open time of the vacuum chamber, the state of the deposition prevention plate, and the like. Also, in the roll-to-roll apparatus, the outgas emission differs in the longitudinal direction of the substrate. Therefore, if the degassing process is performed under a certain condition, the sufficient degassing process cannot be performed.

In order to solve such problems, as shown in Patent Documents 1 to 3, in reactive sputtering, the amount of oxygen in the film formation chamber, light emission of plasma, discharge voltage, etc. are detected, and this detection result is obtained. Accordingly, it is known to control the amount of oxygen supplied to the film forming chamber.
According to these methods, the influence of oxygen resulting from outgassing can be eliminated. However, with these methods, depending on the type of substrate, the state of the substrate, and the plasma state during film formation, an improper product may be produced. There are many cases where inconvenience such as unevenness occurs.

As a result of intensive studies to solve this problem, the present inventors have found that the cause of the quality deterioration is hydrogen gas as outgas.
In vacuum film formation, outgas released from the substrate during film formation is mainly moisture (H ₂ O). Moisture is decomposed in plasma into oxygen gas and hydrogen gas. This hydrogen is taken into the film to be formed, which causes a change in film density and a defect in the film. Further, the hydrogen gas is decomposed in the plasma to become hydrogen atoms and hydrogen radicals, and attacks the substrate. As a result, the surface property of the substrate deteriorates, and the performance and characteristics of the film formed on the surface of the substrate deteriorate.
Such an adverse effect of hydrogen becomes a particularly serious problem in a film that requires high density, such as a gas barrier film.

Hydrogen is generated only after being exposed to plasma. Further, since hydrogen generation varies depending on the state of the plasma, the amount of hydrogen cannot be determined from the amount of water. Therefore, the degassing process that reduces the amount of water by heat treatment cannot sufficiently eliminate the adverse effects of hydrogen. In other words, the ultimate vacuum management and the heating temperature management in the degassing process cannot sufficiently eliminate the adverse effects caused by hydrogen generated in the plasma.
Moreover, the bad influence of oxygen resulting from outgas can be significantly reduced by the method disclosed in Patent Documents 1 to 3. However, these methods of controlling the oxygen supply amount according to discharge luminescence, voltage detection, etc. cannot eliminate the adverse effects of hydrogen gas.
Therefore, the amount of hydrogen gas released during film formation varies greatly depending on the type of substrate, the state of the substrate, and the plasma state.As a result, as described above, the film quality of the film formed deteriorates, Further, in the roll-to-roll apparatus as shown in the illustrated example, the film quality varies in the longitudinal direction of the substrate.

On the other hand, in the present invention, when a functional film is produced by a vacuum film formation method accompanied by plasma generation, a degassing process is performed by using both a heat treatment and a plasma process as a degassing process before the film formation. In the upstream heat treatment chamber 30 so that the hydrogen gas amount in the plasma treatment chamber 32 is detected and the hydrogen gas amount in the plasma treatment chamber 32 is less than or equal to a predetermined amount. The degree of vacuum and / or temperature).
More specifically, the amount of hydrogen gas is detected in the plasma processing chamber 32 where the plasma is the same as that during film formation and hydrogen gas is also generated as outgas because it is in plasma. According to the result, the heat treatment conditions in the heat treatment chamber 30 are adjusted so that the amount of hydrogen gas in the plasma treatment chamber 32 is less than or equal to a predetermined amount. That is, the moisture that becomes hydrogen gas as the outgas is surely set to a predetermined amount or less by the heat treatment.
Therefore, according to the present invention, the amount of hydrogen gas generated in the film formation chamber 16 where film formation is accompanied by generation of plasma can be greatly reduced. As a result, the adverse effect of hydrogen gas during film formation on the substrate Z is sufficiently eliminated, and an appropriate functional film regardless of the type of the substrate Z, the state of the substrate Z, the state of plasma during film formation, etc. In a roll-to-roll apparatus, the film quality in the longitudinal direction of the substrate Z can be made high and constant.

In the present invention, the hydrogen gas detection means 54 is not particularly limited, and any known hydrogen gas detection means in vacuum or plasma can be used.
As an example, a detection means for detecting the amount of hydrogen gas by mass spectrometry (Q-mass) and a detection means for detecting the amount of hydrogen gas by measuring the emission intensity of hydrogen by plasma (plasma emission spectrometry) are preferably exemplified. The

In addition, there is no particular limitation on the control method (feedback control method) of the heat treatment condition according to the detection result of the hydrogen gas amount in order to keep the hydrogen gas amount in the plasma processing chamber 32 below a predetermined amount. A method is available.
For example, if mass spectrometry is used, a threshold value of hydrogen peak intensity in mass spectrometry is set in advance by experiments, simulations, etc., so that the hydrogen peak intensity is below this threshold value. A method for controlling the heat treatment conditions (heating and / or evacuation) is exemplified. Alternatively, the ion intensity of hydrogen may be used instead of the peak intensity.

As an example, when the hydrogen peak intensity measured by the mass spectrometer approaches a threshold value (or when the difference between the measured value and the threshold value is a predetermined amount or less), the heat treatment condition in the heat treatment chamber 30 is increased ( Conversely, if the measured hydrogen peak intensity deviates from the threshold value, the heat treatment condition is weakened. Alternatively, the threshold value of peak intensity is set in stages, and the relationship between each threshold value and the heat treatment condition is tabulated, and the heat treatment condition is controlled using this table according to the measured peak intensity. May be.
In a roll-to-roll apparatus, it is extremely rare for the outgas release state released from the substrate Z to change suddenly, and normally, when the outgas release state changes, the release amount gradually increases. Or decrease. Therefore, the amount of hydrogen gas in the plasma processing chamber 32 can be suitably maintained below a predetermined amount by such a method for controlling the heat treatment conditions.

  If plasma emission analysis is used, as an example, a threshold value of hydrogen plasma emission intensity is set in the same manner by experiments and simulations so that the measured hydrogen emission intensity is below the threshold value. In the same manner as before, the heat treatment conditions may be controlled.

Preferably, the hydrogen partial pressure and the plasma gas partial pressure such as argon gas are detected by mass spectrometry or plasma emission analysis, so that the ratio of hydrogen partial pressure / plasma gas partial pressure is not more than a preset threshold value. The heat treatment conditions are controlled in the same manner as described above.
The threshold value of the hydrogen partial pressure / plasma gas partial pressure ratio is not particularly limited, but is preferably 0.01. By adjusting the processing conditions in the heat treatment chamber 30 so that the hydrogen partial pressure / plasma gas partial pressure ratio is 0.01 or less in the plasma treatment chamber 32, adverse effects due to hydrogen during film formation are largely eliminated. As a result, a higher quality product can be manufactured more stably.

In the manufacturing apparatus 10, the substrate Z subjected to plasma processing in the plasma processing chamber 32 is transferred to the film forming chamber 16 from the slit 80 a of the partition wall 80 that separates the plasma processing chamber 32 and the film forming quality 16.
In the present invention, a second heat treatment chamber is provided downstream of the plasma treatment chamber 32, the substrate Z is subjected to the plasma treatment, and then the substrate Z is again subjected to the heat treatment. Alternatively, the substrate Z may be transported.

The film formation chamber 16 forms a film on the surface of the substrate Z by reactive sputtering. The guide rollers 56a and 56b, the drum 58, the gas introduction means 60, the cathode 62, the high frequency power supply 64, And a vacuum exhaust means 68.
The film formation chamber 16 performs film formation by general reactive sputtering. Therefore, the gas introducing means 60, the cathode 62, and the high frequency power source 64 may be ordinary ones used in a film forming apparatus using reactive sputtering. The cathode 62 also serves as a means for holding the target Tg, and is disposed so as to face the drum 58 that positions the substrate Z at the film forming position.

The drum 58 of the film forming chamber 16 is a cylindrical member that rotates counterclockwise in the drawing around the center line. The substrate Z supplied from the supply chamber 12 and guided along the predetermined path by the guide roller 56a is wound around a predetermined area on the peripheral surface of the drum 58 and supported / guided by the drum 58 while passing through the predetermined transport path. Be transported.
During this transfer, the vacuum evacuation means 68 evacuates, the reaction gas is introduced from the gas supply means 60, the inside of the film forming chamber 16 is set to a predetermined degree of vacuum, and a predetermined power is supplied from the high frequency power source 64 to the cathode 62. Is deposited on the surface of the substrate Z by reactive sputtering.

The drum 58 may be grounded (earthed) so as to act as a counter electrode, or may be connected to a power source such as a high frequency power source.
In the illustrated example, the number of the cathodes 62 facing the drum 58 is one, but a plurality of cathodes (film forming means) may be arranged in the direction in which the substrate Z is transported by the drum 58.

In the present invention, the film formation method on the substrate Z is not limited to reactive sputtering, and various methods can be used as long as the film formation method involves plasma generation, such as normal sputtering without using a reactive gas, plasma CVD, or the like. Is available.
Among them, reactive sputtering as shown in the illustrated example is preferably used in that the effect of the present invention that the damage of the substrate Z and film quality deterioration caused by hydrogen gas as the outgas can be preferably obtained. The

In the production method of the present invention, the film to be formed is not particularly limited, and various inorganic substances can be used according to the functional film to be produced, as long as the film can be formed by a vacuum film formation method with plasma generation. No membranes are available.
In addition, the thickness of the film to be formed is not particularly limited, and the necessary film thickness may be appropriately determined according to the performance required for the film to be formed and the functional film.

For example, when a gas barrier film (water vapor barrier film) is manufactured as a functional film, a silicon nitride film, an aluminum oxide film, a silicon oxide film, or the like may be formed.
Moreover, what is necessary is just to form a silicon oxide film etc. when manufacturing the protective film of various devices and apparatuses, such as a display apparatus like an organic EL display and a liquid crystal display, as a functional film.
Furthermore, when manufacturing an optical film such as a light reflection preventing film, a light reflection film, and various filters as a functional film, a film made of a material having or expressing a desired optical characteristic may be formed. Good.
In particular, since a dense film is required, it is necessary to form a film at a low degree of vacuum. Therefore, it is optimal for the production of a gas barrier film having a large adverse effect due to outgas.

The substrate Z, that is, the functional film formed by reactive sputtering while being supported / conveyed by the drum 58, is formed from a slit 82 a formed in the partition wall 82 that separates the film formation chamber 16 and the winding chamber 18. It is conveyed to the winding chamber 18.
The substrate Z transported to the winding chamber 18 is guided along a predetermined path by the guide roller 70, transported to the winding shaft 25, and wound in a roll shape by the winding shaft 25 as a functional film roll. Provided to the process. In addition, in the manufacturing apparatus 10 shown in the drawing, as a preferred embodiment, the evacuation unit 72 is also arranged in the winding chamber 18, and the winding chamber 18 also corresponds to the film forming pressure in the film forming chamber 16 during film formation. Depressurized to vacuum.

The manufacturing apparatus 10 shown in FIG. 1 provides a plasma processing chamber 32 downstream of the heat processing chamber 30, and controls the heat processing conditions in the heat processing chamber 30 according to the detection result of the hydrogen gas amount by the plasma processing chamber 32. Although feedback control is performed, conversely, even if the plasma treatment is performed first, the adverse effect of hydrogen gas as the outgas can be greatly reduced, and an appropriate functional film can be stably produced.
That is, prior to the heat treatment, plasma treatment is performed to measure the amount of hydrogen gas in the plasma treatment chamber, and the heat treatment conditions in the heat treatment performed after the plasma treatment are controlled according to the measurement result of the hydrogen gas amount. For example, the amount of hydrogen gas in the plasma processing chamber (the detection result by the hydrogen gas amount detecting means) and the appropriate heat treatment conditions corresponding to this amount of hydrogen gas are examined in advance through experiments or simulations, and the relationship between them is determined. A table is prepared, and during the film formation, the heat treatment conditions are set using this table according to the amount of hydrogen gas detected in the plasma treatment chamber.

According to this method, not only a roll-to-roll apparatus using a long substrate as in the illustrated example, but also an apparatus for forming a film on a short substrate such as a sheet-like substrate can be suitably handled. It becomes possible to do.
In other words, the plasma treatment and the measurement of the hydrogen gas amount for setting the heat treatment conditions can provide a suitable effect regardless of whether the heat treatment is performed before or after the heat treatment.
In particular, the plasma treatment and the measurement of the hydrogen gas amount are more preferably performed both before and after the heat treatment. In this case, as an example, the heat treatment condition is set according to the measurement result of the hydrogen gas amount in the plasma treatment before the heat treatment, and the measurement result of the hydrogen gas amount in the plasma treatment after the heat treatment is fed back. Further, a method for controlling / adjusting the heat treatment condition with high accuracy is exemplified.

  As mentioned above, although the manufacturing method and the functional film manufacturing apparatus of the functional film of this invention were demonstrated in detail, this invention is not limited to the said Example, In the range which does not deviate from the summary of this invention, it is various improvement. Of course, you may make changes.

  Hereinafter, the present invention will be described in more detail with reference to specific examples of the present invention.

[Example]
Using the manufacturing apparatus 10 shown in FIG. 1, after performing degassing treatment (heating treatment and plasma treatment) on a long PET film (polyethylene terephthalate film) having a width of 1000 mm and a thickness of 100 μm, reactive sputtering is performed. Thus, an aluminum oxide film having a thickness of 50 nm was formed to prepare a gas barrier film having a length of 1000 m.

In the heat treatment chamber 30, an infrared heater was used as the heating means 38a and 38b, and the heat treatment distance (the length facing the heating means) was 1 m.
The heat treatment was performed by adjusting the heating temperature according to the measurement result of the amount of hydrogen gas in the plasma processing chamber 32, as will be described later, with the heating temperature by the heating means 38a and 38b as the reference. Note that the degree of vacuum in the heat treatment chamber 30 was constant at 1 × 10 ⁻⁴ Pa.
In addition, the evacuation unit 28 was also driven so that the supply chamber 12 had a vacuum degree of 1 × 10 ⁻⁴ Pa.

In the plasma treatment in the plasma treatment chamber 32, argon gas was used as the plasma gas, and the flow rate was 800 sccm. Further, the processing pressure of the plasma processing was 0.5 Pa, and the input power to the cathode 46 was 1000 W.
Further, as the hydrogen gas detection means 40, a mass spectrometer (QMS200 manufactured by Q-mass Balzers) was used.

In this example, a hydrogen gas partial pressure / argon gas partial pressure ratio (hereinafter referred to as a gas partial pressure ratio) in the plasma processing chamber 32 is measured from a measurement result by a mass spectrometer, and this gas partial pressure ratio is always 0. The heating temperature by the heating means 38a and 38b of the heat treatment chamber 30 was adjusted by the degassing control means 40 so as to be 0.01 or less.
Specifically, when the gas partial pressure ratio rises to 0.009 or more, the heating temperature is increased by 10 ° C. from the reference temperature (80 ° C.), and when the gas partial pressure ratio stops increasing. When the temperature was maintained and the increase in the gas partial pressure ratio did not stop, the temperature was further increased by 10 ° C. Further, when the gas partial pressure ratio decreased to 0.009 or less, the heating temperature was returned to the reference temperature.
As a result, the gas partial pressure ratio in the plasma processing chamber 32 did not exceed 0.01 during the plasma processing over the entire area of the substrate Z on which the aluminum oxide film was formed.

In the film formation chamber 16, metal aluminum was used as a target (Tg), oxygen gas was used as a reactive gas, and argon gas was used as a plasma gas. The flow rate of oxygen gas was 200 sccm, and the flow rate of argon gas was 400 sccm.
The input power to the cathode 62 was 2 kW, and the film formation pressure was 1.5 × 10 ⁻¹ Pa. The evacuation means 80 was driven so that the winding chamber 18 also had a vacuum degree of 1.5 × 10 ⁻¹ Pa.

The produced gas barrier film having a length of 1000 m was sampled at 100 m intervals, and the water vapor transmission rate at 40 ° C./90% relative humidity was measured by the Ca method.
As a result, in all the samples, the water vapor transmission rate was 0.05 g / m ² / day or less.

[Comparative example]
A gas barrier film having a length of 1000 m was produced in the same manner as in the above example, except that the heating temperature in the heat treatment chamber 30 was constant at 80 ° C. (reference temperature).
Sampling was performed in exactly the same manner as in Example, and the water vapor transmission rate was measured.
As a result, there were five samples having a water vapor transmission rate exceeding 0.05 g / m ² / day. Moreover, the water vapor | steam permeability | transmittance exceeded 0.08g / m < ² > / day at 3 points | pieces among them.
From the above results, the effects of the present invention are clear.

It is a figure which shows notionally an example of the functional film manufacturing apparatus of this invention which enforces the manufacturing method of the functional film of this invention.

Explanation of symbols

DESCRIPTION OF SYMBOLS 10 (Functional film) manufacturing apparatus 12 Supply chamber 14 Degassing part 16 Deposition chamber 18 Winding chamber 20 Substrate roll 24 Rotating shaft 25 Winding shaft 26, 36a, 36b, 56a, 56b, 70 Guide roll 28, 34, 52, 68, 80 Vacuum evacuation means 30 Heat treatment chamber 32 Plasma treatment chamber 38a, 38b Heating means 40 Degassing control means 42a, 42b Transport roller pair 46, 62 Cathode 48, 64 High frequency power supply 50, 60 Gas supply means 54 Hydrogen gas Detection means 58 drum

Claims (8)

When performing film formation on the surface of the substrate by a vacuum film formation method involving generation of plasma,
Prior to film formation by the vacuum film formation method, a degassing process for performing a heat treatment and a plasma process after the heat treatment is performed, and a hydrogen gas amount is detected and detected in a processing chamber for performing the plasma process. The method for producing a functional film is characterized in that the conditions for the heat treatment are controlled so that the amount of hydrogen gas is less than a predetermined amount.   2. The functional film production according to claim 1, wherein the heat treatment conditions are controlled so that a ratio of hydrogen gas partial pressure / plasma gas partial pressure detected in a treatment chamber in which the plasma treatment is performed is 0.01 or less. Method.   The functional film manufacturing method according to claim 1, wherein the vacuum film forming method is reactive sputtering.   The functional film manufacturing method according to claim 1, wherein the hydrogen gas amount is detected by mass spectrometry or plasma emission spectrometry in a processing chamber in which the plasma treatment is performed. A film forming chamber for forming a film by a vacuum film forming method accompanied by generation of plasma on the surface of the substrate while conveying a long substrate in the longitudinal direction, and disposed upstream of the film forming chamber. A degassing processing unit for performing degassing processing of the substrate while being transported to
The degassing unit includes a heat treatment chamber for performing heat treatment on the substrate, and a plasma treatment chamber disposed downstream of the heat treatment chamber for performing plasma treatment on the substrate. The processing chamber has detection means for detecting the amount of hydrogen gas in the processing chamber, and the heat processing chamber controls the heat treatment conditions for the substrate so that the amount of hydrogen gas by the detection means is less than or equal to a predetermined amount. The functional film manufacturing apparatus characterized by the above-mentioned.   The detection means detects a hydrogen gas partial pressure and a plasma gas partial pressure in the plasma processing chamber, and the heating processing chamber has a ratio of the hydrogen gas partial pressure / plasma gas partial pressure of 0.01 or less. The functional film manufacturing apparatus of Claim 5 which controls the heat processing conditions of the said board | substrate so that it may become.   The functional film manufacturing apparatus according to claim 5 or 6, wherein the film forming chamber forms a film on the surface of the substrate by reactive sputtering.   The functional film manufacturing apparatus according to claim 5, wherein the detection unit detects the amount of hydrogen gas released from the plasma processing chamber by mass spectrometry or plasma emission spectrometry.

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