JP2016108595A - Film deposition method, film deposition apparatus, and member with film - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a film deposition method and a film deposition apparatus capable of forming a film having a low internal stress, an excellent adhesion with a substrate, and a high surface hardness, and a member with the film having a low internal stress, the excellent adhesion with the substrate, and the high surface hardness.SOLUTION: A film deposition method forming a film composed of silicon by a plasma CVD method using a silicon compound as a deposition material, the method includes steps of: starting a film deposition at a substrate temperature of a first temperature of 40-90°C; and completing the film deposition at a substrate temperature of a second temperature of 110-170°C, the second temperature being higher than the first temperature. A difference between the first temperature and the second temperature is 30-100°C.SELECTED DRAWING: None

Description

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

  As a vapor deposition method for forming a thin film, plasma CVD or the like is known (see, for example, Patent Document 1).

  However, the conventional vapor deposition method sometimes causes problems such as warping of a member on which a film is formed (member with a film). In addition, there is a problem that peeling of the film is likely to occur.

  In order to prevent such a problem, the film forming temperature may be lowered, but in such a case, there is a problem that the hardness of the film is lowered and the abrasion resistance is lowered.

JP 2009-184176 A

  An object of the present invention is to provide a film forming method and a film forming apparatus capable of forming a film having high surface hardness while being excellent in adhesiveness with a substrate, and excellent in adhesiveness with a substrate. An object of the present invention is to provide a film-coated member provided with a film having a high surface hardness.

Such an object is achieved by the present invention described below.
In the film forming method of the present invention, film formation is started in a state where the temperature of the base material is set to the first temperature, and the temperature of the base material is set to a second temperature higher than the first temperature. It is characterized by terminating the membrane.

  Thereby, while being excellent in adhesiveness with a base material, the film-forming method which can form a film | membrane with high surface hardness can be provided.

  In the film forming method of the present invention, the first temperature is preferably 40 ° C. or higher and 90 ° C. or lower.

  Thereby, the internal stress of the film | membrane formed can be made smaller, and the adhesiveness of the film | membrane with respect to a base material can be made especially excellent.

  In the film forming method of the present invention, the second temperature is preferably 110 ° C. or higher and 170 ° C. or lower.

  As a result, the internal stress of the film to be formed can be made sufficiently small, and the adhesion of the film to the substrate can be made sufficiently excellent, while the surface hardness of the film can be made particularly high.

  In the film forming method of the present invention, the difference between the second temperature and the first temperature is preferably 30 ° C. or higher and 100 ° C. or lower.

  Thereby, the adhesion between the substrate and the film and the surface hardness of the film can be achieved at a higher level while the film formation efficiency (productivity of the member with the film) is particularly excellent.

In the film formation method of the present invention, the film formation is preferably performed by a plasma CVD method.
Thereby, the adhesion between the base material and the film and the surface hardness of the film can be achieved at a higher level. Further, the film formation efficiency can be made particularly excellent while effectively preventing damage to the member on which the film is formed.

  In the film forming method of the present invention, it is preferable to use a silicon compound as a film forming material and form a film made of silicone.

  Thereby, it can be suitably applied to, for example, a nozzle plate of a droplet discharge device. In the past, when forming a film composed of silicone, it was particularly difficult to achieve both the adhesion between the base material and the film and the surface hardness. Even when the formed film is formed, the adhesion between the base material and the film and the surface hardness of the film can be achieved at a high level. 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.

The film forming apparatus of the present invention is a film forming apparatus for forming a film on a substrate,
A film forming material supply unit for supplying a gaseous film forming material;
A stage on which the substrate is installed;
Temperature adjusting means for adjusting the temperature of the stage or the substrate.

  Thereby, while being excellent in adhesiveness with a base material, the film-forming apparatus which can form a film | membrane with high surface hardness can be provided.

The film forming apparatus of the present invention is a plasma CVD apparatus having a first electrode and a second electrode,
It is preferable that the second electrode functions as the stage.

  Thereby, the adhesion between the base material and the film and the surface hardness of the film can be achieved at a higher level. Further, the film formation efficiency can be made particularly excellent while effectively preventing damage to the member on which the film is formed.

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, while being excellent in adhesiveness with a base material, the member with a film | membrane provided with the film | membrane with high surface hardness can be provided.

The film-coated member of the present invention comprises a base material,
A film-coated member comprising: a film formed using the film forming apparatus of the present invention.

  Thereby, while being excellent in adhesiveness with a base material, the member with a film | membrane provided with the film | membrane with high surface 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 adhesion between the base material and the film and the surface hardness of the film can be achieved at a higher level. Further, the film formation efficiency can be made particularly excellent.

The film-coated member of the present invention is preferably a nozzle plate.
The nozzle plate is a member that is prone to problems such as peeling of the film from the substrate, among members with various films, and is a member that is prone to problems such as deterioration of properties when the film is peeled, In this invention, even if it is a case where it applies to a nozzle plate, the adhesiveness of a base material and a film | membrane and the surface hardness of a film | membrane can be exhibited stably 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.

  Note that in this specification, the expression “above” or “below” is used for a predetermined numerical value with respect to a range including the numerical value.

It is a longitudinal cross-sectional view which shows the outline of suitable embodiment of the film-forming apparatus of this invention typically. It is a schematic plan view of the 1st electrode which comprises the film-forming apparatus of this invention shown in FIG. It is a figure which shows typically the time-dependent change of the base-material temperature at the time of film-forming. 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.

<Film deposition system>
First, the film forming apparatus of the present invention will be described.

In the following description, a case where film formation is performed by a plasma CVD method will be representatively described.
Thereby, the adhesion between the base material and the film and the surface hardness of the film can be achieved at a higher level. Further, the film formation efficiency can be made particularly excellent while effectively preventing damage to the member on which the film is formed.

  FIG. 1 is a longitudinal sectional view schematically showing an outline of a preferred embodiment of a film forming apparatus of the present invention, and FIG. 2 is a schematic diagram of a first electrode constituting the film forming apparatus of the present invention shown in FIG. It is a top view.

  A plasma CVD apparatus 10 as a film forming apparatus of the present invention includes a first electrode 1, a second electrode 2 on which a base material on which a film is to be formed, and a temperature adjusting means for adjusting the temperature of the second electrode 2. 3, a temperature detection means 4 for detecting the temperature of the second electrode 2, a vacuum chamber (chamber) 5 for housing the first electrode 1 and the second electrode 2, an exhaust means 6 for exhausting the inside of the vacuum chamber 5, A gas supply means 7 for supplying gas into the vacuum chamber 5 and a power source 8 are provided.

  The first electrode 1 is electrically connected to a power source (high frequency power source) 8 through a matching circuit (not shown).

  The first electrode 1 has a through-hole (film formation material) for introducing a gas (including a film formation material) supplied from a gas supply means 7 (described later) into the space between the first electrode 1 and the second electrode 2. A plurality of supply units (nozzles) 11 are provided.

  Thereby, the film-forming material can be efficiently supplied toward the base material installed on the second electrode 2, and the ratio of the film-forming material that is not used for film formation can be reduced, so that 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) 11 are provided uniformly over almost the entire surface of the first electrode 1.
Thereby, the effects as described above are more remarkably exhibited.

The shape of the through hole 11 when the first electrode 1 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 11 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.

  The pitch (center-to-center distance) between the adjacent through holes 11 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 substrate or the surface of the surface of the first electrode 1 (the surface on the side facing the second electrode 2) 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.

When the first electrode 1 is viewed in plan from the side where the second electrode 2 is provided, the area of the first electrode 1 is S ₀ [mm ² ], and the total area of the plurality of through holes 11 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 substrate or the surface of the surface of the first electrode 1 (the surface on the side facing the second electrode 2) 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 first electrode 1 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 first electrode 1 may be subjected to a surface treatment.
Thereby, for example, it is possible to improve the corrosion resistance of the first electrode 1 and to improve the resistance to the sputtering phenomenon.

  When the 1st electrode 1 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 second electrode 2 is grounded (earthed), and is configured to generate a potential difference with the first electrode 1.

The second electrode 2 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 second electrode 2 when viewed in plan is not particularly limited, but is circular in this embodiment.
Thereby, a film-forming process can be more suitably performed on a wafer-like base material or the like.

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

  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 as a film forming material to 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. In the past, when forming a film composed of silicone, it was particularly difficult to achieve both the adhesion between the base material and the film and the surface hardness. Even when the formed film is formed, the adhesion between the base material and the film and the surface hardness of the film can be achieved at a high level. 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 temperature adjusting means 3 adjusts the temperature of the second electrode (stage) 2.
Examples of the temperature adjusting means 3 include heating means such as various heaters such as an infrared heater and a heating wire heater, a cooling means using fins or a refrigerant, and the like, which includes both the heating means and the cooling means. Is preferred. Thereby, the temperature of the 2nd electrode (stage) 2 and a base material can be adjusted more suitably.

  By providing the temperature adjusting means 3, for example, the temperature of the base material can be suitably adjusted during film formation. For example, film formation can be started in a state where the first temperature is set, and film formation can be ended in a state where the temperature of the base material is set to a second temperature higher than the first temperature.

  Thereby, as will be described in detail later, the internal stress of the film to be formed can be made small, and the film can have high surface hardness while the film has excellent adhesion to the substrate.

The temperature detection means 4 detects the temperature of the second electrode (stage) 2.
By providing such a temperature detection means 4, the temperature adjustment by the temperature adjustment means 3 can be more appropriately performed using the detection result of the temperature detection means 4. As a result, for example, the internal stress of the film to be formed can be made smaller, the film can be made to have a higher surface hardness while the adhesion of the film to the substrate is more excellent.
Various temperature sensors can be used as the temperature detection means 4.

The plasma CVD apparatus 10 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 temperature adjustment by the temperature adjustment unit. Etc. are controlled.
Thereby, film formation can be performed under suitably controlled conditions.

  According to the film forming apparatus of the present invention as described above, it is possible to efficiently form a film having excellent adhesion to the base material and high surface hardness.

<< Film Formation Method (Film Production Method) >>
Next, the film forming method (film manufacturing method) of the present invention will be described.
FIG. 3 is a diagram schematically showing a change with time of the substrate temperature during film formation.

  In the film forming method of the present invention, film formation is started in a state where the temperature of the base material is set to the first temperature, and the temperature of the base material is set to a second temperature higher than the first temperature. It is characterized by terminating the membrane.

  Thereby, while reducing the internal stress of a film | membrane, while being excellent in adhesiveness with a base material, the film-forming method which can form a film | membrane with high surface hardness can be provided.

  In addition, for example, the formed film can be formed so that the film density and composition change in a gradient direction in the thickness direction, and problems such as delamination can be effectively prevented. .

On the other hand, for example, when the temperature of the base material is kept at a high temperature (for example, temperature T ₂ ) during film formation, the internal stress of the film becomes large, and the adhesion between the base material and the film is sufficient. The film cannot be excellent, and the film is easily peeled off from the substrate due to an external force such as a rapid temperature change or friction.

Further, when the temperature of the base material is kept at a relatively low temperature (for example, temperature T ₁ ) at the time of film formation, the hardness of the formed film becomes low.

  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 reducing 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 11 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.

Here, in the present invention, as described above, film formation is started in a state where the temperature of the base material is set to the first temperature, and the temperature of the base material is set to a second temperature higher than the first temperature. In this state, the film formation is finished. In this embodiment, the first electrode 1 and the temperature of the substrate when a voltage is applied between the second electrode 2 and the first temperature T _1, when the deposited stops generating the plasma is terminated ( For example, when the application of voltage is stopped and the film forming material in the vacuum chamber 5 no longer takes a plasma state, the temperature of the film forming material in the vacuum chamber 5 runs out, etc.), the temperature is higher than the first temperature T _1. the high second temperature _{T 2.} Thereby, the internal stress of a film | membrane is relieve | moderated to a base material, and while being excellent in adhesiveness with a base material, a film | membrane with high surface hardness can be formed stably. In the CVD method, when the substrate temperature is high, the film formation rate increases. When the substrate temperature is low, the film formation rate tends to decrease. In addition, in the CVD method, the temperature of the base material at the start of film formation is set to a relatively low temperature (first temperature T ₁ ), and then the temperature of the base material is increased to improve the efficiency of film formation. However, the film thickness can be adjusted easily and reliably.

The first temperature (T ₁ ) is preferably 40 ° C. or higher and 90 ° C. or lower, and more preferably 60 ° C. or higher and 80 ° C. or lower.

  Thereby, the internal stress of the film | membrane formed can be made smaller, and the adhesiveness of the film | membrane with respect to a base material can be made especially excellent.

In addition, the second temperature (T ₂ ) is preferably 110 ° C. or higher and 170 ° C. or lower, and more preferably 120 ° C. or higher and 150 ° C. or lower.

  As a result, the internal stress of the film to be formed can be made sufficiently small, the adhesion of the film to the substrate can be made sufficiently excellent, and the surface hardness of the film can be made particularly high.

Further, the difference (T ₂ −T ₁ ) between the second temperature and the first temperature is preferably 30 ° C. or higher and 100 ° C. or lower, and more preferably 40 ° C. or higher and 80 ° C. or lower.

  Thereby, the adhesion between the substrate and the film and the surface hardness of the film can be achieved at a higher level while the film formation efficiency (productivity of the member with the film) is particularly excellent.

The time until the temperature of the base material reaches 0.7 × (T ₂ −T ₁ ) [° C.] from T ₁ [° C.] is preferably 60 seconds or more and 200 seconds or less, more preferably 100 seconds or more. More preferably, it is 180 seconds or less.

  Thereby, the adhesion between the substrate and the film and the surface hardness of the film can be achieved at a higher level while the film formation efficiency (productivity of the member with the film) is particularly excellent.

Further, among the film, temperature of the substrate is 0.7 × _(T 2 _-T 1) The thickness of the portion deposited from reaching the [℃] is formed before completion, 150 nm or more 600nm or less It is preferable that it is 300 nm or more and 400 nm or less.

  Thereby, the adhesion between the substrate and the film and the surface hardness of the film can be achieved at a higher level while the film formation efficiency (productivity of the member with the film) is particularly excellent.

  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.

  By the way, in the past, when a film having a large thickness was to be formed, the above-described problem of decrease in adhesion between the substrate and the film was particularly likely to occur. Even if it is formed, the occurrence of the above problems can be reliably prevented.

  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.

  As described above, when the film thickness is relatively thick, the above-described problem has occurred more remarkably. However, in the present invention, even when the film thickness is relatively thick as described above, It is possible to reliably prevent the occurrence of a serious problem. Therefore, when the thickness of the film is within the above range, the effect of the present invention is more remarkably exhibited, and the adhesion between the substrate and the film and the surface hardness of the film are compatible at a higher level. be able to. Further, the film formation efficiency (productivity of the film-coated member) can be made particularly excellent.

  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.

《Member with membrane》
Next, the film-coated member of the present invention will be described.

  The member with a film of the present invention comprises a substrate and a film formed using the film forming method of the present invention and the film forming apparatus of the present invention.

  Thereby, while being excellent in adhesiveness with a base material, the member with a film | membrane provided with the film | membrane with high surface hardness can be provided.

  Note that the base material on which the film is formed using the film forming method and film forming apparatus 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 or the like. 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 include a film formed by using the above-described film formation apparatus and film formation method 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 a droplet discharge head, a liquid repellent film is generally provided in order to prevent excessive wetting and spreading of ink on the nozzle plate, but the nozzle plate is subject to vibration associated with droplet discharge. In general, an operation of wiping off ink adhering many times or adhering by a wiping means is performed. Therefore, the nozzle plate is a member that easily causes problems such as peeling of the film from the substrate, and is a member that easily causes problems such as deterioration of characteristics when the film peels. However, in the present invention, even when applied to the nozzle plate, the above-described effects 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 and the film forming apparatus of the present invention as described above, or a film obtained by performing a predetermined process on the film.
An example of a method for manufacturing such a nozzle plate 86 will be described below.

  First, a substrate (base 861) made of nickel or the like and provided with an opening corresponding to the ink discharge nozzle (through hole) 86A is prepared. The film is formed using a film formation method) and a film formation apparatus (particularly a CVD apparatus). 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 film forming apparatus of the present invention, the configuration of each part can be replaced with an arbitrary configuration that exhibits the same function, and an arbitrary configuration can be added.

  In the above-described embodiment, the plasma CVD apparatus is typically described as the film forming apparatus. However, the film forming apparatus of the present invention is a CVD apparatus other than the plasma CVD apparatus or a film forming apparatus other than the CVD apparatus. Also good.

  In the above-described embodiment, the method using the plasma CVD method as a film forming method is representatively described. However, the film forming method of the present invention can be applied to a CVD method other than the plasma CVD method, It may be.

  Further, in the above-described embodiment, the stage temperature is adjusted by the temperature adjusting unit. However, the temperature of the base material may be directly adjusted. In the above-described embodiment, the temperature detection unit is described as detecting the temperature of the stage. However, the temperature of the base material may be adjusted.

10 ... Plasma CVD equipment (film deposition equipment)
DESCRIPTION OF SYMBOLS 1 ... 1st electrode 11 ... Through-hole (film-forming material supply part, nozzle)
2 ... second electrode 3 ... temperature adjusting means 4 ... temperature detecting means 5 ... vacuum chamber
6 ... Exhaust means 7 ... Gas supply means 8 ... Power supply (high frequency power supply)
1000: Inkjet recording device (droplet discharge device)
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 (12)

  The film formation is started in a state where the temperature of the base material is set to the first temperature, and the film formation is ended in a state where the temperature of the base material is set to a second temperature higher than the first temperature. A film forming method.   The film forming method according to claim 1, wherein the first temperature is 40 ° C. or higher and 90 ° C. or lower.   The film forming method according to claim 1, wherein the second temperature is 110 ° C. or higher and 170 ° C. or lower.   The film forming method according to claim 1, wherein a difference between the second temperature and the first temperature is 30 ° C. or more and 100 ° C. or less.   The film formation method according to claim 1, wherein the film formation is performed by a plasma CVD method.   The film forming method according to claim 1, wherein a silicon compound is used as a film forming material to form a film made of silicone. A film forming apparatus for forming a film on a substrate,
A film forming material supply unit for supplying a gaseous film forming material;
A stage on which the substrate is installed;
And a temperature adjusting means for adjusting the temperature of the stage or the base material. The film forming apparatus is a plasma CVD apparatus having a first electrode and a second electrode,
The film forming apparatus according to claim 7, wherein the second electrode functions as the stage. A substrate;
A film-formed member comprising: a film formed by using the film forming method according to claim 1. A substrate;
A film-coated member comprising: a film formed using the film forming apparatus according to claim 7.   The film-coated member according to claim 9 or 10, wherein the thickness of the film is 0.1 µm or more and 5.0 µm or less.   The film-coated member according to any one of claims 9 to 11, wherein the film-coated member is a nozzle plate.

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