JP2006249470A - Plasma discharge treatment apparatus - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide an ambient-pressure plasma discharge treatment apparatus for forming a hard film of high quality with low turbidity. <P>SOLUTION: The plasma discharge treatment apparatus has: one pair of electrodes; a transporting roller which faces to one pair of the electrodes and transports a substrate; and a power source for generating plasma by applying a high-frequency electric field between one pair of the electrodes or between one pair of the electrodes and the transporting roller. The plasma discharge treatment apparatus also comprises: a mixture-gas-feeding means for supplying a mixture gas to be used in forming a thin film from a space between one pair of the electrodes; a treatment space in which the thin film is deposited on a thin film formed on the substrate surface or the substrate from the mixture gas which has been converted into a plasma state; and an exhaust member for exhausting particles and an exhaust gas produced by the plasma from the treatment space. The exhaust member is provided in the upstream and downstream sides of the treatment space. The exhaust member in the downstream side has a higher flow rate of the exhaust gas than that in the upstream side. <P>COPYRIGHT: (C)2006,JPO&NCIPI

Description

  In particular, the present invention relates to exhaust of exhaust gas from a plasma discharge treatment apparatus.

Conventionally, a method of forming a thin film on a substrate surface by plasma CVD in an environment having a pressure of about 1.333 × 10 ⁻⁶ MPa to 1.333 × 10 ⁻³ MPa is known. There is a problem that continuity is lost due to the necessity of equipment, and there is a problem that processing efficiency is low and productivity is low due to low discharge plasma density. As an improvement, treatment with discharge plasma at or near atmospheric pressure is possible. Technology is disclosed.

  When introducing a mixed gas necessary for the reaction to generate discharge plasma into the discharge space under atmospheric pressure or a pressure near atmospheric pressure, and diffusing the gas, compared to when the gas is diffused under low pressure conditions, The gas mixture tends to be biased, and the formed thin film tends to be non-uniform.

  In particular, when a gas is introduced into a discharge space that forms a continuous film forming space and film formation is performed continuously, a thin film is usually formed by connecting a gas supply pipe to one or several gas supply ports. Although formed, gas hardly diffuses in the discharge space under a pressure near atmospheric pressure, so the gas density is higher at a position closer to the gas inlet, and inevitably gas is located at a position far from the gas inlet. The density tends to decrease.

  Processing unevenness due to the non-uniformity of the introduced gas tends to occur, and these processing unevenness becomes a fatal defect in various optical films such as optical thin films such as antireflection films.

  Further, due to the retention of the raw material gas due to such non-uniformity, for example, when using a reactive gas such as a metal oxide or an organometallic compound, a raw material gas powder due to overreaction or unreacted is generated. The film is deposited and adhered in the suction flow path such as the exhaust side pipe, and further enters the film where it is formed, so that the turbidity of the thin film formed continuously increases, Problems such as softening such as loss of film quality and difficulty in maintaining uniformity in film thickness distribution occur.

Therefore, from the structural point of view, such as the introduction of gas, the method of exhaust, and the design of the processing space in the atmospheric pressure plasma apparatus, studies have been made to ensure the uniformity of the introduced gas, eliminate the generation of powder, and improve the film quality. Yes. For example, in atmospheric pressure plasma CVD, a mixed gas is introduced by controlling the supply amount from a gas supply port provided at one end of the discharge plasma processing space, and an exhaust amount is controlled from an exhaust port provided at the other end. A method of exhausting the air is disclosed (for example, see Reference Patent Document 1).
JP 2001-98093 A

However, in the plasma discharge processing apparatus disclosed in Patent Document 1, the mixed gas is introduced from the gas supply port provided at one end of the discharge plasma processing space and is exhausted from the exhaust port provided at the other end. There is a problem that gas is not easily diffused uniformly in the space and particles are likely to be generated, and the rotation of the roll-shaped rotating cylindrical electrode causes gas to move along with the rotating cylindrical electrode around the rotating cylindrical electrode. The problem is that it becomes difficult to remove particles when the generated particles enter this entrained layer, and the particles that are easily diffused by the moving accompanying layer adhere to or enter the thin film being formed. However, the turbidity of the thin film increases, the film becomes soft, and the quality deteriorates.
In view of the above problems, the present invention is to provide an atmospheric pressure plasma discharge treatment apparatus capable of obtaining a hard and good quality film with low turbidity.

  The above object is achieved by the following invention.

(1) A high frequency electric field is applied between a pair of electrodes, a transport roller that faces the pair of electrodes and transports a substrate, and between the pair of electrodes or between the pair of electrodes and the transport roller. In a plasma discharge treatment apparatus having a power source for generating plasma,
A mixed gas supply means for supplying a mixed gas for forming a thin film from between the pair of electrodes, and a process for depositing the thin film on the surface of the base material or on the thin film formed on the base material by the plasma mixed gas A space, and an exhaust member that discharges particles and exhaust gas generated by the plasma from the processing space,
The exhaust member is provided on an upstream side and a downstream side of the processing space, and an exhaust flow rate by the exhaust member on the downstream side is larger than an exhaust flow rate by the exhaust member on the upstream side. .

  (2) The exhaust member on the downstream side and the exhaust member on the upstream side have a nozzle-like tip, and a gap between the pair of electrode-side tips of the exhaust member and the opposed surface of the pair of electrodes is provided. The plasma discharge processing apparatus according to (1), wherein the gap between the front end of the exhaust member on the side of the transport roller and the surface facing the transport roller is 0.1 mm to 10 mm.

  (3) The exhaust member on the downstream side and the exhaust member on the upstream side are provided for one gas supply path for supplying a mixed gas forming a thin film from between the pair of electrodes. The plasma discharge treatment apparatus according to (1) or (2).

  (4) Any one of (1) to (3), characterized in that the both sides of the transport roller have side exhaust members for sucking and discharging the particles and exhaust gas discharged from the side surface of the transport roller. 2. A plasma discharge treatment apparatus according to 1.

  (5) The plasma discharge processing apparatus according to any one of (1) to (4), wherein the plasma is generated in an environment at or near atmospheric pressure.

  By making the exhaust flow rate by the downstream exhaust member larger than the exhaust flow rate by the upstream exhaust member as described in (1) or (5), the influence of the accompanying air is reduced and the gas flow is made uniform and stable. Further, it is possible to provide an atmospheric pressure plasma discharge treatment apparatus that can flow, and can obtain a uniform, hard, and high-quality film with low turbidity by eliminating particles.

  By adopting the exhaust member shape described in (2), it is possible to reduce the suction of unnecessary air, etc., enable the exhaust of exhaust gas containing particles, etc. efficiently, low turbidity, uniform, hard, good quality It is possible to provide an atmospheric pressure plasma discharge treatment apparatus capable of obtaining a simple film.

  The gas supply means described in (3) reduces the influence of entrained air by exhaust means arranged on both sides, and by eliminating particles, a uniform, hard, good quality film with low turbidity is obtained. The obtained atmospheric pressure plasma discharge treatment apparatus can be provided.

  By providing the side exhaust means described in (4), it is possible to exhaust the exhaust gas containing particles and the like released from the side, and an atmospheric pressure plasma discharge that can obtain a uniform, good quality film with low turbidity A processing device can be provided.

  In each drawing, the same number is attached | subjected about the member etc. which have the same structure and function.

  Further, the upstream side and the downstream side refer to upstream and downstream with respect to the conveyance direction of the base material.

  In the present invention, the atmospheric pressure and the vicinity of the atmospheric pressure refer to 20 kPa to 110 kPa, preferably 93 kPa to 104 kPa. Performed in an environment near atmospheric pressure.

  Below, for example, it is possible to form a thin film with uniform nm level smoothness, which is impossible with a wet method such as a spray method or a spin coat method, and there is no need for a vacuum chamber or the like. Furthermore, the atmospheric pressure plasma discharge treatment apparatus of the present invention, which has an effect of obtaining a hard and good quality film with low turbidity by having means for removing exhaust gas and particles, will be described.

  FIG. 1 is a schematic view showing an example of the first embodiment of the atmospheric pressure plasma discharge treatment apparatus of the present invention.

In FIG. 1, an atmospheric pressure plasma discharge treatment apparatus 10 (hereinafter simply referred to as an atmospheric pressure plasma discharge treatment apparatus 10) of a first embodiment for forming a thin film outside a discharge space is
A rotatable roll-shaped base material transport roll 11 having a function of holding and transporting the base material F; and a fixed electrode 12 arranged at a predetermined distance from the outer peripheral surface of the base material transport roll 11;
A gas supply means 14 for supplying at least a mixed gas G of a thin film forming gas and a discharge gas between a pair of fixed electrodes (discharge region) forming the fixed electrode 12;
Of the pair of fixed electrodes forming the fixed electrode 12, the first high-frequency power source 21 that supplies the first high-frequency power to the first fixed electrode 121 and the second high-frequency power to the second fixed electrode 122 are supplied. A second high frequency power supply 22 to
A processing space 17 for forming a thin film that is a facing surface between the substrate transport roll 11 and the fixed electrode 12.
A first exhaust means 15 disposed on the upstream side in the substrate transport direction of the processing space 17 for exhausting the exhaust gas 150 containing particles generated in
And a second exhaust unit 16 disposed on the downstream side of the processing space 17 in the substrate transport direction for discharging the exhaust gas 150 containing particles generated in the processing space 17.

  Here, the base material transport roll 11 also has a function as a back roller that stably maintains the gap distance between the outer peripheral surface of the base material transport roll 11 and the fixed electrode 12.

The first exhaust means 15 mainly sucks the exhaust gas 154 containing particles flowing upstream from the downstream side toward the upstream side. The first exhaust means 15 is a negative blower generated by driving the first blower 151 and the first blower 151. A first mass flow controller 152 that adjusts the flow rate of exhaust gas by pressure, a first nozzle 153 that is an exhaust member that sucks the exhaust gas 154 containing particles flowing upstream, and a first exhaust gas that exhausts the exhaust gas 150 containing particles. An exhaust duct 155,
The second discharge means 16 mainly sucks the exhaust gas 164 containing particles flowing downstream from the upstream side toward the downstream side, and the second blower 161 and the negative pressure generated by driving the second blower 161. A second mass flow controller 162 that adjusts the flow rate of exhaust gas, a second nozzle 163 that is an exhaust member that sucks the exhaust gas 164 containing particles flowing downstream, and a first exhaust that exhausts the exhaust gas 150 containing particles. A duct 155.

  The first blower 151 and the second blower 161 are blowers that suck the exhaust gas 150 containing particles and discharge it outside the atmospheric pressure plasma discharge processing apparatus. The exhaust from the first blower 151 and the second blower 161. The sum of the flow rates has an exhaust capacity of at least 1.0 times, preferably 1.5 times or more, more preferably 3 times or more than the supply amount of the mixed gas G from the gas supply means 14.

  If the exhaust capability is low, sufficient exhaust cannot be performed and particles are diffused in the atmospheric pressure plasma discharge treatment apparatus, or powder is deposited inside the exhaust means such as an exhaust duct.

  Reference numeral 18 denotes entrained air generated as the base material transport roll 11 rotates, and moves in the same direction as the rotational direction of the base material transport roll 11.

  Then, particles P or the like released into the processing space 17 enter the entrained air 18 or are swept away, so that many particles P or the like diffuse to the downstream side in the rotation direction of the substrate transport roll 11 around the atmospheric pressure plasma discharge processing apparatus 10. Resulting in.

  In order to reduce the influence by exhausting the exhaust gas 150 containing particles diffused largely downstream by the accompanying air 18, the sum of the exhaust flow rates of the first mass flow controller 152 and the second mass flow controller 162 is the gas supply means. The exhaust gas flow rate of the second mass flow controller 162 is adjusted to be at least 1.0 times or more, preferably 1.2 to 3 times the supply flow rate of the mixed gas G from the first mass flow controller 152. It is adjusted to be larger than the exhaust flow rate.

  If the exhaust flow rate is small, sufficient exhaust cannot be performed and particles are diffused in the atmospheric pressure plasma discharge treatment apparatus, or powder is deposited inside the discharge means such as a nozzle.

  Here, the flow rates of the second mass flow controller 162 and the exhaust flow rate of the first mass flow controller 152 are controlled according to the rotation speed of the substrate transport roll 11 so that the flow rate of the both changes at a constant rate. Also good.

  And the base material conveyance roll 11 conveys the base material F by the drive means not shown in the state which closely contacted the base material F to the surrounding surface.

  The fixed electrode 12 includes a first fixed electrode 121 and a second fixed electrode 122 that form a pair, and the first fixed electrode 121 and the second fixed electrode 122 face each other with a predetermined gap therebetween. The opposing region forms the discharge region 13, and the first fixed electrode 121, the second fixed electrode 122, and the outer peripheral surface of the substrate transport roll 11 are opposed to each other with a predetermined gap therebetween, A processing space 17 whose surface forms a thin film is formed.

The first high frequency power source 21 is a power source capable of outputting a voltage ω ₁ , a voltage for generating an electric field strength V _1, and a current I ₁ , and the second high frequency power source 22 generates a frequency ω ₂ and an electric field strength V ₂ . A power source capable of outputting voltage and current I ₂ generates a high-frequency electric field in which the frequency ω ₁ and the frequency ω ₂ are superimposed on the discharge region 13.

Here, when the discharge start electric field strength is VI so that the discharge starts stably with respect to the discharge gas such as nitrogen and the thin film forming gas can be stably excited even after the discharge starts, the relationship between the output of each power source Has a relationship of ω ₁ <ω ₂ and V ₁ ≧ VI> V ₂ or V ₁ > VI ≧ V ₂ , and the current I ₁ of the _first high-frequency electric field is preferably 0.3 mA / cm ² to 20 mA / cm ^2, more preferably from ^{1.0mA / cm 2 ~20mA / cm 2} . The current I ₂ of the second high-frequency electric field is preferably 10 mA / cm ^{2 to} 100 mA / cm ² , more preferably 20 mA / cm ^{2 to} 100 mA / cm ² , and the output density of the second high-frequency electric field is 1 W. / Cm ² or more.

  The gas supply means 14 uniformly mixes the thin film forming gas and the discharge gas into a mixed gas G, and supplies the mixed gas G to the discharge region 13 via the gas supply path 141.

  Here, the type of gas, the amount of the gas mixture G of the thin film forming gas and the discharge gas supplied from the gas supply means 14, and the first high frequency power supply 21 and the second high frequency power supply 22 are applied. By selecting the frequency, voltage waveform, voltage value, current, etc., it is possible to form a thin film such as an antireflection film or an antifouling film and to treat the surface of the thin film such as an oxidation treatment of the thin film. Become.

  A method for forming a thin film will be described below by taking as an example a case where a ceramic layer is formed on a substrate F as an example of film formation by the atmospheric pressure plasma discharge processing apparatus 10 described above.

  The base material F is transported to the facing region between the base material transport roll 11 and the fixed electrode 12 in a state of being closely attached along the outer periphery of the base material transport roll 11.

The gas supply means 14 supplies a mixed gas G that forms a ceramic layer in the discharge space 13, and the first power supply 21 and the second power supply 22 provide a gap between the first fixed electrode 121 and the second fixed electrode 122. A high frequency electric field in which the frequency ω ₁ and the frequency ω ₂ are superposed, which satisfy the conditions of the frequency ω, the electric field strength V, and the current I, is applied, and the mixed gas G is excited by the generated plasma.

  The excited mixed gas G ′ is pushed out by the mixed gas and discharged into the processing space 17. Then, the mixed gas G ′ excited on the substrate F in the processing space 17 is exposed, and a ceramic layer is deposited and formed on the surface of the substrate F.

  When the mixed gas G is excited in the discharge space 13 and when a thin film is deposited on the base material F in the processing space 17, the excited mixed gas G ′ remaining without being deposited, or the overreacted mixed gas. Etc. become particles P and are discharged into the processing space 17 in a state of being mixed with the excited mixed gas G ′.

In order to generate such problems that the particles P or the like adhere to or enter the substrate surface or the formed ceramic layer, the turbidity of the thin film increases, the film becomes soft, and the quality deteriorates.
The first exhaust means 15 and the second exhaust means 16 suck and exhaust the exhaust gas 150 containing particles.

  FIG. 2 is a schematic view showing an example of the second embodiment of the atmospheric pressure plasma discharge treatment apparatus of the present invention.

In FIG. 2, the atmospheric pressure plasma discharge treatment apparatus 30 (hereinafter simply referred to as the atmospheric pressure plasma discharge treatment apparatus 30) of the second form for forming a thin film in the discharge space is as follows.
A rotatable roll-shaped base material transport roll 11 having a base material holding and transport function, and a fixed electrode 123 arranged at a predetermined distance from the outer peripheral surface of the base material transport roll 11;
A gas supply means 14 for supplying at least a mixed gas G of a thin film forming gas and a discharge gas to a processing space 32 which passes through the fixed electrode interior 31 and is a discharge space and forms a thin film;
A first high-frequency power source 21 that supplies a first high-frequency power to the substrate transport roll 11; a second high-frequency power source 22 that supplies a second high-frequency power to the fixed electrode 123;
A first exhaust means 15 disposed on the upstream side in the transport direction of the base material for discharging the exhaust gas 150 containing particles generated in the processing space 32 which is also the opposing surface of the base material transport roll 11 and the fixed electrode 123;
And a second exhaust unit 16 disposed on the downstream side in the transport direction of the base material for exhausting the exhaust gas 150 containing particles generated in the processing space 32.

  Here, the substrate transport roll 11 also has a function as a back roller that stably maintains the gap distance between the outer peripheral surface of the substrate transport roll 11 and the fixed electrode 123.

The first exhaust means 15 sucks mainly the exhaust gas 154 containing particles flowing upstream from the downstream side toward the upstream side, and the negative pressure generated by driving the first blower 151 and the first blower 151. A first mass flow controller 152 that adjusts the flow rate of exhaust gas, a first nozzle 153 that is an exhaust member that sucks the exhaust gas 154 containing particles flowing upstream, and a second exhaust that exhausts the exhaust gas 150 containing particles. A duct 155,
The second discharge means 16 mainly sucks the exhaust gas 164 containing particles flowing downstream from the upstream side toward the downstream side, and is based on the negative pressure generated by driving the second blower 161 and the second blower 161. A second mass flow controller 162 that adjusts the flow rate of exhaust gas, a second nozzle 163 that is an exhaust member that sucks exhaust gas 164 containing particles flowing downstream, and a first exhaust duct that exhausts exhaust gas 150 containing particles 165.

  The first blower 151 and the second blower 161 are blowers that suck the exhaust gas 150 containing particles and discharge it outside the atmospheric pressure plasma discharge processing apparatus. The exhaust from the first blower 151 and the second blower 161. The sum of the flow rates has an exhaust capacity that is at least 1.0 times, preferably 1.5 times or more, more preferably 3 to 5 times the supply amount of the mixed gas G from the gas supply means 14.

  If the exhaust capability is low, sufficient exhaust cannot be performed and particles are diffused in the atmospheric pressure plasma discharge treatment apparatus, or powder is deposited inside the exhaust means such as an exhaust duct.

  Reference numeral 18 denotes entrained air generated as the base material transport roll 11 rotates, and moves in the same direction as the rotational direction of the base material transport roll 11.

  Then, particles P or the like released into the processing space 32 enter or flow into the accompanying air 18, so that many particles P or the like are diffused downstream in the rotation direction of the base material transport roll 11 around the atmospheric pressure plasma discharge processing apparatus 30. Resulting in.

  In order to reduce the influence of exhaust gas 150 containing particles diffused to the downstream side by the accompanying air 18, the sum of the exhaust flow rates of the first mass flow controller 152 and the second mass flow controller 162 is the gas supply. The exhaust flow rate of the second mass flow controller 162 is adjusted to at least 1.0 times or more, preferably 1.2 to 3 times the supply flow rate of the mixed gas G from the means 14, and the first mass flow controller 162 It is adjusted to be larger than the exhaust flow rate of 152.

  If the exhaust flow rate is small, sufficient exhaust cannot be performed and particles are diffused in the atmospheric pressure plasma discharge treatment apparatus, or powder is deposited inside the discharge means such as a nozzle.

  Here, the flow rates of the second mass flow controller 162 and the exhaust flow rate of the first mass flow controller 152 are controlled according to the rotation speed of the substrate transport roll 11 so that the flow rate of the both changes at a constant rate. Also good.

  And the base material conveyance roll 11 conveys the base material F by the drive means not shown in the state which closely contacted the base material F to the surrounding surface.

  The opposed surface of the fixed electrode 123 and the outer periphery of the substrate transport roll 11 is opposed to each other with a predetermined gap, and the opposed surface forms a processing space 32.

The first high frequency power source 21 is a power source capable of outputting a voltage and current I ₁ having a frequency ω ₁ and an electric field strength V _1, and the second high frequency power source 22 is a voltage having a frequency ω ₂ and an electric field strength V ₂ , A high-frequency electric field in which the frequency ω ₁ and the frequency ω ₂ are superimposed is generated in the processing space 32 by a power source capable of outputting the current I ₂ .

Here, assuming that the discharge starting electric field strength is VI so that the discharge starts stably with respect to the discharge gas such as nitrogen and the thin film forming gas can be stably excited even after the discharge starts, the output of each power source The relationship is ω ₁ <ω ₂ and V ₁ ≧ VI> V ₂ or V ₁ > VI ≧ V ₂ , and the current I ₁ of the _first high-frequency electric field is preferably 0.3 mA / cm. ^{2 ~20mA} / cm ^2, more preferably from ^{1.0mA / cm 2 ~20mA / cm 2} . The current I ₂ of the second high-frequency electric field is preferably 10 mA / cm ^{2 to} 100 mA / cm ² , more preferably 20 mA / cm ^{2 to} 100 mA / cm ² , and the output density of the second high-frequency electric field is 1 W. / Cm ² or more.

  The gas supply means 14 uniformly mixes the thin film forming gas and the discharge gas to form a mixed gas G, and supplies the mixed gas G to the processing space 32 through the gas supply path 141 and the fixed electrode interior 31.

  Here, the type of gas, the amount of the gas mixture G of the thin film forming gas and the discharge gas supplied from the gas supply means 14, and the first high frequency power supply 21 and the second high frequency power supply 22 are applied. By selecting the frequency, voltage waveform, voltage value, current, etc., it is possible to form a thin film such as an antireflection film or an antifouling film and to treat the surface of the thin film such as an oxidation treatment of the thin film. Become.

  A method of forming a thin film will be described below by taking as an example a case where a ceramic layer is formed on a substrate F as an example of film formation by the above-described atmospheric pressure plasma discharge processing apparatus 30.

  The base material F is transported to a facing region between the base material transport roll 11 and the fixed electrode 123 in a state of being closely attached along the outer periphery of the base material transport roll 11.

The gas supply means 14 supplies a mixed gas G that forms a ceramic layer in the processing space 32, and the first power source 21 and the second power source 22 provide the above-described frequency ω between the fixed electrode 123 and the substrate transport roll 11. A high frequency electric field in which the frequency ω ₁ and the frequency ω ₂ are superimposed, which satisfies the conditions of the electric field strength V and the current I, is applied, and the mixed gas G is excited by the generated plasma.

  The mixed gas G ′ excited on the substrate F in the processing space 32 is exposed, and a ceramic layer is deposited and formed on the surface of the substrate F.

  When the mixed gas G is excited in the processing space 32 and when a thin film is deposited on the base material F in the processing space 32, the excited mixed gas G ′, the overreacted mixed gas, etc. that are not deposited are left. Particles P are discharged into the processing space 32 in a state of being mixed with the excited mixed gas G ′.

In order to generate such problems that the particles P or the like adhere to or enter the substrate surface or the formed ceramic layer, the turbidity of the thin film increases, the film becomes soft, and the quality deteriorates.
The first exhaust means 15 and the second exhaust means 16 suck and exhaust the exhaust gas 150 containing particles.

  As described above, in the atmospheric pressure plasma discharge processing apparatus 10 or the atmospheric pressure plasma discharge processing apparatus 30, the mixed gas is supplied from substantially the center in the transport direction of the base material F of the fixed electrode, and the upstream side and the downstream side of the processing space 17. Exhaust means for exhaust gas is arranged on each side, and especially by increasing the exhaust flow rate on the downstream side, it is possible to remove particles and the like, while reducing the influence of entrained air, and uniform base of the excited mixed gas It becomes possible to make a flow in the conveying direction of the material F, and to form a high-quality thin film.

  FIG. 3 is an explanatory diagram when a plurality of atmospheric pressure plasma discharge treatment units are arranged.

  Hereinafter, a case where a plurality of the atmospheric pressure plasma discharge treatment apparatuses 30 described above are arranged as the atmospheric pressure plasma discharge treatment unit will be described as an example. It goes without saying that a plurality of the atmospheric pressure plasma discharge treatment apparatuses 10 can be arranged in the same manner.

  The fixed electrode 123, the gas supply means 14, the first exhaust means 15, and the second exhaust means 16 are used as a set of atmospheric pressure plasma discharge units 19, and a plurality of sets of atmospheric pressure plasma discharge units 19 are base materials. They are arranged concentrically around the transport roll 11.

  Each gas supply unit may supply the same gas or different gases.

  Alternatively, one gas supply unit 14 may be provided, and a predetermined amount of mixed gas may be adjusted and supplied to each fixed electrode 123 by a supply gas flow rate adjusting unit (not shown).

  The second high-frequency power source 22 is connected to each fixed electrode 123, and the first high-frequency power source 21 is connected to the base material transport roll 11, and each fixed electrode 123 and the base material transport are turned on when both power sources are turned on. A high frequency electric field is generated in a region facing the roll 11 to excite the mixed gas G supplied from the gas supply means 14.

  One high-frequency power source on the fixed electrode side may be provided for each atmospheric pressure plasma discharge unit 19 according to the thin film to be formed. In this case, the frequency and power of each high frequency power supply may be the same or different.

  The excited mixed gas G ′ is a discharge space and forms a thin film on the surface of the base material F or the other thin film formed on the surface of the base material that is transported by the base material transport roll 11 in the processing space 32 that forms the thin film. Deposit and form.

  Here, for each atmospheric pressure plasma discharge unit 19, the exhaust flow rate of the second exhaust means 16 on the downstream side and the exhaust gas of the first exhaust means 15 on the upstream side according to the supply amount of the mixed gas by each gas supply means 14. Further, the exhaust flow rate of the second exhaust means 16 on the downstream side is made larger than the exhaust flow rate of the first exhaust means 15 on the upstream side.

  Reference numerals 64 and 67 are guide rollers for stably guiding the substrate F to the substrate transport roll 11.

  Further, the fixed electrode 123 and the substrate transport roll 11 are adjusted so that the surface temperature thereof becomes a predetermined temperature by temperature adjusting means for adjusting the temperature of the electrode and the roll (not shown).

  As described above, by providing gas supply means and exhaust gas exhaust means for each atmospheric pressure plasma discharge unit 19, it is possible to adjust the gas flow rate for each atmospheric pressure plasma discharge unit 19. By making it possible to prevent gas from being mixed between the plasma discharge units 19, it is possible to form a high-quality film.

In the above first high frequency power supply 21 of a frequency omega ₁ and described in FIGS. 1, 2, 3, the second RF power supply 22 of a frequency omega ₂ power below can be preferably used.
As the first high frequency power supply,
Applied power symbol Manufacturer Frequency Product name A1 Shinko Electric 3kHz SPG3-4500
A2 Shinko Electric 5kHz SPG5-4500
A3 Kasuga Electric 15kHz AGI-023
A4 Shinko Electric 50kHz SPG50-4500
A5 HEIDEN Research Laboratories 100kHz * PHF-6k
A6 Pearl Industry 200kHz CF-2000-200k
A7 Pearl Industry 400kHz CF-2000-400k
And the like, and any of them can be used.

As the second high frequency power supply,
Applied power supply symbol Manufacturer Frequency Product name B1 Pearl Industry 800kHz CF-2000-800k
B2 Pearl Industry 2MHz CF-2000-2M
B3 Pearl Industry 13.56MHz CF-5000-13M
B4 Pearl Industry 27MHz CF-2000-27M
B5 Pearl Industry 150MHz CF-2000-150M
And the like, and any of them can be preferably used.

  Of the above power supplies, * indicates a HEIDEN Laboratory impulse high-frequency power supply (100 kHz in continuous mode). Other than that, it is a high-frequency power source that can apply only a continuous sine wave.

  The waveform of the high frequency electric field is not particularly limited. There are a continuous sine wave continuous oscillation mode called a continuous mode, an intermittent oscillation mode called ON / OFF intermittently called a pulse mode, and either of them may be adopted, but at least the second electrode side (second The high-frequency electric field is preferably a continuous sine wave because a denser and better quality film can be obtained.

Moreover, the 1st filter 23 is installed between the base material conveyance roll 11 and the 1st power supply 21, and it is easy to pass the electric current from the 1st power supply 21 to the base material conveyance roll 11, and 2nd power supply The current from the second power source 22 to the first power source 21 is less likely to pass through,
A second filter 24 is installed between the fixed electrode 123 and the second power source 22 to facilitate passage of current from the second power source 22 to the fixed electrode 123, and to ground the current from the first power source 21. Thus, it is difficult to pass a current from the first power source 21 to the second power source.

  Next, for example, a thin film material supplied as a mixed gas G when a ceramic layer is formed by the atmospheric pressure plasma discharge treatment apparatuses 10 and 30 will be described.

  As conditions for forming the ceramic layer, metal carbide, metal nitride, metal oxide, metal sulfide are selected by selecting an organometallic compound that is a raw material (also referred to as a raw material), a decomposition gas, a decomposition temperature, and an input power. Products, metal halides, and mixtures thereof (metal oxynitrides, metal oxide halides, metal nitride carbides, etc.) can be formed.

  For example, when a silicon compound is used as a raw material compound and oxygen is used as a decomposition gas, silicon oxide is generated. Further, if a zinc compound is used as a raw material compound and carbon disulfide is used as a cracked gas, zinc sulfide is generated. This is because highly active charged particles and active radicals exist in the plasma space at a high density, so that multistage chemical reactions are accelerated at high speed in the plasma space, and the elements present in the plasma space are thermodynamic. This is because it is converted into an extremely stable compound in a very short time.

  Specifically, an inorganic oxide is preferable as a thin film material constituting the ceramic layer, and silicon oxide, aluminum oxide, silicon oxynitride, aluminum oxynitride, magnesium oxide, zinc oxide, indium oxide, tin oxide, or a mixture thereof. Can be mentioned.

As these organometallic compounds,
As silicon compounds, silane, tetramethoxysilane, tetraethoxysilane, tetra n-propoxysilane, tetraisopropoxysilane, tetra n-butoxysilane, tetrat-butoxysilane, dimethyldimethoxysilane, dimethyldiethoxysilane, diethyldimethoxysilane, Diphenyldimethoxysilane, methyltriethoxysilane, ethyltrimethoxysilane, phenyltriethoxysilane, (3,3,3-trifluoropropyl) trimethoxysilane, hexamethyldisiloxane, bis (dimethylamino) dimethylsilane, bis (dimethyl Amino) methylvinylsilane, bis (ethylamino) dimethylsilane, N, O-bis (trimethylsilyl) acetamide, bis (trimethylsilyl) carbodiimide, diethylaminoto Methylsilane, dimethylaminodimethylsilane, hexamethyldisilazane, hexamethylcyclotrisilazane, heptamethyldisilazane, nonamethyltrisilazane, octamethylcyclotetrasilazane, tetrakisdimethylaminosilane, tetraisocyanatosilane, tetramethyldisilazane, tris ( Dimethylamino) silane, triethoxyfluorosilane, allyldimethylsilane, allyltrimethylsilane, benzyltrimethylsilane, bis (trimethylsilyl) acetylene, 1,4-bistrimethylsilyl-1,3-butadiyne, di-t-butylsilane, 1,3 -Disilabutane, bis (trimethylsilyl) methane, cyclopentadienyltrimethylsilane, phenyldimethylsilane, phenyltrimethylsilane, propargyltri Tylsilane, tetramethylsilane, trimethylsilylacetylene, 1- (trimethylsilyl) -1-propyne, tris (trimethylsilyl) methane, tris (trimethylsilyl) silane, vinyltrimethylsilane, hexamethyldisilane, octamethylcyclotetrasiloxane, tetramethylcyclotetrasiloxane , Hexamethylcyclotetrasiloxane, M silicate 51, and the like.

  Examples of the titanium compound include titanium methoxide, titanium ethoxide, titanium isopropoxide, titanium tetraisoporooxide, titanium n-butoxide, titanium diisopropoxide (bis-2,4-pentanedionate), titanium. Examples thereof include diisopropoxide (bis-2,4-ethylacetoacetate), titanium di-n-butoxide (bis-2,4-pentanedionate), titanium acetylacetonate, and butyl titanate dimer.

  Zirconium compounds include zirconium n-propoxide, zirconium n-butoxide, zirconium t-butoxide, zirconium tri-n-butoxide acetylacetonate, zirconium di-n-butoxide bisacetylacetonate, zirconium acetylacetonate, zirconium acetate, Zirconium hexafluoropentanedioate and the like can be mentioned.

  Examples of the aluminum compound include aluminum ethoxide, aluminum triisopropoxide, aluminum isopropoxide, aluminum n-butoxide, aluminum s-butoxide, aluminum t-butoxide, aluminum acetylacetonate, and triethyldialuminum tri-s-butoxide. Can be mentioned.

  The boron compounds include diborane, tetraborane, boron fluoride, boron chloride, boron bromide, borane-diethyl ether complex, borane-THF complex, borane-dimethyl sulfide complex, boron trifluoride diethyl ether complex, triethylborane, trimethoxy. Examples include borane, triethoxyborane, tri (isopropoxy) borane, borazole, trimethylborazole, triethylborazole, triisopropylborazole, and the like.

  Examples of tin compounds include tetraethyltin, tetramethyltin, di-n-butyltin diacetate, tetrabutyltin, tetraoctyltin, tetraethoxytin, methyltriethoxytin, diethyldiethoxytin, triisopropylethoxytin, diethyltin, Dimethyltin, diisopropyltin, dibutyltin, diethoxytin, dimethoxytin, diisopropoxytin, dibutoxytin, tin dibutyrate, tin diacetoacetonate, ethyltin acetoacetonate, ethoxytin acetoacetonate, dimethyltin diacetoacetonate Examples of tin halides such as tin hydrogen compounds include tin dichloride and tin tetrachloride.

  Other organometallic compounds include, for example, antimony ethoxide, arsenic triethoxide, barium 2,2,6,6-tetramethylheptanedionate, beryllium acetylacetonate, bismuth hexafluoropentanedionate, dimethylcadmium, calcium 2,2,6,6-tetramethylheptanedionate, chromium trifluoropentanedionate, cobalt acetylacetonate, copper hexafluoropentanedionate, magnesium hexafluoropentanedionate-dimethyl ether complex, gallium ethoxide, tetraethoxygermane , Tetramethoxygermane, hafnium t-butoxide, hafnium ethoxide, indium acetylacetonate, indium 2,6-dimethylaminoheptanedionate Ferrocene, lanthanum isopropoxide, lead acetate, tetraethyl lead, neodymium acetylacetonate, platinum hexafluoropentanedionate, trimethylcyclopentadienylplatinum, rhodium dicarbonylacetylacetonate, strontium 2,2,6,6-tetramethyl Examples include heptanedionate, tantalum methoxide, tantalum trifluoroethoxide, tellurium ethoxide, tungsten ethoxide, vanadium triisopropoxide oxide, magnesium hexafluoroacetylacetonate, zinc acetylacetonate, and diethylzinc.

  In addition, as a decomposition gas for decomposing a raw material gas containing these metals to obtain an inorganic compound, hydrogen gas, methane gas, acetylene gas, carbon monoxide gas, carbon dioxide gas, nitrogen gas, ammonia gas, nitrous oxide Examples include gas, nitrogen oxide gas, nitrogen dioxide gas, oxygen gas, water vapor, fluorine gas, hydrogen fluoride, trifluoroalcohol, trifluorotoluene, hydrogen sulfide, sulfur dioxide, carbon disulfide, and chlorine gas.

  Various metal carbides, metal nitrides, metal oxides, metal halides, and metal sulfides can be obtained by appropriately selecting a source gas containing a metal element and a decomposition gas.

  A discharge gas that tends to be in a plasma state is mixed with these reactive gases, and the gas is sent to the plasma discharge generator.

  As such a discharge gas, nitrogen gas and / or 18th group atom of the periodic table, specifically, helium, neon, argon, krypton, xenon, radon, etc. are used. Among these, nitrogen, helium, and argon are preferably used, and nitrogen is particularly preferable because of low cost.

  The discharge gas and the reactive gas are mixed, and a film is formed by supplying the mixed gas as a mixed gas to a plasma discharge generator (plasma generator). Although the ratio of the discharge gas and the reactive gas varies depending on the properties of the film to be obtained, the reactive gas is supplied with the ratio of the discharge gas being 50% or more with respect to the entire mixed gas.

  FIG. 4 is a perspective view showing an example of the structure of the metal base material of the electrode and the dielectric material coated thereon.

  FIG. 4 shows the concept of the first electrode 121, the second electrode 122, the fixed electrode 123, the base material transport roll 11, and the like described above. The conductive metal base material 41 is covered with the dielectric 42. It has been done.

  A high-frequency power source (not shown) is connected via a cable (not shown) connected to the metallic base material 41 or, if necessary, an armature and a brush (not shown) provided on the shaft portion 43 of the metallic base material 41. Connected).

  Of the electrodes, at least one of a pair of electrodes that generate a high-frequency electric field is covered with a dielectric 42.

  Examples of the conductive metal base material 41 include metals such as titanium metal or titanium alloy, silver, platinum, stainless steel, aluminum, and iron, composite materials of iron and ceramics, or composite materials of aluminum and ceramics. Although titanium metal or titanium alloys are particularly preferred.

  The dielectric 42 coated on the surface of the metallic base material 41 is obtained by thermal spraying ceramics as a dielectric and then sealing with an inorganic compound sealing material.

  The dielectric 42 only needs to be covered with about 1 mm in one piece. As the ceramic material used for thermal spraying, alumina, silicon nitride, or the like is preferably used. Among these, alumina is particularly preferable because it is easily processed. The dielectric layer may be a lining-processed dielectric provided with an inorganic material by lining.

  The electrode covering the dielectric is preferably a combination having a small difference in linear thermal expansion coefficient between the metallic matrix and the dielectric. For example, the metallic matrix is pure titanium or a titanium alloy, and the dielectric is Ceramic sprayed coating is particularly preferable. Besides, the metallic base material is pure titanium or titanium alloy, the dielectric is glass lining, the metallic base material is a composite material of ceramics and iron, and the dielectric is ceramic sprayed coating, metallic The base material is a composite material of ceramics and iron, the dielectric is a glass lining, the metallic base material is a composite material of ceramics and aluminum, the dielectric is a ceramic sprayed coating, the metallic base material is a composite material of ceramics and aluminum, Examples of the dielectric include glass lining.

  By such a combination, there is no deterioration of the electrode in use, in particular, cracking, peeling, dropping off, etc., and it can withstand long-time use under severe conditions.

Return the story back to the exhaust means,
FIG. 5 is an explanatory diagram of the exhaust unit 15 and the second exhaust unit 16.

  Hereinafter, the first exhaust unit 15 and the second exhaust unit 16 will be further described.

  FIG. 5A shows a part of the first exhaust means 15 that sucks the exhaust gas 154 mainly containing particles flowing upstream, and FIG. 5B sucks the exhaust gas 164 mainly containing particles flowing downstream. A part of the second discharging means 16 is shown.

  In FIG. 5A, the excited mixed gas G 'is exposed to the surface of the substrate F to be conveyed by the substrate conveyance roll 11 rotating in the direction of the arrow to form a thin film (not shown).

  The particles P and the like are floating in the excited mixed gas G ′.

  After the formation of the thin film, the exhaust gas G1 containing particles P and the like pushed out with the supply of the mixed gas G is sucked from the first nozzle 153 of the first exhaust means 15 and discharged.

The lower side (A part) of the upstream tip of the first fixed electrode 121 is designated 121a, the lower side (B part) of the upstream tip of the fixed electrode 123 is designated 123a, and the first nozzle 153 is also shown. When the upper side (C portion) of the tip of the nozzle is 153a and the lower side (D portion) of the tip of the first nozzle 153 is 153b,
The gap d3 between the A portion 121a and the B portion 123a and the C portion 153a is 10 mm or less, preferably 0 to 3 mm. If it is too wide, the outside air is sucked, exhaust efficiency is lowered, and particles cannot be discharged sufficiently.

  Further, the gap d4 between the D portion 153b and the surface of the base material transport roll 11 is determined based on the thickness of the base material to be transported, but the gap d4 does not contact the base material F, and unnecessary discharge outside the discharge space. If it is too wide, the outside air will be sucked in and the exhaust efficiency will be reduced and particles etc. will not be discharged sufficiently, so it is 10 mm or less, preferably 0.1 to 3 mm. .

  In FIG. 5 (b), exhaust gas G 1 including particles P and the like that have been formed with the supply of the mixed gas G after forming a thin film is sucked and discharged from the second nozzle 163 of the second exhaust means 16. .

The illustrated lower side (E portion) of the downstream tip of the second fixed electrode 122 is 122b, the illustrated lower side (F portion) of the downstream tip of the fixed electrode 123 is 123b, and the second nozzle 163. When the upper side (H part) of the tip of the nozzle is 163a and the lower side (J part) of the tip of the second nozzle 163 is 163b,
The gap d5 between the E portion 122b and the F portion 123b and the H portion 163a is 10 mm or less, preferably 0 to 3 mm. If it is too wide, the outside air is sucked, exhaust efficiency is lowered, and particles cannot be discharged sufficiently.

  In addition, the gap d6 between the J portion 163b and the surface of the base material transport roll 11 is determined based on the thickness of the base material to be transported. Since external air is sucked in and exhaust efficiency decreases and particles or the like cannot be sufficiently discharged, the thickness is 10 mm or less, preferably 0.1 to 3 mm.

  The first nozzle 153, the second nozzle 163, the first exhaust duct 155, and the second exhaust duct 165 are preferably made of metal in order to prevent adhesion to the inside of the member due to static electricity, but the first nozzle 153 And all or at least the tip of the second nozzle 163 is preferably made of an insulating material such as glass epoxy in order to prevent unnecessary discharge of the high-frequency voltage from the electrode and the substrate transport roll.

  FIG. 6 is an explanatory view of the exhaust unit 15 and the second exhaust unit 16 of FIG. 4 as viewed from above.

  6A is a view of the first exhaust unit 15 and the second exhaust unit 16 of FIG. 5 as viewed from above, and FIG. 6B is an exhaust unit 15 and the second exhaust unit of FIG. FIG. 6C is a view of the tip portion of the nozzle as viewed from XY in FIGS. 6A and 6B.

  In FIGS. 6A and 6C, the first nozzle 153 and the second nozzle 163 have the same internal structure, and therefore the first nozzle 153 will be described as an example.

  The first nozzle 153 has an exhaust gas exhaust path 1531 connected to the first exhaust duct 155, the exhaust path 1531 branches to become a second exhaust path 1532, and the second exhaust path 1532 further branches. The third exhaust path 1533 is further branched to form a fourth exhaust path 1534, and the tip of the fourth exhaust path 1534 becomes an intake port 1535 for sucking exhaust gas containing particles. ing.

  W1 is the width dimension of the exhaust gas suction part 1536 of the first nozzle 153, and W2 is the width dimension of the base material transport roll 11.

  Each width dimension has a relationship of W1 ≧ W2, and the dimension obtained by subtracting W2 from W1 is 0 to 500 mm, preferably 50 to 200 mm. If the amount is too small, it becomes difficult to sufficiently suck the exhaust gas 150 including particles in the vicinity of both ends of the substrate transport roll 11, and if it is too large, external air is sucked and the exhaust efficiency is lowered and particles and the like cannot be discharged sufficiently.

  The branching structure branched from the exhaust path 1531 to the fourth exhaust path 1534 makes the suction flow rate of the exhaust gas from each intake port 1535 aligned in the width direction of the substrate transport roll 11 uniform, and forms a thin film on the substrate F In the width direction.

  In order to obtain a uniform suction flow rate in the width direction, it is preferable to have a branching structure as described above. However, the exhaust gas exhaust path 1531 is not directly branched and is directly connected to the fourth exhaust path 1534. It may be configured as shown (not shown).

  Further, the concave portion 1536 of the first nozzle 153 also has a function of further uniforming the exhaust gas suction flow rate in the width direction.

  In FIG. 6B, since the upstream nozzle 153 'and the downstream nozzle 163' have the same internal structure, the upstream nozzle 153 'will be described as an example.

  The upstream nozzle 153 ′ has an exhaust gas exhaust path 1531 connected to the first exhaust duct 155, and the exhaust path 1531 is connected to a cavity 1537 serving as a temporary storage part of the exhaust gas to be sucked. Each intake path 1538 that communicates with each intake port 1535 aligned in the width direction of the substrate transport roll 11 is connected.

  Although the configuration having a plurality of intake ports (intake ports 1535) has been described above, the intake ports may be continuous slit-shaped intake ports (not shown).

  FIG. 7 is an explanatory view of the exhaust means on the side of the substrate transport roll.

  The side exhaust member 161 is an exhaust plate for the exhaust gas 150 including particles disposed on both surfaces of the base material transport roll 11 so as not to diffuse the exhaust gas 150 including particles emitted from both side surfaces of the base material transport roller 11 to the outside. is there.

  The exhaust gas 150 including particles sucked by the side exhaust member 161 is exhausted by an exhaust gas exhaust unit 163 having a filter (not shown) that collects particles and the like through an exhaust gas path 162.

  The shape of the side exhaust plate 161 has a dimension that is inside the outer peripheral surface of the base material transport roll 11 and outside the inside of the fixed electrode 123 in the diameter direction of the base material transport roll 11. In the tangential direction, it has dimensions that are respectively outside the both ends of the fixed electrode 123.

  Each of the inner and outer overlap dimensions is 10 to 100 mm. If the overlap is too large, the operability is hindered, and if it is too small, the exhaust gas 150 containing particles discharged from both side surfaces of the substrate transport roll 11 is increased.

  Since the rest of the configuration is the same as that of FIG.

  Further, the side exhaust plate 161 and the first exhaust unit 15 and / or the second exhaust unit 16 may be integrated.

It is the schematic which shows one example of the 1st form of the atmospheric pressure plasma discharge processing apparatus of this invention. It is the schematic which shows one example of the 2nd form of the atmospheric pressure plasma discharge processing apparatus of this invention. It is explanatory drawing at the time of arranging a plurality of atmospheric pressure plasma discharge processing units. It is a perspective view which shows an example of the structure of the metal base material of an electrode, and the dielectric material coat | covered on it. It is explanatory drawing of the exhaust means 15 and the 2nd exhaust means 16. FIG. It is explanatory drawing which looked at the exhaust means 15 and the 2nd exhaust means 16 of FIG. 4 from the top. It is explanatory drawing of the exhaust means of a base material conveyance roll side surface.

Explanation of symbols

DESCRIPTION OF SYMBOLS 10, 30 Atmospheric pressure plasma discharge processing apparatus 11 Base material conveyance roll 12 Square tube type fixed electrode 13 Discharge area 14 Gas supply means 15, 35 First exhaust means 16, 36 Second exhaust means 17 Processing space 18 Entrained air 19 Atmospheric pressure plasma discharge unit 21 First high-frequency power source 22 Second high-frequency power source 150 Exhaust gas containing particles 153 First nozzle 163 Second nozzle 154 Exhaust gas containing particles flowing upstream 164 Exhaust gas containing particles flowing downstream G gas mixture G 'excited gas mixture P particle

Claims (5)

Plasma is generated by applying a high-frequency electric field between the pair of electrodes, the transport roller that faces the pair of electrodes and transports the substrate, and between the pair of electrodes or between the pair of electrodes and the transport roller A plasma discharge treatment apparatus having a power source
A mixed gas supply means for supplying a mixed gas for forming a thin film from between the pair of electrodes, and a process for depositing the thin film on the surface of the base material or on the thin film formed on the base material by the plasma mixed gas A space, and an exhaust member that discharges particles and exhaust gas generated by the plasma from the processing space,
The exhaust member is provided on an upstream side and a downstream side of the processing space, and an exhaust flow rate by the exhaust member on the downstream side is larger than an exhaust flow rate by the exhaust member on the upstream side. . The exhaust member on the downstream side and the exhaust member on the upstream side have a nozzle-like tip, and a gap between the pair of electrode-side tips of the exhaust member and the facing surface of the pair of electrodes is 10 mm or less. The plasma discharge processing apparatus according to claim 1, wherein a gap between a front surface of the exhaust member facing the transport roller and the transport roller is 0.1 mm to 10 mm. 2. The exhaust member on the downstream side and the exhaust member on the upstream side are provided for one gas supply path for supplying a mixed gas forming a thin film from between the pair of electrodes. Or the plasma discharge processing apparatus of 2. The plasma discharge according to any one of claims 1 to 3, further comprising a side exhaust member that sucks and discharges the particles and exhaust gas emitted from the side surface of the transport roller on both side surfaces of the transport roller. Processing equipment. The plasma discharge processing apparatus according to any one of claims 1 to 4, wherein the plasma is generated in an environment at or near atmospheric pressure.

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