JP2016108611A - Plasma cvd device, film deposition method, film, and member with film - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a plasma CVD device and a film deposition method capable of forming a film of high hardness, and to provide a film of high hardness and a member with a film of high hardness.SOLUTION: A plasma CVD device includes a first electrode 1 where a substrate on which a film is formed is installed, and a second electrode 2 arranged oppositely to the first electrode. At least part of the first electrode is supported by a support member 3 with a heat insulation layer 50 in between. Preferably, the first electrode is supported by the support member with a spacer 4 having a volume heat capacity of 2.00[J cmK] or more at 100°C in between.SELECTED DRAWING: Figure 1

Description

  The present invention relates to a plasma CVD apparatus, a film forming method, a film, and a member with a film.

  As a thin film forming apparatus, a plasma CVD apparatus is known (see, for example, Patent Document 1).

  In general, a plasma CVD apparatus has a vacuum chamber in which electrodes for supplying power are arranged, and a base material (semiconductor wafer, glass substrate, etc.) to be processed is installed in the vacuum chamber, and the vacuum chamber is decompressed. A film is formed on the substrate by introducing a reactive gas into the vacuum chamber, supplying power to the electrode, generating plasma in the vacuum chamber, and depositing a substance on the substrate by a chemical reaction .

  However, in the conventional plasma CVD apparatus, the characteristics inherent to the constituent material of the film may not be obtained. In particular, even if the constituent material of the film is originally hard, the formed film may have insufficient hardness.

JP 2009-184176 A

  An object of the present invention is to provide a plasma CVD apparatus and a film forming method capable of forming a film having high hardness, to provide a film having high hardness, and to provide a film-coated member provided with a film having high hardness. It is to provide.

Such an object is achieved by the present invention described below.
The plasma CVD apparatus of the present invention includes a first electrode on which a substrate on which a film is formed is installed,
A plasma CVD apparatus having a second electrode disposed opposite to the first electrode,
At least a part of the first electrode is supported by a support through a heat insulating layer.

  Thereby, the plasma CVD apparatus which can form a film | membrane with high hardness can be provided.

  In the plasma CVD apparatus of the present invention, the first electrode is preferably supported by the support via a spacer.

  Thereby, a heat insulation layer can be reliably provided between a 1st electrode and a support body by simple structure. Further, the first electrode can be stably supported, and the reliability of the entire apparatus can be made particularly excellent.

In the plasma CVD apparatus of the present invention, the volumetric heat capacity of the spacer at 100 ° C. is preferably 2.00 [J · cm ⁻³ · K ⁻¹ ] or more.

  Thereby, the unintentional temperature fluctuation of the base material due to heat conduction from the first electrode 1 to the spacer 4 can be more effectively prevented, and the hardness of the formed film can be further improved. .

  In the plasma CVD apparatus of the present invention, it is preferable that temperature detecting means for detecting the temperature of the base material or the first electrode is provided, and the output of the high-frequency power source is controlled based on the detected temperature.

  Thereby, the unintentional temperature fluctuation of the base material at the time of film-forming can be prevented more effectively, and the hardness of the film to be formed can be more reliably improved.

In the plasma CVD apparatus of the present invention, the volumetric heat capacity of the first electrode at 100 ° C. is preferably 2.00 [J · cm ⁻³ · K ⁻¹ ] or more.

  Thereby, the unintentional temperature fluctuation of the base material at the time of film-forming can be prevented more effectively, and the hardness of the film formed can be made more excellent.

  In the plasma CVD apparatus of the present invention, it is preferable that the first electrode is movable and configured to be able to come into contact with the support after completion of film formation.

  Thus, during film formation, the substrate (film-equipped member) on which the film is formed is suitably cooled after the film formation is completed, while effectively preventing an unintended temperature change of the substrate. Can do. As a result, the productivity of the member with a film can be made particularly excellent. In addition, for example, when the temperature of the base material or the first electrode rises more than necessary during film formation, the first electrode and the base material are suitably cooled by bringing the first electrode into contact with the support. Can do.

In the plasma CVD apparatus of the present invention, the support is preferably made of a material having a thermal conductivity at 100 ° C. of 100 [W · m ⁻¹ · K ⁻¹ ] or higher.

  Thereby, after the film formation is completed, the first electrode 1 and the support 3 are brought into contact with each other, whereby the base material (film-equipped member) on which the film is formed can be more suitably cooled, and the production of the film-equipped member is produced. The property can be further improved.

In the film forming method of the present invention, a voltage is applied between the first electrode and a second electrode different from the first electrode in a state where a substrate on which a film is formed is placed on the first electrode. A film forming method for forming a film on the base material by plasma CVD,
The film formation is performed in a state where at least a part of the first electrode is supported by a support through a heat insulating layer.
Thereby, the film-forming method which can form a film | membrane with high hardness can be provided.

  In the film forming method of the present invention, the first electrode is movable, maintains a state separated from the support during film formation, and contacts the support after completion of film formation. preferable.

  Thereby, the base material (member with a film | membrane) in which the 1st electrode and the film | membrane were formed can be cooled efficiently. As a result, the film-coated member can be safely taken out from the plasma CVD apparatus, and the productivity of the film-coated member can be further improved.

The film of the present invention is formed using the plasma CVD apparatus of the present invention.
Thereby, a film | membrane with high hardness can be provided.

The film of the present invention is formed using the film forming method of the present invention.
Thereby, a film | membrane with high hardness can be provided.

The film-coated member of the present invention comprises a base material,
And a film formed using the plasma CVD apparatus of the present invention.
Thereby, the member with a film | membrane provided with the film | membrane with high hardness can be provided.

The film-coated member of the present invention comprises a base material,
And a film formed using the film forming method of the present invention.
Thereby, the member with a film | membrane provided with the film | membrane with high hardness can be provided.

  In the member with a film of the present invention, the thickness of the film is preferably 0.1 μm or more and 5.0 μm or less.

  Thereby, the hardness of a film | membrane can be made more excellent, making the adhesiveness with respect to the base material of the film | membrane formed sufficiently excellent.

The film-coated member of the present invention is preferably a nozzle plate.
The nozzle plate is a member that is required to have particularly high hardness among the various film-coated members so that it can withstand repeated wiping, but in the present invention, even when applied to the nozzle plate, The hardness of the portion where the film is provided can be stably increased over a long period of time. That is, when the film-coated member is a nozzle plate, the effects of the present invention are more remarkably exhibited.

It is a longitudinal cross-sectional view which shows the outline of suitable embodiment of the plasma CVD apparatus of this invention typically. It is a typical top view of the 2nd electrode which comprises the plasma CVD apparatus of this invention shown in FIG. In the plasma CVD apparatus of this invention shown in FIG. 1, it is sectional drawing which shows typically the state which the 1st electrode and the support body contacted. It is sectional drawing which shows typically suitable embodiment of the inkjet head provided with the nozzle plate to which this invention was applied. 1 is a schematic view showing a preferred embodiment of an ink jet recording apparatus to which a film-coated member of the present invention is applied.

  Hereinafter, preferred embodiments of the present invention will be described in detail with reference to the accompanying drawings.

<< Plasma CVD equipment >>
First, the plasma CVD apparatus (film forming apparatus) of the present invention will be described.

  FIG. 1 is a longitudinal sectional view schematically showing an outline of a preferred embodiment of a plasma CVD apparatus (film formation apparatus) of the present invention, and FIG. 2 is a second view of the plasma CVD apparatus of the present invention shown in FIG. FIG. 3 is a cross-sectional view schematically showing a state in which the first electrode and the support are in contact with each other in the plasma CVD apparatus of the present invention shown in FIG.

  The plasma CVD apparatus 10 of the present invention supports a first electrode 1 on which a base material on which a film is to be formed is installed, a second electrode 2 disposed opposite to the first electrode, and the first electrode 1. A support 3, a vacuum chamber (chamber) 5 that accommodates the first electrode 1 and the second electrode 2, an exhaust means 6 that exhausts the inside of the vacuum chamber 5, and a gas supply means 7 that supplies gas into the vacuum chamber 5. And a power source (high frequency power source) 8 and a cooling means 9.

  The second electrode 2 is electrically connected to a power source (high frequency power source) 8 through a matching circuit (not shown).

  The second electrode 2 has a through-hole (film formation material) through which a gas (including a film formation material) supplied from a gas supply means 7 described later is introduced into the space between the first electrode 1 and the second electrode 2. A plurality of supply units and nozzles) 21 are provided.

  Thereby, the film-forming material can be efficiently supplied toward the base material installed on the first electrode 1, the proportion of the film-forming material not used for film formation can be reduced, and the film can be efficiently formed. It can be performed. Moreover, the unintentional dispersion | variation in the film thickness of the film | membrane formed in a base material can be prevented effectively.

Further, the through holes (nozzles) 21 are provided uniformly over almost the entire surface of the second electrode 2.
Thereby, the effects as described above are more remarkably exhibited.

The shape of the through hole 21 when the second electrode 2 is viewed in plan is not particularly limited, but is preferably circular.
Thereby, supply of gas can be performed more smoothly.

  The diameter of the through hole 21 is preferably from 0.1 mm to 2.0 mm, and more preferably from 0.2 mm to 1.5 mm.

  Thereby, it is possible to supply a sufficient amount (a supply amount per unit time) of the gas while preventing the gas injection pressure from becoming extremely high. As a result, the film formation efficiency (productivity of the film-coated member) can be made particularly excellent, and the occurrence of unintentional film thickness variations can be more effectively prevented.

  In the present specification, for a given numerical value, the expressions “above” and “below” are used for a range including the numerical value, and the expressions “less than” and “exceeded” are used for a range not including the numerical value. Shall.

  The pitch (center-to-center distance) between adjacent through holes 21 is preferably 1.0 mm or more and 22.5 mm or less, and more preferably 1.5 mm or more and 3.0 mm or less.

  Thereby, the gas supplied to each part of the base material or the surface of the second electrode 2 (the surface on the side facing the first electrode 1) while sufficiently increasing the area of the part functioning as the conductive portion or Variation in the amount of reaction product of the film forming material can be suppressed. As a result, it is possible to form a film in which generation of unintentional film thickness variation and the like is more effectively prevented with higher productivity.

The area of the second electrode 2 when the second electrode 2 is viewed from the side where the first electrode 1 is provided is S ₀ [mm ² ], and the total area of the plurality of through holes 21 is S ₂ [mm ² ]. In this case, it is preferable to satisfy the relationship of 0.0007 ≦ S ₂ / S ₀ ≦ 0.02, and it is more preferable to satisfy the relationship of 0.002 ≦ S ₂ / S ₀ ≦ 0.012.

  Thereby, the gas supplied to each part of the base material or the surface of the second electrode 2 (the surface on the side facing the first electrode 1) while sufficiently increasing the area of the part functioning as the conductive portion or Variation in the amount of reaction product of the film forming material can be suppressed. As a result, it is possible to form a film in which generation of unintentional film thickness variation and the like is more effectively prevented with higher productivity.

The second electrode 2 may be made of any material as long as it has conductivity. For example, various metals such as aluminum can be used.
Further, the surface of the second electrode 2 may be subjected to a surface treatment.

  Thereby, for example, it is possible to improve the corrosion resistance of the second electrode 2 and improve the resistance to the sputtering phenomenon.

  When the 2nd electrode 2 is mainly comprised with aluminum, an alumite process is employable as said surface treatment. Thereby, the effects as described above can be more remarkably exhibited.

  The first electrode 1 has a function of holding a base material (member) on which a film is formed, is grounded, and is configured to generate a potential difference with the second electrode 2. ing.

  The first electrode 1 is supported by a support 3 via spacers (leg portions) 4. The heat insulating layer (gap) 50 is interposed between the first electrode 1 and the support 3 due to the presence of the spacer 4.

  With such a configuration, unintentional temperature fluctuations of the base material during film formation can be prevented. As a result, the film quality of the formed film can be stabilized. In particular, a high hardness film can be stably formed.

  In addition, the support 3 supports the first electrode 1 via the spacers (leg portions) 4 so that the heat insulating layer 50 is reliably provided between the first electrode 1 and the support 3 with a simple configuration. Can do. Moreover, since the 1st electrode 1 can be supported stably, the reliability as the whole apparatus can be made especially excellent.

  On the other hand, if a heat insulating layer is not provided between the first electrode and the support, the temperature of the substrate placed on the first electrode is unstable due to heat transfer from the first electrode to the support. It becomes. In plasma CVD, the characteristics (film quality) of the film to be formed vary greatly depending on the temperature of the base material on which the film is formed. Therefore, with such a configuration, a film having a high hardness can be stably formed. Can not.

Although the 1st electrode 1 may be comprised with what kind of material, the volumetric heat capacity in 100 degreeC of the 1st electrode 1 is 2.00 [J * cm ^<-3 > * K ^<-1 >] or more. Is preferably 2.43 [J · cm ⁻³ · K ⁻¹ ] or more.

  Thereby, the unintentional temperature fluctuation of the base material at the time of film-forming can be prevented more effectively, and the hardness of the film formed can be made more excellent.

The constituent material of the first electrode 1 preferably has a thermal conductivity at 100 ° C. of 250 [W · m ⁻¹ · K ⁻¹ ] or less, and 50 [W · m ⁻¹ · K ⁻¹ ]. The following are more preferable.

  Thereby, the unintentional temperature fluctuation of the base material at the time of film-forming can be prevented more effectively, and the hardness of the film formed can be made more excellent.

The first electrode 1 usually has an area equal to or larger than the area of the base material on which the film is to be formed.
The shape of the first electrode 1 in plan view is not particularly limited, but in the present embodiment, it is a circular shape.
Thereby, a film-forming process can be more suitably performed on a wafer-like base material or the like.

The first electrode 1 usually has the same shape and size as the second electrode 2.
Thereby, more stable film formation can be performed.

The spacer 4 may be made of any material, but the volumetric heat capacity of the spacer 4 at 100 ° C. is preferably 2.00 [J · cm ⁻³ · K ⁻¹ ] or more. .43 [J · cm ⁻³ · K ⁻¹ ] or more is more preferable.

  Thereby, the unintentional temperature fluctuation of the base material due to heat conduction from the first electrode 1 to the spacer 4 can be more effectively prevented, and the hardness of the formed film can be further improved. .

The constituent material of the spacer 4 preferably has a thermal conductivity at 100 ° C. of 250 [W · m ⁻¹ · K ⁻¹ ] or less, and 50 [W · m ⁻¹ · K ⁻¹ ] or less. More preferably.

  Thereby, the unintentional temperature fluctuation of the base material at the time of film-forming can be prevented more effectively, and the hardness of the film formed can be made more excellent.

  Further, in the present embodiment, the spacer (leg part) 4 is movable, and the first electrode 1 is configured to be movable. At the time of film formation, while the heat insulating layer 50 is interposed between the first electrode 1 and the support 3, the first electrode 1 is supported after the film formation is finished as shown in FIG. It is comprised so that the body 3 can be contacted.

  With such a configuration, the substrate on which the film is formed (at the end of film formation) while effectively preventing the unintended temperature change of the substrate as described above during film formation. The member with a film) can be suitably cooled. As a result, the productivity of the member with a film can be made particularly excellent. Further, for example, when the temperature of the base material or the first electrode 1 rises more than necessary during film formation (when an abnormal temperature rise occurs), the first electrode 1 is brought into contact with the support, The first electrode 1 and the substrate can be suitably cooled. As a result, the safety of the plasma CVD apparatus 10 can be enhanced, and damage to the base material can be effectively prevented.

The support 3 may be made of any material, but the constituent material of the support 3 has a thermal conductivity at 100 ° C. of 100 [W · m ⁻¹ · K ⁻¹ ] or more. It is preferable that it is 150 [W * m ^{< -1} > * K ^<-1 >] or more.

  Thereby, after the film formation is completed, the first electrode 1 and the support 3 are brought into contact with each other, whereby the base material (film-equipped member) on which the film is formed can be more suitably cooled, and the production of the film-equipped member is produced. The property can be further improved.

  In the present embodiment, cooling means 9 for cooling the support 3 is arranged inside the support 3.

  Thereby, after completion | finish of film-forming, the base material (member with a film | membrane) in which the film | membrane was formed can be cooled more suitably, and the productivity of a member with a film | membrane can be made further excellent. Further, for example, by controlling the operation of the cooling means 9, the cooling rate of the first electrode can be adjusted more suitably. In addition, in a plasma CVD apparatus having a structure in which an electrode on which a substrate on which a film is to be formed is placed is in contact with a support, the support is cooled by a cooling means. However, in the present invention, there is a case where the cooling means is provided in this way. However, it is possible to reliably prevent the occurrence of the above problems.

  The cooling means 9 may be any type, but for example, it is preferable that a cooling medium (for example, cooling water, ammonia, fluorocarbons, isobutane, carbon dioxide, etc.) is circulated therein. .

  Although the thickness of the heat insulation layer 50 at the time of film-forming is not specifically limited, It is preferable that they are 1 mm or more and 200 mm or less, and it is more preferable that they are 1 mm or more and 100 mm or less.

  Thereby, the effect by having a heat insulation layer as mentioned above can be exhibited more notably, preventing the enlargement etc. of the plasma CVD apparatus 10 effectively.

  In addition, the plasma CVD apparatus 10 of the present embodiment includes a temperature detection unit 60 that detects the temperature of the first electrode 1. And it is comprised so that the output of the high frequency power supply 8 may be controlled based on the temperature detected by the temperature detection means 60.

  Thereby, the unintentional temperature fluctuation of the base material at the time of film-forming can be prevented more effectively, and the hardness of the film to be formed can be more reliably improved.

Various temperature sensors can be used as the temperature detection means 60.
The vacuum chamber 5 is configured such that the gas is supplied by the gas supply means 7 after the internal air is exhausted by the exhaust means 6.

  As the exhaust means 6, for example, various pumps such as an oil rotary pump, a dry pump, a turbo molecular pump (TMP), and a mechanical booster pump (MBP) can be used.

As the gas supply means 7, for example, a gas cylinder can be used.
The gas includes at least a film forming material, and may further include a carrier gas such as an inert gas (a mixed gas of the film forming material and the carrier gas).

The film forming material varies depending on the composition of the film to be formed. For example, when forming a film composed of silicon nitride, a combination of a Si-containing gas such as SiH ₄ and an N-containing gas such as NH ₃ is used. Can be used. In the case of forming an insulating film (PPSi film) that can be applied to a nozzle plate or the like of a droplet discharge device described later, OMTS (octamethyltrisiloxane) or the like can be used as a film forming material. . As a film forming material, tetraethyl orthosilicate (TEOS) or the like can be preferably used.

  In particular, it is preferable to use a silicon compound (for example, OMTS, TEOS, etc.) as a film forming material and form a film made of silicone.

  Thereby, for example, it can be suitably applied to a nozzle plate or the like of a droplet discharge device described later. Further, conventionally, when forming a film composed of silicone, the problem that the hardness of the film to be formed cannot be stably improved has been more prominent. Then, even when a film made of silicone is formed, the hardness of the formed film can be stably improved. That is, when a silicon compound is used as a film forming material and a film made of silicone is formed, the effect of the present invention is more remarkably exhibited.

  Moreover, as carrier gas, argon, hydrogen, nitrogen etc. can be used suitably, for example.

  In the illustrated configuration, one gas supply means 7 is provided, but a plurality of gas supply means 7 may be provided.

  Thereby, for example, gases having different compositions can be supplied individually. More specifically, when a gas containing a film forming material and a gas not containing a film forming material are separately supplied or a plurality of types of film forming materials are used, a gas containing a first film forming material The gas containing the second film forming material different from the first film forming material can be supplied individually. Thus, by individually supplying a plurality of types of gas, for example, management of a container (such as a gas cylinder) that stores the gas becomes easy. In addition, the mixing ratio of plural kinds of gases can be easily adjusted.

The plasma CVD apparatus 10 also has a control unit (not shown). The control unit applies a voltage applied by the power supply 8, a gas supply amount from the gas supply unit 7, an exhaust amount by the exhaust unit 6, and a cooling unit 9. Temperature adjustment and the like are controlled.
Thereby, film formation can be performed under suitably controlled conditions.

  According to the plasma CVD apparatus of the present invention as described above, a film having high hardness can be stably formed.

<< Film Formation Method (Film Production Method) >>
Next, the film forming method (film manufacturing method) of the present invention will be described.

In the film forming method of the present invention, a voltage is applied between the first electrode and a second electrode different from the first electrode in a state where a substrate on which a film is formed is placed on the first electrode. A film forming method for forming a film on the substrate by plasma CVD, wherein the film is formed in a state where at least a part of the first electrode is supported by a support through a heat insulating layer. Features.
Thereby, a film with high hardness can be stably formed.

  Hereinafter, an example of a method for forming a film using the above-described plasma CVD apparatus (film forming apparatus) 10 will be described.

  In the manufacturing method of the present embodiment, the pressure reduction step (1a) for reducing the pressure inside the vacuum chamber 5 by the exhaust means 6 and the first electrode 1 and the second electrode 2 from the gas supply means 7 through the through holes 21 are performed. A film forming material supply step (1b) for supplying a gas containing a film forming material in between, and a plasma generating step for generating plasma by applying a voltage between the first electrode 1 and the second electrode 2 by the power source 8 (1c).

<Decompression step>
First, prior to supplying gas to the inside of the vacuum chamber 5, the inside of the vacuum chamber 5 is decompressed by the exhaust means 6.

  Thereby, the inside of the vacuum chamber 5 can be efficiently replaced with the gas supplied from the gas supply means 7.

  Although the pressure inside the vacuum chamber 5 in the state decompressed in the pressure reduction process is not particularly limited, it is preferably 0.01 Pa or more and 1 Pa or less, and more preferably 0.1 Pa or more and 0.5 Pa or less.

  Thereby, the inside of the vacuum chamber 5 can be replaced with the gas supplied from the gas supply means 7 more efficiently, and the film formation efficiency (productivity of the member with the film) is particularly excellent. Can do.

  On the other hand, if the pressure inside the vacuum chamber 5 in a state where the pressure is reduced in the pressure reducing step exceeds the upper limit value, the replacement efficiency of the gas inside the vacuum chamber 5 is lowered.

  In addition, if the pressure inside the vacuum chamber 5 in a state where the pressure is reduced in the pressure reducing step is less than the lower limit value, it is difficult not only to further improve the replacement efficiency of the gas inside the vacuum chamber 5, but also the pressure reducing step. Therefore, the film formation efficiency (productivity of the film-coated member) decreases. In addition, excessive decompression increases the load on the exhaust means 6 and the like, which is disadvantageous from the viewpoint of stable operation of the plasma CVD apparatus 10 and longer life.

<Film forming material supply process>
Thereafter, a gas containing a film forming material is supplied into the vacuum chamber 5 in a decompressed state.

  Thereby, the inside of the vacuum chamber 5 can contain each component, such as film-forming material, with a desired content rate. As a result, film formation can be suitably advanced in the subsequent plasma generation step.

  The pressure inside the vacuum chamber 5 in a state where gas is supplied in the film forming material supply step is not particularly limited, but is preferably 0.1 Pa or more and 900 Pa or less, and more preferably 1 Pa or more and 500 Pa or less. .

  Thereby, the film-forming efficiency (productivity of the film-coated member) in the subsequent plasma generation step can be made particularly excellent.

<Plasma generation process>
Thereafter, a voltage is applied between the first electrode 1 and the second electrode 2 by the power source 8.

  As a result, the gas enters a plasma state, and the film forming material is excited and becomes chemically active. Then, the film forming material in a chemically active state chemically reacts to form a film composed of a reaction product of the film forming material on the substrate.

  At this time, as shown in FIG. 1, due to the presence of the spacer 4, a heat insulating layer (void) 50 is interposed between the first electrode 1 and the support 3. Thereby, the unintentional temperature fluctuation of the base material during film formation in this step can be effectively prevented.

The temperature of the substrate in this step varies depending on the kind of film forming material, the composition of the film to be formed, etc., but is preferably 60 ° C. or higher and 170 ° C. or lower, and more preferably 100 ° C. or higher and 150 ° C. or lower. preferable.
Thereby, the hardness of the film | membrane formed can be made higher.

  Moreover, the base material provided to this process may be heat-treated (pre-heat treated) in advance. As a result, unintentional temperature fluctuations during film formation can be prevented, and a film having a high hardness can be more reliably formed. The pre-heat treatment may be performed, for example, before the substrate is introduced into the plasma CVD apparatus 10 (in the vacuum chamber 5), or may be performed within the plasma CVD apparatus 10.

  When pre-heat treatment is performed on the substrate, the pre-heat treatment is preferably performed so that the temperature of the substrate at the start of this step (plasma generation step) is a value within the above-described range.

  As described above, according to the present invention, unintentional temperature fluctuations during film formation can be prevented.

Specifically, the difference between the maximum temperature _{T max} and the minimum temperature _{T min} of the substrate in this step _(T max _{-T min)} is preferably at 10 ° C. or less, and more preferably at 5 ° C. or less .

  In this step, in order to continuously advance the reaction of the film forming material, it is usually performed while supplying gas from the gas supply means 7.

  Although the thickness of the film | membrane formed at this process is not specifically limited, It is preferable that they are 0.1 micrometer or more and 5.0 micrometers or less, and it is more preferable that they are 0.2 micrometer or more and 1.5 micrometers or less.

  Thereby, the hardness of a film | membrane can be made more excellent, making the adhesiveness with respect to the base material of the film | membrane formed sufficiently excellent. Further, in the past, when a film having a relatively large thickness was formed in this way, it was particularly susceptible to adverse effects due to unintended temperature fluctuations during film formation. Even when a film having a large thickness is formed, it is possible to reliably prevent the occurrence of the above problems. That is, when the thickness of the film is within the above range, the effect of the present invention is more remarkable.

  Moreover, the surface hardness of the film | membrane calculated | required by the nanoindentation method is preferably 1.3 GPa or more, and more preferably 1.5 GPa or more.

  As a result, the abrasion resistance of the film can be made particularly excellent, and a member (a member with a film) provided with the film is suitably applied to, for example, a nozzle plate of a droplet discharge device described later. be able to.

  The surface hardness of the film by the nanoindentation method is, for example, a scanning probe microscope (for example, manufactured by Digital Instruments, trade name “NanoScope III”, etc.) and a nano indenter (for example, trade name, manufactured by Heiditron). Using a TRIBOSCOPE etc., a Berkovich indenter is used as a hardness measurement indenter, and a load-displacement curve obtained from measurement under the conditions of measurement load: 30 μN, measurement temperature: 23 ° C., relative humidity: 55% it can.

  In order to prevent the pressure inside the vacuum chamber 5 from increasing with the supply of gas from the gas supply means 7 (in order to maintain the degree of vacuum), in this step, the exhaust means 6 may perform exhaust.

  The pressure inside the vacuum chamber 5 in the plasma generation step is not particularly limited, but is preferably 0.1 Pa or more and 900 Pa or less, and more preferably 1 Pa or more and 500 Pa or less.

  Thereby, the efficiency of film formation (productivity of a member with a film) can be made particularly excellent.

<Cooling process>
After the film formation on the substrate is completed, the first electrode 1 is moved and the first electrode 1 and the support 3 are brought into contact as shown in FIG.

  Thereby, the 1st electrode 1 and the base material (member with a film | membrane) in which the film | membrane was formed can be cooled efficiently. As a result, the film-coated member can be safely taken out from the plasma CVD apparatus 10 and the productivity of the film-coated member can be further improved.

<Membrane, membrane-attached member>
Next, the film | membrane and member with a film | membrane of this invention are demonstrated.

The film of the present invention is formed using the film forming method of the present invention described above and the plasma CVD apparatus of the present invention.
Thereby, a film | membrane with high hardness can be provided.

Moreover, the member with a film of the present invention comprises a substrate and a film formed using the above-described film forming method of the present invention and the plasma CVD apparatus of the present invention.
Thereby, the member with a film | membrane provided with the film | membrane with high hardness can be provided.

  Note that the base material on which the film is formed using the plasma CVD apparatus and film forming method of the present invention as described above may be used as a member with a film as it is, or the base material on which the film is formed is cut. The material subjected to the above processing may be used as the film-coated member of the present invention.

  In addition, the film included in the film-coated member may be a film formed by using the plasma CVD apparatus and the film forming method described above as it is, or may have been subjected to other processing after film formation. May be.

  The film-coated member of the present invention may be used for any application, and can be applied to, for example, a semiconductor device.

  The film-coated member of the present invention can be suitably applied to, for example, a nozzle plate constituting a droplet discharge head (inkjet head) of a droplet discharge device (inkjet recording device). A droplet discharge head (inkjet head) has a fine structure, and a slight dimensional deviation greatly affects the droplet discharge characteristics. In addition, in order to prevent excessive wetting and spreading of ink on the nozzle plate, a droplet repellent head is generally provided with a liquid repellent film. However, in the nozzle plate, the wiping means wipes off the adhered ink. Work is generally done. Therefore, the nozzle plate is a member that is required to have particularly high hardness among the various film-coated members so that it can withstand repeated wiping, but in the present invention, it is a case where it is applied to the nozzle plate. However, the effects as described above can be stably exhibited over a long period of time. That is, when the film-coated member is a nozzle plate, the effects of the present invention are more remarkably exhibited.

  There are various types of droplet discharge devices (inkjet recording devices) such as home use, office use, and industrial use. In particular, droplet discharge devices (inkjet recording devices) for textile printing are generally wiped. Since a member having a large frictional force, such as cloth, is used as the member, the above-described problem is likely to occur. However, the present invention is applied to a nozzle plate or the like constituting a droplet discharge apparatus (inkjet recording apparatus) for textile printing. Can also be suitably applied.

<Inkjet head>
Hereinafter, an inkjet head provided with a nozzle plate as an example of the film-coated member of the present invention will be described.

  FIG. 4 is a cross-sectional view schematically showing a preferred embodiment of an inkjet head having a nozzle plate to which the present invention is applied.

  An ink jet head (droplet discharge head) 100 shown in FIG. 4 is formed at a desired position on the vibration plate 82, a silicon substrate 81 on which an ink reservoir 87 is formed, a vibration plate 82 formed on the silicon substrate 81, and the like. The lower electrode 83, the lower electrode 83, the piezoelectric thin film 84 formed at a position corresponding to the ink reservoir 87, the upper electrode 85 formed on the piezoelectric thin film 84, and the lower surface of the silicon substrate 81. And a nozzle plate 86 joined to each other. The nozzle plate 86 is provided with an ink discharge nozzle (through hole) 86 </ b> A communicating with the ink reservoir 87.

  In the inkjet head 100, ink is supplied to the ink reservoir 87 via an ink flow path (not shown). Here, when a voltage is applied to the piezoelectric thin film 84 via the lower electrode 83 and the upper electrode 85, the piezoelectric thin film 84 is deformed to create a negative pressure in the ink reservoir 87 and apply pressure to the ink. With this pressure, ink is ejected from the nozzle, and ink jet recording is performed.

  For example, the inkjet head 100 is formed by integrally forming a thin film piezoelectric element including a lower electrode 83, a piezoelectric thin film 84, and an upper electrode 85 by a thin film process using a Si thermal oxide film as a vibration plate 82, and an upper portion thereof. In addition, a chip made of a single crystal silicon substrate 81 in which a cavity (ink reservoir) 87 is formed and a nozzle plate 86 having an ink discharge nozzle 86A for discharging ink may be joined. it can.

  Here, the piezoelectric thin film 84 is composed of, for example, a three-component PZT in which lead magnesium niobate is added as a third component as a material having a high piezoelectric strain constant d31 so that a larger displacement amount can be obtained. Can be used. The thickness of the piezoelectric thin film 84 can be about 2 μm.

  The nozzle plate 86 includes a base portion 861 and a liquid repellent film 862 that is selectively provided on the outer surface side of the base portion 861 (the surface side opposite to the surface facing the silicon substrate 81).

  The liquid repellent film 862 is a film formed by using the film forming method of the present invention as described above, a plasma CVD apparatus, or a film obtained by subjecting the film to a predetermined treatment.

An example of a method for manufacturing such a nozzle plate 86 will be described below.
First, a substrate (base portion 861) made of nickel or the like and provided with an opening corresponding to the ink discharge nozzle (through hole) 86A is prepared, and the film forming method and plasma CVD apparatus of the present invention are applied to this substrate. To form a film. At this time, octamethyltrisiloxane is used as a film forming material, and a film composed of the polymer is formed. Thereafter, the formed film is subjected to a warming aging process (annealing process) in a nitrogen atmosphere to form a plasma polymerized film as a liquid repellent film 862 on the surface, thereby obtaining the nozzle plate 86. Can do.

<< Equipment with membrane-coated member (electronic equipment) >>
Next, an apparatus provided with the above-described film-coated member will be described.

  The film-coated member of the present invention may be used for any application as described above, but can be used as a component member of various devices (for example, electronic devices).

  Hereinafter, as an example of an apparatus (electronic apparatus) including a film-coated member, an ink jet recording apparatus (droplet discharge apparatus) including the above-described ink jet head will be described.

  FIG. 5 is a schematic view showing a preferred embodiment of an ink jet recording apparatus to which the film-coated member of the present invention is applied.

  As shown in FIG. 5, an ink jet recording apparatus (droplet discharge apparatus) 1000 includes ink jet head units (recording head units) 91A and 91B, cartridges 92A and 92B, a carriage 93, an apparatus main body 94, and a carriage shaft. 95, a drive motor 96, a timing belt 97, and a platen 98.

  The recording head units 91A and 91B including the ink jet head 100 (including the film-coated member of the present invention) as described above are provided with detachable cartridges 92A and 92B constituting the ink supply means. A carriage 93 on which 91B is mounted is provided on a carriage shaft 95 attached to the apparatus main body 94 so as to be movable in the axial direction. The recording head units 91A and 91B can eject, for example, a black ink composition and a color ink composition, respectively.

  Then, the driving force of the driving motor 96 is transmitted to the carriage 93 via a plurality of gears and a timing belt 97 (not shown), so that the carriage 93 on which the recording head units 91A and 91B are mounted is moved along the carriage shaft 95. The On the other hand, the apparatus main body 94 is provided with a platen 98 along the carriage shaft 95, and a recording sheet S, which is a recording medium such as paper fed by a not-shown paper feed roller, is wound around the platen 98. It is designed to be transported.

  As mentioned above, although preferred embodiment of this invention was described, this invention is not limited to these.

  For example, in the plasma CVD apparatus of the present invention, the configuration of each part can be replaced with any configuration that exhibits the same function, and any configuration can be added.

  In the above-described embodiment, the case where the first electrode is supported by the support via the spacer is representatively described. However, at least a part of the first electrode is attached to the support via the heat insulating layer. What is necessary is just to be supported, and what kind of form may be supported. For example, the first electrode may be supported on the wall surface (support) of the vacuum chamber by a wire.

  In the above-described embodiment, the cooling unit is described as being installed inside the support, but the installation site of the cooling unit is not particularly limited. Moreover, the plasma CVD apparatus may not include a cooling unit.

In the above-described embodiment, the temperature detection unit is described as detecting the temperature of the first electrode. However, the temperature of the base material may be adjusted.
In addition, the plasma CVD apparatus may not include a temperature detection unit.

10 ... Plasma CVD equipment (film deposition equipment)
DESCRIPTION OF SYMBOLS 1 ... 1st electrode 2 ... 2nd electrode 21 ... Through-hole (film-forming material supply part, nozzle)
3 ... support 4 ... spacer (leg)
5 ... Vacuum chamber
6 ... Exhaust means 7 ... Gas supply means 8 ... Power supply (high frequency power supply)
9 ... Cooling means 50 ... Heat insulation layer (void)
60 ... temperature detection means 1000 ... ink jet recording apparatus (droplet ejection apparatus)
100: Inkjet head (droplet ejection head)
DESCRIPTION OF SYMBOLS 81 ... Silicon substrate 82 ... Diaphragm 83 ... Lower electrode 84 ... Piezoelectric thin film 85 ... Upper electrode 86 ... Nozzle plate 86A ... Ink discharge nozzle (through-hole)
861 ... Base 862 ... Liquid repellent film 87 ... Ink reservoir (cavity)
91A ... Inkjet head unit (recording head unit)
91B ... Inkjet head unit (recording head unit)
92A ... cartridge 92B ... cartridge 93 ... carriage 94 ... main body 95 ... carriage shaft 96 ... drive motor 97 ... timing belt 98 ... platen S ... recording sheet

Claims (15)

A first electrode on which a substrate on which a film is formed is installed;
A plasma CVD apparatus having a second electrode disposed opposite to the first electrode,
At least a part of the first electrode is supported by a support through a heat insulating layer.   The plasma CVD apparatus according to claim 1, wherein the first electrode is supported by the support via a spacer. 3. The plasma CVD apparatus according to claim 1, wherein the spacer has a volumetric heat capacity at 100 ° C. of 2.00 [J · cm ⁻³ · K ⁻¹ ] or more.   The plasma CVD apparatus according to any one of claims 1 to 3, further comprising a temperature detection unit configured to detect a temperature of the base material or the first electrode, and controlling an output of the high-frequency power source based on the detected temperature. 5. The plasma CVD apparatus according to claim 1, wherein the volumetric heat capacity of the first electrode at 100 ° C. is 2.00 [J · cm ⁻³ · K ⁻¹ ] or more.   6. The plasma CVD apparatus according to claim 1, wherein the first electrode is movable and configured to be able to contact the support after the film formation is completed. The plasma CVD apparatus according to claim 1, wherein the support is made of a material having a thermal conductivity at 100 ° C. of 100 [W · m ⁻¹ · K ⁻¹ ] or more. . A voltage is applied between the first electrode and a second electrode different from the first electrode in a state where a substrate on which a film is formed is placed on the first electrode, and the base is formed by a plasma CVD method. A film forming method for forming a film on a material,
A film forming method comprising performing film formation in a state where at least a part of the first electrode is supported by a support through a heat insulating layer.   The film forming method according to claim 8, wherein the first electrode is movable, maintains a state of being separated from the support during film formation, and contacts the support after completion of film formation.   A film formed using the plasma CVD apparatus according to claim 1.   A film formed using the film forming method according to claim 8. A substrate;
A film-formed member comprising: a film formed using the plasma CVD apparatus according to claim 1. A substrate;
A film-coated member comprising: a film formed by using the film forming method according to claim 8.   The film-attached member according to claim 12 or 13, wherein the thickness of the film is 0.1 µm or more and 5.0 µm or less.   The member with a film according to any one of claims 12 to 14, wherein the member with a film is a nozzle plate.

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