JP4077372B2 - Deposition equipment - Google Patents

Description

[0001]
BACKGROUND OF THE INVENTION
The present invention relates to a film forming apparatus for forming a film by injecting aerosolized fine particles onto a substrate or the like, and more particularly to a film forming apparatus capable of forming a thick film having a dense film quality and high adhesion strength with good uniformity. .
[0002]
[Prior art]
Recently, there is a demand for downsizing, high performance, and multi-functionality of electronic devices and electronic components constituting the electronic devices. In order to realize these requirements, it is important to integrate and form different materials having various functions. Until now, in the field of circuit boards, semiconductor elements, and passive electronic components, for example, by forming a structure by a combination of a resin material and a metal material, and a ceramic material and a metal material, an electronic component or the like that meets the above requirements can be obtained. Has been realized.
[0003]
However, since the process body of a structure formed by a combination of a resin material and a ceramic material is greatly different from each other, a composite method in which both characteristics are sufficiently exhibited has not yet been realized. As one of the attempts, there is a technique in which ceramic powder or the like is mixed in a resin to form a composite, but the present situation is that a material that sufficiently satisfies the required characteristics has not been obtained. For example, in the development of a dielectric film having a high dielectric constant, there is a limit to the packing rate of ceramics in the resin material even in the combination of high dielectric ceramics and resin material, and only a material having a dielectric constant of several tens can be obtained. Absent.
[0004]
The aerosol deposition method in which an inorganic material film is formed on a substrate by spraying an aerosol in which inorganic material fine particles are dispersed in a gas from a nozzle and depositing it on the substrate can form a ceramic film at room temperature. As a result, it is expected to realize compounding and integration with resin materials without impairing the original characteristics of the materials, and research and development in the field of electronic parts are starting to become active.
[0005]
[Patent Document 1]
Japanese Patent Laid-Open No. 3-231096
[0006]
[Patent Document 2]
JP 2003-89866 A
[0007]
[Problems to be solved by the invention]
By the way, as shown in FIG. 1, the fine particle flow 13 ejected from the nozzle 10 by the aerosol deposition method has a high velocity at the central portion of the emission port 10A of the nozzle 10, and the flow velocity increases toward the end of the emission port 10A. Decrease. Of the film 12 deposited on the substrate 11, the portion 14 where the fine particles ejected from the central portion of the exit port 10 </ b> A are deposited has good film density and good film adhesion strength with the substrate 11. The portion 15 where the fine particles emitted from the end portion of 10A are deposited is insufficient in the velocity of the fine particle flow, so that the denseness and the film adhesion strength with the substrate 11 (or the previously deposited film) are lowered and easily peeled off. There is a problem of end.
[0008]
Further, even if an attempt is made to further form a film on the surface of the poorly adhesive portion 15, the poorly adhesive portion 15 previously formed by the flow of fine particles is peeled off, so that the film cannot be thickened. .
[0009]
Accordingly, the present invention has been made in view of the above problems, and an object of the present invention is to provide a film forming apparatus capable of forming a film having high density and high adhesion strength with good uniformity.
[0010]
[Means for Solving the Problems]
According to one aspect of the present invention, there is provided a film forming apparatus having a fine particle injection nozzle for injecting an aerosolized fine particle material onto a substrate in a film formation chamber to deposit the fine particle material, and the fine particle injection nozzle is injected from the fine particle injection nozzle. Provided with a shielding unit that blocks a particulate flow having a velocity of the particulate flow within a predetermined range of the particulate flow, and the shielding unit is integrated with a particulate injection nozzle. Is done.
[0011]
According to the present invention, there is provided shielding means for shutting off the fine particle flow ejected from the fine particle jet nozzle, and the shutting means shuts off the fine particle flow having a speed slower than a predetermined speed, and is above the predetermined speed on the substrate. A particulate stream having a velocity of Therefore, the film formed on the substrate is dense and has high film adhesion strength. Further, since the shielding means is integrated with the fine particle injection nozzle, continuous film formation is possible by moving the substrate or the fine particle injection nozzle, and the adhesion strength of the formed film is high. The film thickness can be increased easily. As a result, a thick film having a large area can be formed efficiently.
[0012]
According to another aspect of the present invention, there is provided a film forming apparatus having a fine particle injection nozzle for spraying an aerosolized fine particle material onto a substrate moving in a film forming chamber to deposit the fine particle material, the fine particle injection nozzle There is provided a film forming apparatus characterized by having a gas injection nozzle for injecting and removing a part of the deposited thick film by injecting a gas.
[0013]
According to the present invention, a gas injection nozzle is provided adjacent to the fine particle injection nozzle, and the gas injection nozzle injects a gas onto the thick film formed by depositing the fine particle material, whereby the film adhesion strength of the thick film is increased. Remove the low part. Therefore, it is possible to leave only a portion where the film is dense and the film adhesion strength is large. As a result, a film can be further formed on this portion, and a thick film with high film quality and high adhesion strength with the substrate can be formed with good uniformity.
[0014]
According to another aspect of the present invention, there is provided a film forming apparatus having a fine particle injection nozzle for spraying an aerosolized fine particle material onto a substrate in a film formation chamber to deposit the fine particle material, wherein the fine particle injection nozzle includes: A flow path for aerosolized particulate material is provided at the tip of the nozzle, and the area of the flow path is gradually reduced from upstream to downstream, and the particulate material flows in a spiral flow in the flow path. There is provided a film forming apparatus provided with guide means for forming.
[0015]
According to the present invention, the flow path area gradually decreases at the tip of the fine particle injection nozzle, and the guide means for forming the flow of the fine particle material in a spiral shape is provided. Accordingly, the carrier gas of the fine particle material is compressed and becomes a fine particle flow having a spiral flow and is ejected from the fine particle ejection nozzle, and reaches the substrate while maintaining the speed without being diffused. As a result, since the velocity of the fine particle flow impinging on the substrate is large and uniform, a thick film having a dense film quality and high adhesion strength with the substrate can be formed with good uniformity.
[0016]
In the case where an aerosolized fine particle material is introduced into a film forming chamber and formed into a film by injecting the fine particle material onto the substrate from the fine particle injection nozzle, the fine particle material is injected from the fine particle injection nozzle while the substrate is moved. The thick film may be deposited to form a thick film, and a gas may be sprayed from a gas spray nozzle to remove a part of the thick film and to be discharged in the substrate moving direction. A thick film is formed while moving the substrate, and a portion of the thick film having a low film adhesion strength is removed by jetting a gas, so that only a portion having a high film adhesion strength can be left and continuously formed. Can be membrane. Further, since the removed particulate material is discharged in the direction in which the thick film has already been formed, it does not scatter in the direction of the substrate surface on which a film is to be formed.
[0017]
DETAILED DESCRIPTION OF THE INVENTION
Hereinafter, embodiments of the present invention will be described with reference to the drawings. Hereinafter, a film formed by depositing a particulate material by the film forming apparatus according to the present invention is referred to as an AD film.
[0018]
(First embodiment)
FIG. 2 is a schematic configuration diagram of a film forming apparatus according to an embodiment of the present invention. Referring to FIG. 2, the film forming apparatus 20 generally includes an aerosol generator 21 that aerosolizes the particulate material 27, and the aerosolized particulate material 27 is ejected from the particulate ejection nozzle 22 to form an AD film on the substrate 23. The film forming chamber 24 is formed.
[0019]
A gas cylinder 25, a mass flow controller 26, and a valve 28 are connected to the aerosol generator 21 via piping. The mass flow controller 26 controls a carrier gas such as high-pressure argon filled in the gas cylinder 25. The amount of fine particles generated in the container 29 of the aerosol generator 21 and the amount of aerosolized fine particles ejected in the film forming chamber 24 can be controlled. As the carrier gas, an inert gas such as helium, neon, or nitrogen can be used in addition to argon gas. When oxide ceramics having a perovskite structure is used as the fine particle material 27, the carrier gas may be an oxidizing gas such as oxygen or air. Oxygen vacancies in the oxide ceramic fine particle material 27 can be compensated during film formation.
[0020]
In addition, the aerosol generator 21 is provided with a vibrator 30 for converting fine particles into primary particles by ultrasonic vibration, electromagnetic vibration, or mechanical vibration. A dense and uniform AD film can be formed by forming primary particles.
[0021]
The film formation chamber 24 is provided with a fine particle injection nozzle 22 connected from the aerosol generator 21 via a pipe 31, and a substrate holder 32 that holds the substrate 23 facing the fine particle injection nozzle 22. An XYZ stage 33 that moves 23 is connected to the substrate holder 32.
[0022]
The fine particle injection nozzle 22 has a mask 34 that blocks the flow of fine particles below a predetermined speed and prevents the fine particle injection nozzle 22 from reaching the substrate 23, and a discharge gas that induces the fine particle material divided by the mask 34 by injecting gas. An injection nozzle 35 is provided. A gas such as dry air is introduced into the discharge gas injection nozzle 35 through the mass flow controller 38 and the valve 39 from the outside of the film forming chamber 24 by a high-pressure gas cylinder 36.
[0023]
Further, a mechanical booster 40 and a rotary pump 41 are connected to the film forming chamber 24 for reducing the pressure in the film forming chamber 24 and exhausting the carrier gas.
[0024]
Next, a method for forming a film with the film forming apparatus will be described. First, the aerosol generator 21 is filled with fine particles having an average particle diameter of 10 nm to 1 μm as a forming material, and is discharged from the gas cylinder 25, for example, 19.6 Pa to 49 Pa (2 to 5 kg / cm 2). ² ) Is supplied to the film forming chamber 24 as a carrier gas, and is vibrated by the vibrator 58 to aerosolize the fine particles. The aerosolized fine particles are transported together with the carrier gas through the pipe 31 to the film forming chamber 24 set to a pressure lower than the pressure in the container 29 of the aerosol generator 21. In the film forming chamber 24, fine particles are jetted together with the carrier gas from the fine particle jet nozzle 22 to form a fine particle flow, and the fine particle material is deposited on the substrate 23 and the like to form an AD film.
[0025]
The injection speed can be controlled by the shape of the fine particle injection nozzle 22, the pressure of the introduced carrier gas, and the pressure difference between the aerosol generator 21 and the film formation chamber 24, and is preferably 3 m / sec to 400 m / sec (preferably Is set in a range of 200 m / second to 400 m / second). By setting the spray speed within this range, a thick film having high adhesion strength with the substrate 23 can be formed. When the fine particles collide with the substrate 23, the contaminated layer and moisture on the surface of the substrate 23 are removed to activate the surface. Further, the surface of the fine particles themselves is similarly activated by the collision of the fine particles. As a result, the fine particles are bonded to the surface of the substrate 23, and the fine particles are bonded to each other, so that a dense AD film having high adhesion strength is formed. Note that if the jetting speed is higher than 400 m / sec, the substrate 23 may be damaged, and if it is lower than 3 m / sec, sufficient adhesion strength cannot be ensured.
[0026]
The fine particle flow sprayed from the fine particle spray nozzle 22 and spread by the mask 34 provided in the fine particle spray nozzle 22 is cut out before reaching the substrate 23.
[0027]
FIG. 3 is an enlarged sectional view showing the emission port 22A of the fine particle injection nozzle 22. As shown in FIG. Referring to FIG. 3, the mask 34 is provided between the emission port 22 </ b> A of the fine particle injection nozzle 22 and the substrate 23, and the opening 34 </ b> A and a concave portion 34 </ b> B that guides the cut out fine particle flow are formed.
[0028]
Of the fine particle flow ejected from the emission port 22A of the particle ejection nozzle 22, the flow of particles passing through the opening 34A of the mask 34 is deposited on the substrate 23 to form an AD film 42. On the other hand, the particulate flow blocked by the mask 34 flows toward the concave portion 34 </ b> B of the mask 34 and does not reach the surface of the substrate 23.
[0029]
Here, the size of the opening 34A is appropriately determined depending on the shape of the emission port 22A of the fine particle injection nozzle 22, but is determined as follows, for example. First, in a state where the mask 34 is not provided, the incident direction is set to a substantially vertical direction from the particle injection nozzle 22 to the substrate 23, and the particle material is injected onto the substrate 23. The spraying conditions are the same as those for the AD film forming apparatus 20 described above. For example, TiO with an average particle diameter of 0.5 μm, which is surface-treated with aluminum hydroxide, is used for the fine particle material. ₂ A thick film is formed using a fine particle material.
[0030]
Next, the thickness distribution of the AD film is measured, and the range from the maximum thickness to a portion having a thickness of 90% of the maximum thickness is set as the range of the opening. That is, if the particle density in the particle flow is considered to be constant, the velocity of the particle flow is considered to be proportional to the deposition rate. Therefore, the velocity of the particle flow is sufficient in the range up to 90% of the maximum thickness. The film adhesion strength is sufficiently secured. By forming the opening 34A of the mask 34 in this way, variation in the film adhesion strength of the deposited AD film 42 can be reduced, and a dense AD film 42 can be formed.
[0031]
The position of the mask 34 is preferably as close as possible to the substrate 23. For example, the distance between the mask 34 and the substrate 23 is set to 5 mm.
[0032]
4 is a view as seen from above the fine particle injection nozzle shown in FIG. Referring to FIG. 4, a discharge gas injection nozzle 35 is provided behind the emission port 22 </ b> A of the fine particle injection nozzle 22 in the substrate movement direction indicated by the arrow X. The discharge gas injection nozzle 35 injects a gas that guides the fine particles of the low-speed fine particle flow separated by the mask 34 in the substrate movement direction X. In this way, the surface of the substrate 23 on which the particulate material is deposited is prevented from being contaminated by the particulates. The gas is selected from dry air, nitrogen, argon, helium and the like, and the gas velocity is appropriately selected.
[0033]
According to the present embodiment, by providing a mask between the fine particle injection nozzle 22 and the substrate 23 that cuts out and discharges the fine particle flow whose velocity of the fine particle flow is lower than a predetermined speed, the film quality is dense on the substrate 23. In addition, the AD film 42 having high adhesion strength can be easily formed.
[0034]
(Second Embodiment)
A film forming apparatus according to an embodiment of the present invention includes a portion of an AD film having a low adhesion strength by injecting a gas onto an AD film that is injected from a fine particle injection nozzle that moves relative to a substrate and on which a fine particle material is deposited. It is characterized by having a gas injection nozzle that removes water.
[0035]
FIG. 5 is a schematic configuration diagram of a film forming apparatus according to an embodiment of the present invention. In the figure, portions corresponding to the portions described above are denoted by the same reference numerals, and description thereof is omitted. Referring to FIG. 5, a removal gas injection nozzle 51 is provided adjacent to the fine particle injection nozzle 22 in the film formation chamber 24 of the film formation apparatus 50. A high-pressure gas cylinder 36 is connected to the removal gas injection nozzle in the same manner as the discharge gas injection nozzle 35 of the first embodiment, and one or a mixed gas selected from dry air, nitrogen, helium, and argon is used. Is supplied.
[0036]
FIG. 6 is an enlarged sectional view showing the emission ports of the fine particle injection nozzle and the discharge gas injection nozzle. Referring to FIG. 6, a known fine particle spray nozzle can be used as the fine particle spray nozzle 22. On the side of the substrate movement direction (indicated by arrow X) with respect to the fine particle injection nozzle, a removal gas injection nozzle 51 for removing the portion 52B having a low film adhesion strength of the AD film 52 is provided.
[0037]
When the film is formed by ejecting the particulate material from the particulate ejection nozzle 22 while moving the substrate 23, the particulate flow ejected from the emission port end 22B on the substrate movement direction (indicated by arrow X) side of the particulate ejection nozzle 22 is The film 52B is formed on the portion 52A of the AD film having a high adhesion strength that is formed by spraying, for example, from the vicinity of the center 22C of the exit port other than the exit end portion 22B. Since this film 52B is formed by a slow flow of fine particles, it has low density and low adhesion strength. By removing the film 52B by injecting gas from the removal gas injection nozzle 51, it is possible to leave only the portion 52A of the AD film with good film quality.
[0038]
Further, the ejection direction of the removal gas ejection nozzle 51 is preferably slightly in the substrate movement direction X from the direction perpendicular to the substrate surface 23. The removed AD film 52B can prevent contamination of the substrate surface on which the AD film will be formed.
[0039]
FIG. 7 is a top view of the fine particle injection nozzle and the removal gas injection nozzle. Referring to FIG. 7, the removal gas injection nozzle 51 is formed wider in the lateral direction than the fine particle injection nozzle 22 in the substrate movement direction (indicated by the arrow X). Not only the surface portion 52B of the AD film 52 sprayed and deposited from the fine particle spray nozzle 22, but also the portion 52C of the AD film formed in the lateral direction with low density and low adhesion strength is removed from the removal gas spray nozzle 51. It can be removed by the injected gas, and only the thick film portion 52A with good film quality can be left.
[0040]
The removal gas injection nozzle 51 may be a single wide nozzle, or may be a combination of, for example, three nozzles 51A to 51C as shown in FIG. By selecting the flow velocity of the gas injected from the three nozzles 51A to 51C, the surface portion of the thick film and the portions on both sides in the width direction can be efficiently removed. The three nozzles 51 </ b> A to 51 </ b> C may be aligned or may not be aligned, and regions where gas is injected may overlap each other.
[0041]
Further, the distance between the fine particle injection nozzle 22 and the removal gas injection nozzle 51 is preferably 10 mm or more. It can be prevented that the flow of the fine particles injected from the fine particle injection nozzle 22 interferes with the gas injected from the gas injection nozzle 51 for removal to disturb the speed and direction of both.
[0042]
According to the present embodiment, by removing the portions 52B and 52C having a low film adhesion strength using the removal gas injection nozzle 51, only the dense and high AD film portion 52A can be left, Therefore, continuous film formation can be performed efficiently, and the area of the AD film can be easily increased.
[0043]
(Third embodiment)
FIG. 9 is a cross-sectional view of the emission port of the fine particle injection nozzle used in the film forming apparatus according to the third embodiment of the present invention.
[0044]
Referring to FIG. 9, the emission port 60 of the fine particle injection nozzle has a generally tapered channel 61 from the upstream side 60 </ b> A to the downstream side 60 </ b> B where the fine particle material aerosolized by the carrier gas is conveyed. And continued along the inner wall 61A of the flow path 61. Convex The shaped member 62 is provided in a spiral shape.
[0045]
With such a channel 61, the particulate material flows in a spiral shape with the carrier gas in the channel 61. For example, in the channel indicated by the symbol YA, the fine particle material flows from the back of the page to the front, and in the channel indicated by the symbol YB from the front of the page. It flows in the back and is injected from the opening 60C on the downstream side 60B. The injected fine particle flow is added with a velocity component in the rotation direction having a rotation center coaxial with the emission port 60 in addition to the velocity component in the injection direction, and reaches the substrate 23 while forming a spiral flow, thereby reaching the AD film. 63 is formed. As a result, the diffusion of the fine particle flow ejected from the opening 60C of the emission port 60 is suppressed, and the AD film 63 is deposited on the substrate 23 in the same range as the size of the opening 60C of the emission port 60. Further, since the diffusion of the fine particle flow is suppressed, the speed of the fine particle flow reaching the substrate 23 is increased as compared with the case of a normal fine particle injection nozzle to which no velocity component in the rotation direction is added, and the velocity distribution on the substrate is increased. Since it is uniform, it is possible to form an AD film that is denser, has higher film adhesion strength, and has a uniform film quality.
[0046]
For example, the outlet 60 has a channel area of 150 mm upstream 60A. ² , Downstream side 60B 20mm ² Spiral Convex The length of the portion where the shaped member 62 is formed (upstream 60A to downstream 60B direction) is 30 mm, Convex The helical pitch of the member 62 is 5 mm, Convex Radius of the member ( Convex The position of the base of the shaped member) is set so that the upstream side 60A is 10 mm and the downstream side 60B is 5 mm. In addition, the flow path 61 of the emission port 60 is not limited as long as the particulate material flowing in the flow path 61 forms a spiral flow. Convex It is not limited to the shaped member 62 but may be a groove, a pipe or the like. Further, the entire configuration of the AD film forming apparatus is the same as that shown in FIG. 2, and a mask similar to the mask of the first embodiment may be provided.
[0047]
As the fine particle material used in the present invention, for example, a dielectric film suitable for a circuit board, a capacitor or the like containing a passive component includes, for example, TiO 2. ₂ , MgO, SiO ₂ , AlN, Al ₂ O _Three And oxide ceramics having a perovskite structure such as Pb-based PbTiO. _Three , PbZrO _Three , Pb (Zr _1-x Ti _x ) O _Three PZT represented by the general formula (0 ≦ x ≦ 1), (Pb _1-y La _y ) (Zr _1-x Ti _x ) O _Three PLZT, Pb (Mg) represented by the general formula (0 ≦ x, y ≦ 1) _1/3 Nb _2/3 ) O _Three , Pb (Ni _1/3 Nb _2/3 ) O _Three , Pb (Zn _1/3 Nb _2/3 ) O _Three Ba-based BaTiO _Three , BaTi _Four O ₉ , Ba ₂ Ti ₉ O ₂₀ , Ba (Zn _1/3 Ta _2/3 ) O _Three , Ba (Zn _1/3 Nb _2/3 ) O _Three , Ba (Mg _1/3 Ta _2/3 ) O _Three , Ba (Mg _1/3 Ta _2/3 ) O _Three , Ba (Co _1/3 Ta _2/3 ) O _Three , Ba (Co _1/3 Nb _2/3 ) O _Three , Ba (Ni _1/3 Ta _2/3 ) O _Three , Ba (Zr _1-x Ti _x ) O _Three , (Ba _1-x Sr _x ) TiO _Three Others, ZrSnTiO _Four , CaTiO _Three , MgTiO _Three , SrTiO _Three Is mentioned.
[0048]
Furthermore, examples of the fine particle material used in the present invention include ruthenium oxide (RuO) for a resistor film suitable for, for example, a circuit board incorporating a passive component and a resistor. ₂ ), Rhenium oxide (ReO) ₂ ), Iridium oxide (IrO ₂ ) And other oxide ceramics having a perovskite structure, such as SrVO _Three , CaVO _Three , LaTiO _Three , SrMoO _Three , CaMoO _Three , SrCrO _Three , CaCrO _Three , LaVO _Three , GdVO _Three , SrMnO _Three , CaMnO _Three NiCrO _Three , BiCrO _Three , LaCrO _Three , LnCrO _Three , SrRuO _Three , CaRuO _Three , SrFeO _Three , BaRuO _Three LaMnO _Three , LnMnO _Three LaFeO _Three , LnFeO _Three , LaCoO _Three , LaRhO _Three LaNiO _Three , PbRuO _Three , Bi ₂ Ru ₂ O ₇ , LaTaO _Three , BiRuO _Three Etc., LaB ₆ Is mentioned.
[0049]
Still further, as the fine particle material used in the present invention, for example, a conductor film suitable for a wiring layer of a circuit board incorporating a passive component, an inductor, etc., in addition to Cu, Ag, Au, Pt, Pd, Al Or the metal material containing the alloy which consists of these elements is mentioned.
[0050]
Furthermore, the fine particle material may be coated with a surface treatment or fine particles by adding a fine particle binder made of an aluminum compound or a lead compound. According to the study of the present inventor, it has been confirmed that a thick film, particularly an AD film having a dense film quality can be formed in the range of 5 μm to 1 mm, compared with the case where the above-mentioned fine particle material is used alone. The addition amount or the coating amount of the fine particle binder is 0.1% by mass to 50% by mass (more preferably) based on the weight (100 parts by mass) of the weight of the dielectric material as the main agent and the weight of the fine particle binder. Is preferably set to 0.1 mass% to 20 mass%.
[0051]
As the aluminum compound, Al ₂ O _Three LiAlO ₂ , MgAl ₂ O _Four , CaAl ₂ O _Four , SrAl ₂ O _Four , BaAl ₂ O _Four , Y _Three Al _Five O ₁₂ , AlN, Al ₂ O _Three ・ NH ₂ O, boehmite (γ-AlOOH), aluminum hydroxide (Al (OH)) _Three ), Aluminum alkoxide (Al (OR) _Three (R: alkyl group)), mullite (3Al ₂ O _Three ・ 2SiO ₂ ), Spinel (MgO · Al ₂ O _Three ), Cordierite (2Al ₂ O _Three ・ 2MgO ・ 5SiO ₂ ), Anorthite (CaO · Al ₂ O _Three ・ 2SiO ₂ ), Gehlenite (2CaO · Al ₂ O _Three ・ SiO ₂ ) And the like. Of these aluminum compounds, Al ₂ O _Three , Boehmite (γ-AlOOH), aluminum hydroxide (Al (OH)) _Three ), Aluminum alkoxide (Al (OR) _Three (R: alkyl group)) is preferred.
[0052]
As the lead-based compound, Pb ₂ FeNbO ₆ , Pb ₂ FeTaO ₆ , Pb ₂ YbNbO ₆ , Pb ₂ YbTO ₆ , Pb ₂ LuNbO ₆ , Pb ₂ LuTaO, Pb _Three NiNb ₂ O ₉ , Pb _Three NiTa ₂ O ₉ , Pb _Three ZnNb ₂ O ₉ , Pb _Three Fe ₂ WO ₉ , Pb ₂ CdWO ₆ , PbTiO _Three , PbZrO _Three , PbSnO _Three , PbHfO _Three , PbO and the like. Examples according to the present invention will be described below.
[0053]
[Example 1]
In this example, the AD film forming apparatus according to the first embodiment was used. The fine particle spray nozzle 22 of the AD film forming apparatus 20 is provided with a mask 34.
[0054]
First, BaTiO with an average particle size of 0.3 μm _Three The fine particle material was filled in a glass container, and while being heated at about 150 ° C., the water adhering to the powder surface was removed by vacuum degassing.
[0055]
Then BaTiO _Three Particulate material is put in an aerosol generator and high purity nitrogen gas (gas pressure: 2 kg / cm) ² , Gas flow rate: 4 L / min) and aerosolized. This aerosolized BaTiO _Three The fine particle material was introduced into the film forming chamber and sprayed for 30 minutes from the fine particle spray nozzle. The film forming chamber was previously set in a vacuum atmosphere of 10 Pa or less.
[0056]
BaTiO formed on glass substrate _Three The thickness of the film was about 100 μm. Further, the water absorption rate of the film is 0.1% or less, and the adhesion strength between the substrates of the film is 5 kg / mm. ² It was strong with the above. As a comparison, when a film was formed under the same conditions using a fine particle injection nozzle without a mask (comparative example), it was 3% of the formed film, and the adhesion strength between substrates of the film was 1.5 kg / mm. ² It was the following. Therefore, it was found that the membrane of this example had significantly fewer pores that adsorb water than the comparative example, and the membrane was dense.
[0057]
The water absorption was evaluated by immersing the substrate on which the thick film was formed in water for 1 hour, and dividing the difference in mass before and after that by the mass of the thick film. The water absorption rate of the thick film was accepted as 0.5% or less. The lower the water absorption, the fewer the pores that adsorb water and the higher the density of the film.
[0058]
The adhesion strength was measured using the Sebastian method. In this Sebastian method, the substrate on which the thick film of this embodiment is formed is fixed, and an adhesion tester is fixed to the surface of the thick film with an adhesive. Then, when the adhesion tester is pulled up and the thick film is peeled off from the substrate, the lifting force per unit area (kg / mm) ² ) Is used as an index of adhesion, and the greater the pulling force, the greater the adhesion.
[0059]
[Example 2]
In this example, the AD film forming apparatus according to the second embodiment was used.
[0060]
Al with an average particle size of 0.35 μm ₂ O _Three The fine particle material was filled in a glass container and vacuum deaerated while being heated at about 150 ° C. to remove moisture formed on the powder surface.
[0061]
Next, the raw material powder is put into an aerosol generator, and high purity helium gas (gas pressure: 2 kg / cm). ² , Gas flow rate: 4 L / min) was introduced to make an aerosol. This aerosolized Al ₂ O _Three The fine particle material was introduced into the film forming chamber, and the glass substrate was sprayed for 30 minutes from the fine particle spray nozzle. A known laval type nozzle was used as the fine particle injection nozzle. Note that the film formation chamber is previously set to a vacuum atmosphere of 10 Pa or less. Meanwhile, dry air (gas pressure: 1 kg / cm ² , Gas flow rate: 2 L / min) on the substrate surface, and Al deposited on the substrate ₂ O _Three The part with low film adhesion strength was removed from the film.
[0062]
Al formed on a glass substrate ₂ O _Three The film thickness was about 50 μm. The water absorption rate of the film is 0.1% or less, and the adhesion strength between the substrates of the film is 5 kg / mm. ² It was strong with the above.
[0063]
[Example 3]
In this example, the AD film forming apparatus according to the third embodiment was used.
[0064]
Al obtained by surface treatment with aluminum isopropoxide, which is a kind of aluminum alkoxide, and firing at 1000 ° C. in the atmosphere ₂ O _Three TiO with an average particle size of 0.3 μm coated with a film ₂ A fine particle material (manufactured by Teika) was prepared.
This Al ₂ O _Three Coated TiO ₂ Fine particle material (Al ₂ O _Three (Amount: 5% by mass) was put in a glass container and vacuum deaerated while being heated at about 150 ° C. to remove water adhering to the surface of the fine particles.
[0065]
Then Al ₂ O _Three Coated TiO ₂ Particulate material is put in an aerosol generator and high purity nitrogen gas (gas pressure: 2 kg / cm) ² , Gas flow rate: 4 L / min) and aerosolized. This aerosolized Al ₂ O _Three Coated TiO ₂ The fine particle material was introduced into the film forming chamber and sprayed for 30 minutes from the fine particle spray nozzle. Note that the film formation chamber was previously set to a vacuum atmosphere of 10 Pa or less.
[0066]
Al formed on a glass substrate ₂ O _Three Containing TiO ₂ The thickness of the film was about 100 μm. The water absorption rate of the film is 0.1% or less, and the adhesion strength between the substrates of the film is 5 kg / mm. ² It was strong with the above.
[0067]
Although the preferred embodiments of the present invention have been described in detail above, the present invention is not limited to the specific embodiments, and various modifications and changes can be made within the scope of the present invention described in the claims. Is possible.
[0068]
For example, the emission port of the fine particle injection nozzle used in the film forming apparatus according to the third embodiment can be used in the film forming apparatuses according to the first and second embodiments. Moreover, you may combine 1st Embodiment and 2nd Embodiment.
[0069]
In addition, the following additional notes are disclosed regarding the above description.
(Supplementary Note 1) A film forming apparatus having a fine particle injection nozzle for injecting an aerosolized fine particle material onto a substrate in a film forming chamber to deposit the fine particle material,
Of the fine particle flow ejected from the fine particle ejection nozzle, there is a shielding means for blocking the fine particle flow in a range where the velocity of the fine particle flow is a predetermined value or less,
A film forming apparatus, wherein the shielding means is integrated with a fine particle injection nozzle.
(Additional remark 2) While moving the said board | substrate, while spraying fine particle material from the said fine particle injection nozzle and depositing on a board | substrate,
2. The film forming apparatus according to claim 1, further comprising a gas injection nozzle that injects a gas that guides the blocked fine particle flow in the moving direction of the substrate.
(Additional remark 3) It is the film-forming apparatus which has the fine particle injection nozzle which inject | sprays aerosolized fine particle material on the board | substrate which moves in a film-forming chamber, and deposits fine particle material,
A film forming apparatus having a gas injection nozzle adjacent to the fine particle injection nozzle for removing a part of the deposited thick film by injecting a gas.
(Additional remark 4) It is the film-forming apparatus which has the fine particle injection nozzle which inject | sprays aerosolized fine particle material on a board | substrate in a film-forming chamber, and deposits fine particle material,
The fine particle injection nozzle is provided with a flow path of aerosolized fine particle material at the nozzle tip,
The area of the flow path is gradually reduced from upstream to downstream,
A film forming apparatus characterized in that guide means for forming a spiral flow of the particulate material is provided in the flow path.
(Additional remark 5) The said guidance means was provided in the inner wall in the said flow path. Convex The film forming apparatus as set forth in appendix 4, wherein the film forming apparatus is a shaped member.
(Additional remark 6) It is the film-forming method which introduce | transduces the aerosol-form fine particle material into a film-forming chamber, and injects it on a board | substrate from a fine particle injection nozzle,
While moving the substrate, the fine particle material is ejected from the fine particle spray nozzle and deposited on the substrate to form a thick film,
A film forming method, wherein gas is injected from a gas injection nozzle to remove a part of the thick film and to discharge in the substrate moving direction.
(Supplementary note 7) The part of the thick film is a surface portion of the thick film or / and a portion in a width direction of the thick film that forms a line or a band in the substrate moving direction. Film forming method.
[0070]
【The invention's effect】
As is apparent from the above detailed description, according to the present invention, the portion of the fine particle flow ejected from the fine particle ejection nozzle is blocked, the film formed by the slow fine particle flow is removed, or Uniform the velocity of the fine particle flow. As a result, a film having high density and high adhesion strength can be formed with good uniformity.
[Brief description of the drawings]
FIG. 1 is a diagram showing a state where fine particle material is deposited by being ejected from a fine particle spray nozzle.
FIG. 2 is a schematic configuration diagram of a film forming apparatus according to the first embodiment of the present invention.
FIG. 3 is an enlarged sectional view showing an emission port of a fine particle injection nozzle used in the film forming apparatus according to the first embodiment.
4 is a view as seen from above the fine particle injection nozzle shown in FIG. 3;
FIG. 5 is a schematic configuration diagram of a film forming apparatus according to a second embodiment of the present invention.
FIG. 6 is an enlarged cross-sectional view showing an emission port of a fine particle injection nozzle and a discharge gas injection nozzle used in a film forming apparatus according to a second embodiment.
7 is a top view of the fine particle injection nozzle and the removal gas injection nozzle shown in FIG. 6;
FIG. 8 is a top view of a fine particle injection nozzle and another removal gas injection nozzle.
FIG. 9 is a cross-sectional view of an emission port of a fine particle injection nozzle used in a film forming apparatus according to a third embodiment of the present invention.
[Explanation of symbols]
20, 50 Deposition equipment
21 Aerosol generator
22 Fine particle injection nozzle
23 Substrate
24 Deposition chamber
34 Mask
34A opening
35 Exhaust gas injection nozzle
51 Gas injection nozzle for removal
52 AD film
60 Outlet of fine particle injection nozzle

Claims (4)

A fine particle injection nozzle that deposits the fine particle material by spraying the aerosolized fine particle material onto a substrate that moves in the deposition chamber;
Shielding means for blocking a particulate flow having a velocity of the particulate flow within a predetermined range of the particulate flow ejected from the particulate ejection nozzle;
A gas injection nozzle for injecting a gas for guiding the blocked fine particle flow in the moving direction of the substrate;
The film forming apparatus, wherein the shielding means is integrated with the fine particle injection nozzle.   2. The film forming apparatus according to claim 1, further comprising a gas jet nozzle that jets and removes a part of the fine particle material deposited on the substrate adjacent to the fine particle jet nozzle. The fine particle injection nozzle is provided with a flow path for the fine particle material at the nozzle tip.
The area of the flow path is gradually reduced from upstream to downstream, and guide means for forming a spiral flow of the particulate material in the flow path is provided. 2. The film forming apparatus according to 2. The film forming apparatus according to claim 3 , wherein the guide means is a continuous convex member provided on an inner wall in the flow path.

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