JP2011111664A - Method for depositing functional film, and functional film deposited body - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To consistently form a functional film containing functional particles on a surface of a base material while increasing the purity of the functional particles. <P>SOLUTION: By using an open-type head 24 for performing the atmospheric control with inert gas, a step of discharging the functional particles 4 in the liquid onto a substrate 3 with the desired distribution by the mist jet technology, and a step of depositing a thin film 8 by the atmospheric-pressure plasma chemical transport method thereafter are alternately repeated. <P>COPYRIGHT: (C)2011,JPO&amp;INPIT

Description

  The present invention relates to a functional film forming method and a functional film forming body, and more particularly to a method of forming a functional film containing functional fine particles on the surface of a base material such as a semiconductor substrate, a glass substrate, or a resin substrate.

  As a method for forming a thick functional film containing functional fine particles on the surface of a base material such as a glass substrate or a plastic substrate, there is a process of fixing using the binding force of a binder. For example, a method in which functional fine particles are dispersed in a suitable solvent, and this is applied to the surface of a substrate and dried, or a method in which nanoparticles are stirred in a solvent and a film is formed by spin coating or ink jet technique There is.

  Patent Document 1 discloses a technique for forming a film containing fine particles by spraying a carrier gas in which a reaction gas and fine particles are mixed to a plasma generating portion. In this technology, functional fine particles are mixed in a film forming gas for performing film formation by plasma CVD, so that functional fine particles are mixed in a plasma generation region to form a functional film (for example, patents). Reference 1).

JP 2006-320333 A

  However, in the method of immobilizing the functional fine particles using the binding force of the binder, the functional fine particles are in a state embedded in the binder, so that it is difficult to increase the purity of the functional fine particles. There was a problem that the function could not be fully exhibited.

  In addition, in the method of forming a film by mixing functional fine particles in a plasma CVD film forming gas, it is difficult to stably continue plasma discharge, which causes a problem in film formation. On the other hand, if the particle size of the functional fine particles is made very small in order to continue the plasma discharge stably, it is impossible to form a functional film containing functional fine particles having a large particle size of submicron or micron unit. was there.

  The present invention has been made in view of the above, and a functional film forming method capable of stably forming a functional film containing functional fine particles on the surface of a substrate while increasing the purity of the functional fine particles And it aims at obtaining a functional film formation object.

  In order to solve the above-described problems and achieve the object, the functional film forming method of the present invention includes a step of attaching functional fine particles mixed in a liquid to the surface of a substrate, and the functional fine particles are attached. And a step of forming a thin film by plasma on the substrate.

  According to the present invention, there is an effect that it is possible to stably form the functional film containing the functional fine particles on the surface of the base material while increasing the purity of the functional fine particles.

FIG. 1 is a perspective view showing a schematic configuration of Embodiment 1 of a functional film forming apparatus according to the present invention. FIG. 2 is a perspective view showing a schematic configuration of Embodiment 2 of the functional film forming apparatus according to the present invention. FIG. 3 is a perspective view showing a schematic configuration of Embodiment 3 of the functional film forming apparatus according to the present invention. FIG. 4 is a perspective view showing a schematic configuration of Embodiment 4 of the functional film forming apparatus according to the present invention. FIG. 5 is a sectional view showing a schematic configuration of the functional film forming apparatus according to the fifth embodiment of the present invention. FIG. 6 is a cross-sectional view showing a schematic configuration of the functional film forming apparatus according to the sixth embodiment of the present invention. FIG. 7 is a sectional view showing a schematic configuration of the functional film forming apparatus according to the seventh embodiment of the present invention. FIG. 8 is a cross-sectional view showing a schematic configuration of the functional film forming apparatus according to the eighth embodiment of the present invention. FIG. 9 is a cross-sectional view showing a schematic configuration of the functional film forming apparatus according to the ninth embodiment of the present invention. FIG. 10 is a sectional view showing a schematic configuration of the functional film forming apparatus according to the tenth embodiment of the present invention. FIG. 11 is a cross-sectional view showing a schematic configuration of the eleventh embodiment of the functional film forming apparatus according to the present invention. FIG. 12 is a perspective view showing a schematic configuration of the twelfth embodiment of the functional film forming apparatus according to the present invention. FIG. 13 is a sectional view showing a schematic configuration of the twelfth embodiment of the functional film forming apparatus according to the present invention. FIG. 14 is a cross-sectional view showing a schematic configuration of the functional film forming apparatus according to the thirteenth embodiment of the present invention.

  Embodiments of a functional film forming method according to the present invention will be described below in detail with reference to the drawings. Note that the present invention is not limited to the embodiments.

Embodiment 1 FIG.
FIG. 1 is a perspective view showing a schematic configuration of Embodiment 1 of a functional film forming apparatus according to the present invention. The vacuum chamber 7 is a perspective view so that the inside can be seen. In FIG. 1, the functional film forming apparatus includes a coating mechanism that applies a liquid mixed with functional fine particles 4 to the surface of a substrate 3 and a thin film 8 that is sputtered onto the substrate 3 to which the functional fine particles 4 are attached. A membrane mechanism is provided separately. Here, the application mechanism of the functional fine particles 4 is provided with a liquid discharge port 1 that discharges the liquid mixed with the functional fine particles 4 to the surface of the substrate 3 and a spin mechanism 2 that rotates while holding the substrate 3. ing. The film forming mechanism of the thin film 8 is provided with a vacuum chamber 7 that isolates the substrate 3 from the outside air, a target 5 that supplies the raw material of the thin film 8, and a high frequency power source 6 that applies high frequency power to the target 5.

  Next, a method for forming a functional film using this functional film forming apparatus will be described. The liquid in which the functional fine particles 4 are mixed is discharged from the liquid discharge port 1 toward the substrate 3 rotated by the spin mechanism 2 to perform spin coating.

  Next, the substrate 3 to which the functional fine particles 4 are attached is disposed immediately below the target 5 in the vacuum chamber 7, and high frequency power is applied to the target 5 via the high frequency power source 6, thereby forming the thin film 8 by sputtering. Is deposited. If the film thickness is insufficient in one process, these processes may be alternately repeated a plurality of times. Alternatively, the functional fine particles 4 and the thin films 8 may be alternately deposited after the thin films 8 are formed on the substrate 3.

  As described above, according to the first embodiment described above, the functional film mixed with the functional fine particles 4 can be rapidly formed by alternately repeating the application of the functional fine particles 4 by spin coating and the film formation of the thin film 8 by sputtering. There is an effect that it becomes possible to form a film. Since the functional particle deposition area and the plasma generation area are separated, it is possible to generate plasma without mixing fine particles such as the functional fine particles 4 into the plasma, and the plasma discharge can be continued stably. There is also an effect that the film formation becomes possible. In addition, by adjusting the size of the functional fine particles 4 mixed in the liquid, there is an effect that a functional film in which the functional fine particles 4 having a desired size are mixed can be created. Furthermore, there is an effect that the configuration of the functional fine particles 4 and the thin film 8 can be freely set.

  Examples of the functional fine particles 4 include metal fine particles including silver nanoparticles, copper nanoparticles, and gold nanoparticles, phosphor fine particles, magnetic fine particles, photocatalyst fine particles, oxide fine particles, transparent conductive fine particles, diamond, and Si fine particles. In particular, fine particles having a diameter of several microns or less are preferable. The functional fine particles 4 may be organic particles containing proteins, amino acids, genes or viruses. Further, the functional fine particles 4 may be capsule-shaped. As the size, functional fine particles 4 having a diameter of several nm to several μm can be contained. The liquid in which the functional fine particles 4 are mixed may be water, an organic solvent such as alcohol, tetradecane, or decanol, or an acid or alkaline liquid. Also, the target 5 can be made of various materials such as a metal including a non-magnetic material and a magnetic material, an oxide metal, carbon, and Si. As the substrate 3, for example, a glass substrate, a resin substrate, a semiconductor substrate, or the like can be used, and a flexible tape, a flexible film, or the like may be used. Further, instead of the substrate 3, a wire, tube or spherical base material may be used.

Further, the application method is not limited to spin coating, and the same effect can be obtained by a method such as spray coating or spraying as long as the functional fine particles 4 can be deposited on the substrate 3. . It goes without saying that the same effect can be obtained not only by sputtering but also by a method such as plasma CVD in which a thin film material gas is introduced without using the target 5 or the like. Thin film source gas includes TEOS, HMDS, silica film, oxide film material such as TiO ₂ and ITO, nitride film such as SiN and TiN, carbide film such as SiC and TiC, DLC, diamond, nanotube, nanofiber, etc. Carbon-based materials can be used. Although the gaseous thin film source gas can be introduced as it is, the solid or liquid raw material may be used as the thin film source gas after being gasified.

Embodiment 2. FIG.
FIG. 2 is a perspective view showing a schematic configuration of Embodiment 2 of the functional film forming apparatus according to the present invention. The vacuum chamber 7 is a perspective view so that the inside can be seen. In FIG. 2, this functional film forming apparatus includes a coating mechanism that applies a liquid mixed with functional fine particles 4 to the surface of the substrate 3, and a thin film 8 that is sputtered onto the substrate 3 to which the functional fine particles 4 are attached. A membrane mechanism is provided integrally. Here, the liquid discharge port 1 is drawn onto the substrate 3 in the vacuum chamber 7 through the target 5, and the spin mechanism 2 is accommodated in the vacuum chamber 7.

  Next, a method for forming a functional film using this functional film forming apparatus will be described. In the vacuum chamber 7 in the atmospheric pressure state, the liquid in which the functional fine particles 4 are mixed is discharged from the liquid discharge port 1 toward the substrate 3 rotated by the spin mechanism 2 to perform spin coating.

  Next, the inside of the vacuum chamber 7 is evacuated, and a high frequency power is applied to the target 5 via the high frequency power source 6, thereby forming the thin film 8 by sputtering. If the film thickness is insufficient in one process, these processes may be alternately repeated a plurality of times. Alternatively, the functional fine particles 4 and the thin films 8 may be alternately deposited after the thin films 8 are formed on the substrate 3. Specific materials such as the functional fine particles 4 and the thin film 8 are the same as those described in the first embodiment.

  Thus, according to the second embodiment described above, the application of the functional fine particles 4 by spin coating and the film formation of the thin film 8 by sputtering can be repeated in the same apparatus. There is an effect that the functional film can be formed at a higher speed. Further, as in the first embodiment, the present invention is not limited to spin coating or sputtering, and the same effect can be obtained by a technique such as spray coating or plasma CVD. Moreover, there is an effect that a functional film in which the functional fine particles 4 having a desired size are mixed can be similarly produced.

Embodiment 3 FIG.
FIG. 3 is a perspective view showing a schematic configuration of Embodiment 3 of the functional film forming apparatus according to the present invention. The vacuum chamber 7 and the atmosphere control member 10 are perspective views so that the inside can be seen. In FIG. 3, this functional film forming apparatus includes a coating mechanism for applying a liquid mixed with functional fine particles 4 to the surface of the substrate 3 in a desired atmosphere, and a thin film on the substrate 3 to which the functional fine particles 4 are attached. A film forming mechanism for sputtering 8 is provided separately. Here, in addition to the configuration shown in FIG. 1, the functional fine particle 4 application mechanism includes an atmosphere control member 10 that can control the atmosphere at the location where the liquid mixed with the functional fine particles 4 is applied, and the atmosphere control member 10. An inert gas inflow passage 9 through which the active gas flows is provided. The atmosphere control member 10 is not necessarily a chamber-shaped member configured to cover the substrate 3, but may be anything as long as the atmosphere can be substantially controlled by an air curtain or the like that blocks outside air.

  Next, a method for forming a functional film using this functional film forming apparatus will be described. The functional fine particles 4 are mixed toward the substrate 3 rotated by the spin mechanism 2 while flowing an inert gas such as nitrogen, helium or argon from the inert gas inflow path 9 into the atmosphere control member 10. The liquid is discharged from the liquid discharge port 1 and spin coated.

  Next, the substrate 3 to which the functional fine particles 4 are attached is disposed immediately below the target 5 in the vacuum chamber 7, and high frequency power is applied to the target 5 via the high frequency power source 6, thereby forming the thin film 8 by sputtering. Is deposited. If the film thickness is insufficient in one process, these processes may be alternately repeated a plurality of times. Alternatively, the functional fine particles 4 and the thin films 8 may be alternately deposited after the thin films 8 are formed on the substrate 3. Specific materials such as the functional fine particles 4 and the thin film 8 are the same as those described in the first embodiment.

  As described above, according to the above-described third embodiment, the functional fine particles 4 are applied to the surface of the substrate 3 in a space in which the atmosphere is controlled. Therefore, in addition to the effects of the first embodiment, the functional fine particles 4 are oxidized. It is possible to obtain the effect of preventing the deterioration of the material.

Embodiment 4 FIG.
FIG. 4 is a perspective view showing a schematic configuration of Embodiment 4 of the functional film forming apparatus according to the present invention. The atmosphere control vacuum chamber 11 is a perspective view so that the inside can be seen. In FIG. 4, this functional film forming apparatus includes a coating mechanism for applying a liquid mixed with functional fine particles 4 to the surface of the substrate 3 in a desired atmosphere, and a thin film on the substrate 3 to which the functional fine particles 4 are attached. A film forming mechanism for sputtering 8 is integrally provided. Here, in this film forming mechanism, an atmosphere control vacuum chamber 11 is provided instead of the vacuum chamber 7 of FIG. 3, and the liquid discharge port 1 is drawn onto the substrate 3 in the atmosphere control vacuum chamber 11 through the target 5. In addition, the spin mechanism 2 is accommodated in the atmosphere control vacuum chamber 11. The atmosphere control vacuum chamber 11 is provided with an inert gas inflow passage 9 through which an inert gas flows.

  Next, a method for forming a functional film using this functional film forming apparatus will be described. While flowing an inert gas such as nitrogen, helium or argon from the inert gas inflow path 9 into the atmosphere control vacuum chamber 11, the substrate 3 is rotated by the spin mechanism 2 in the atmosphere control vacuum chamber 11. Then, the liquid in which the functional fine particles 4 are mixed is discharged from the liquid discharge port 1 and spin coated.

  Next, the inside of the atmosphere control vacuum chamber 11 is evacuated, and a high frequency power is applied to the target 5 via the high frequency power source 6 to form the thin film 8 by sputtering. If the film thickness is insufficient in one process, these processes may be alternately repeated a plurality of times. Alternatively, the functional fine particles 4 and the thin films 8 may be alternately deposited after the thin films 8 are formed on the substrate 3. Specific materials such as the functional fine particles 4 and the thin film 8 are the same as those described in the first embodiment.

  As described above, according to the fourth embodiment described above, in order to form the functional film in which the functional fine particles 4 are mixed in the atmosphere controlled atmosphere, in addition to the effects of the second embodiment, the functional fine particles 4 are oxidized. It is possible to obtain the effect of preventing alteration such as.

Embodiment 5 FIG.
FIG. 5 is a sectional view showing a schematic configuration of the functional film forming apparatus according to the fifth embodiment of the present invention. In FIG. 5, this functional film forming apparatus includes an application mechanism for applying a liquid mixed with functional fine particles 4 to the surface of the substrate 3, and a thin film 8 applied to the atmospheric pressure plasma on the substrate 3 to which the functional fine particles 4 are adhered. A film forming mechanism for forming a film is separately provided. Here, the application mechanism of the functional fine particles 4 is provided with a spray head 12 for spraying a liquid mixed with the functional fine particles 4 onto the surface of the substrate 3 and a stage 13 for holding the substrate 3. In the film forming mechanism of the thin film 8, an upper electrode 31a to which a high frequency power is applied, a lower electrode 31b to which a ground potential is applied, a target 5 for supplying a raw material for the thin film 8, and a high frequency power to the upper electrode 31a are applied. A high frequency power source 6 is provided.

  Next, a method for forming a functional film using this functional film forming apparatus will be described. The liquid in which the functional fine particles 4 are mixed is spray coated from the spray head 12 toward the substrate 3 on the stage 13. Here, the spray head 12 and the stage 13 can be applied to the entire surface of the substrate 3 by relative movement by a mechanism (not shown).

  Next, the substrate 3 to which the functional fine particles 4 are attached is disposed on the lower electrode 31b, and high-frequency power is applied to the upper electrode 31a via the high-frequency power source 6, thereby generating atmospheric pressure plasma from the target 5. A thin film 8 is formed. If the film thickness is insufficient in one process, these processes may be alternately repeated a plurality of times. Alternatively, the functional fine particles 4 and the thin films 8 may be alternately deposited after the thin films 8 are formed on the substrate 3. Specific materials such as the functional fine particles 4 and the thin film 8 are the same as those described in the first embodiment.

  As described above, according to the above-described fifth embodiment, since the functional film in which the functional fine particles 4 are mixed under atmospheric pressure is formed, in addition to the effects of the first embodiment, time required for evacuation is eliminated. Therefore, the film can be formed at a higher speed.

Embodiment 6 FIG.
FIG. 6 is a cross-sectional view showing a schematic configuration of the functional film forming apparatus according to the sixth embodiment of the present invention. In FIG. 6, this functional film forming apparatus includes an application mechanism for applying a liquid mixed with functional fine particles 4 to the surface of the substrate 3, and a thin film 8 applied to the atmospheric pressure plasma on the substrate 3 to which the functional fine particles 4 are adhered. A film forming mechanism for forming a film is separately provided. Here, the application mechanism of the functional fine particles 4 is provided with a mist jet head 19 that sprays a liquid mixed with the functional fine particles 4 onto the surface of the substrate 3 and a stage 13 that holds the substrate 3. The mist jet head 19 includes a vibration wave reflector 14 having a parabolic cross section, a piezoelectric vibrator 17 bonded to the upper surface of the vibration wave reflector 14 via an insulating material 16, and a vibration wave. A nozzle plate 15 bonded to the lower surface of the reflector 14 is provided. The nozzle plate 15 is disposed so that the entrance of the nozzle plate 15 is located at the focal point P1 of the parabolic surface of the vibration wave reflector 14, and is attached toward the tip of the discharge port. The liquid mixed with the functional fine particles 4 is filled in the liquid chamber 20 surrounded by the side wall of the vibration wave reflector 14 and the insulating material 16. A drive electrode (not shown) is provided on the upper surface of the piezoelectric vibrator 17, and a common electrode (not shown) is provided on the lower surface. A high frequency voltage is applied between the drive electrode and the common electrode by a driver, and functions. The liquid in which the conductive fine particles 4 are mixed is sprayed.

  Next, a method for forming a functional film using this functional film forming apparatus will be described. In the mist jet head 19, when the piezoelectric vibrator 17 is vibrated, the vibration wave from the piezoelectric vibrator 17 is reflected by the side wall surface of the vibration wave reflector 14 through the insulating material 16, and the ejection holes of the nozzle plate 15. The liquid in which the functional fine particles 4 are mixed is discharged from the discharge hole as a mist flow 18 and applied to the surface of the substrate 3 on the stage 13. Here, the mist jet head 19 and the stage 13 can be applied to the entire surface of the substrate 3 by relative movement by a mechanism (not shown).

  Next, the substrate 3 to which the functional fine particles 4 are attached is disposed on the lower electrode 31b, and high-frequency power is applied to the upper electrode 31a via the high-frequency power source 6, thereby generating atmospheric pressure plasma from the target 5. A thin film 8 is formed. If the film thickness is insufficient in one process, these processes may be alternately repeated a plurality of times. Alternatively, the functional fine particles 4 and the thin films 8 may be alternately deposited after the thin films 8 are formed on the substrate 3. Specific materials such as the functional fine particles 4 and the thin film 8 are the same as those described in the first embodiment.

  As described above, according to the sixth embodiment described above, by using the mist jet head 19, the functional fine particles 4 can be attached to the surface of the substrate 3 as the fine mist flow 18. In addition to the effect, there is an effect that a more uniform functional film can be formed.

Embodiment 7 FIG.
FIG. 7 is a sectional view showing a schematic configuration of the functional film forming apparatus according to the seventh embodiment of the present invention. In FIG. 7, this functional film forming apparatus includes a coating mechanism for applying a liquid mixed with functional fine particles 4 to the surface of the substrate 3 in a desired atmosphere, and a thin film on the substrate 3 to which the functional fine particles 4 are attached. A film forming mechanism for forming the film 8 in a desired atmosphere using atmospheric pressure plasma is separately provided. Here, in addition to the configuration shown in FIG. 5, the functional fine particle 4 application mechanism includes an atmosphere control member 10a that can control the atmosphere at the location where the liquid in which the functional fine particles 4 are mixed, and the atmosphere control member 10a. An inert gas inflow passage 9a through which the active gas flows is provided. The film forming mechanism for the thin film 8 includes, in addition to the configuration shown in FIG. 5, an atmosphere control member 10b that can control the atmosphere at the position where the thin film 8 is formed, and an inert gas inflow passage that allows an inert gas to flow into the atmosphere control member 10b. 9b is provided. The atmosphere control members 10a and 10b do not necessarily have a chamber shape configured to cover the substrate 3, but may be anything as long as the atmosphere can be substantially controlled by an air curtain or the like that blocks outside air. .

  Next, a method for forming a functional film using this functional film forming apparatus will be described. While flowing an inert gas such as nitrogen, helium or argon from the inert gas inflow path 9a into the atmosphere control member 10a, the liquid mixed with the functional fine particles 4 is directed from the spray head 12 to the substrate 3 on the stage 13. Spray coat. Here, the spray head 12 and the stage 13 can be applied to the entire surface of the substrate 3 by relative movement by a mechanism (not shown).

  Next, the substrate 3 to which the functional fine particles 4 are attached is disposed on the lower electrode 31b, and an inert gas such as nitrogen, helium or argon is allowed to flow into the atmosphere control member 10b from the inert gas inflow passage 9b. Then, high-frequency power is applied to the upper electrode 31a via the high-frequency power source 6 to generate atmospheric pressure plasma from the target 5, and the thin film 8 is formed. If the film thickness is insufficient in one process, these processes may be alternately repeated a plurality of times. Alternatively, the functional fine particles 4 and the thin films 8 may be alternately deposited after the thin films 8 are formed on the substrate 3. Specific materials such as the functional fine particles 4 and the thin film 8 are the same as those described in the first embodiment.

  Thus, according to the seventh embodiment described above, in order to form a functional film in which the functional fine particles 4 are mixed under atmosphere control, in addition to the effects of the fifth embodiment, oxidation of the functional fine particles 4 and the like. It is possible to obtain the effect of preventing the deterioration of the material.

Embodiment 8 FIG.
FIG. 8 is a cross-sectional view showing a schematic configuration of the functional film forming apparatus according to the eighth embodiment of the present invention. In FIG. 8, this functional film forming apparatus includes a coating mechanism for applying a liquid mixed with functional fine particles 4 to the surface of the substrate 3 in a desired atmosphere, and a thin film on the substrate 3 to which the functional fine particles 4 are attached. A film forming mechanism for forming the film 8 in a desired atmosphere using atmospheric pressure plasma is separately provided. Here, in addition to the configuration of FIG. 6, the functional fine particle 4 application mechanism includes an atmosphere control member 10 c that can control the atmosphere where the liquid in which the functional fine particles 4 are mixed, and the atmosphere control member 10 c. An inert gas inflow passage 9c through which the active gas flows is provided. The film forming mechanism of the thin film 8 is the same as the film forming mechanism of the thin film 8 in FIG. The atmosphere control member 10c is not necessarily a chamber-shaped member configured to cover the substrate 3, but may be anything as long as the atmosphere can be substantially controlled by an air curtain or the like that blocks outside air.

  Next, a method for forming a functional film using this functional film forming apparatus will be described. In the mist jet head 19, when an inert gas such as nitrogen, helium or argon is allowed to flow into the atmosphere control member 10c from the inert gas inflow path 9c, The vibration wave is reflected by the side wall surface of the vibration wave reflector 14 through the insulating material 16 and focused on the discharge hole of the nozzle plate 15, and the liquid mixed with the functional fine particles 4 from the discharge hole is formed as a mist flow 18. It is discharged and applied to the surface of the substrate 3 on the stage 13. Here, the mist jet head 19 and the stage 13 can be applied to the entire surface of the substrate 3 by relative movement by a mechanism (not shown).

  Next, the substrate 3 to which the functional fine particles 4 are attached is disposed on the lower electrode 31b, and an inert gas such as nitrogen, helium or argon is allowed to flow into the atmosphere control member 10b from the inert gas inflow passage 9b. Then, high-frequency power is applied to the upper electrode 31a via the high-frequency power source 6 to generate atmospheric pressure plasma from the target 5, and the thin film 8 is formed. If the film thickness is insufficient in one process, these processes may be alternately repeated a plurality of times. Alternatively, the functional fine particles 4 and the thin films 8 may be alternately deposited after the thin films 8 are formed on the substrate 3. Specific materials such as the functional fine particles 4 and the thin film 8 are the same as those described in the first embodiment.

  As described above, according to the eighth embodiment described above, by using the mist jet head 19, the functional fine particles 4 can be attached to the surface of the substrate 3 as a fine mist flow 18. In addition to the effect, there is an effect that a more uniform functional film can be formed.

Embodiment 9 FIG.
FIG. 9 is a cross-sectional view showing a schematic configuration of the functional film forming apparatus according to the ninth embodiment of the present invention. In FIG. 9, this functional film forming apparatus includes a coating mechanism for applying a liquid mixed with functional fine particles 4 to the surface of the substrate 3 in a desired atmosphere, and a thin film on the substrate 3 to which the functional fine particles 4 are attached. A film forming mechanism for forming the film 8 in atmospheric pressure plasma in a desired atmosphere is integrally provided. Here, the application mechanism of the functional fine particles 4 is provided with a spray head 12 that sprays a liquid mixed with the functional fine particles 4 onto the surface of the substrate 3 and a stage 32 that holds the substrate 3. The thin film 8 is formed by a jet type plasma head 22 for jetting reactive species that contribute to the film formation generated by atmospheric pressure plasma, a target 5 for supplying the raw material of the thin film 8, and a jet type plasma head 22. A high-frequency power source 6 for applying high-frequency power is provided. Further, in this functional film forming apparatus, an atmosphere control member 10d capable of controlling the atmosphere of a portion where the liquid mixed with the functional fine particles 4 is applied, and an inert gas inflow passage for allowing an inert gas to flow into the atmosphere control member 10d. 9d and a reaction gas inflow passage 21 through which the reaction gas flows into the atmosphere control member 10d is provided.

  Next, a method for forming a functional film using this functional film forming apparatus will be described. While flowing an inert gas such as nitrogen, helium or argon from the active gas inflow path 9d into the atmosphere control member 10d, the liquid mixed with the functional fine particles 4 is directed from the spray head 12 toward the substrate 3 on the stage 32. Spray coat.

  Next, high-frequency power is applied to the ejection-type plasma head 22 via the high-frequency power source 6 while flowing the reaction gas from the reaction gas inflow path 21 into the atmosphere control member 10d, whereby the target 5 and the reaction gas are converted into atmospheric pressure plasma. The thin film 8 is formed by causing reactive species that contribute to film formation to be ejected from the ejection type plasma head 22. Examples of the reactive gas include simple substances such as helium, argon, nitrogen gas, and hydrogen gas, and mixed gases. The same effect can be obtained by a film forming method such as plasma CVD in which the thin film material gas is introduced without using the target 5 or the like. If the film thickness is insufficient in one process, these processes may be alternately repeated a plurality of times. Alternatively, the functional fine particles 4 and the thin films 8 may be alternately deposited after the thin films 8 are formed on the substrate 3. Specific materials such as the functional fine particles 4 and the thin film 8 are the same as those described in the first embodiment.

  The spray head 12, the ejection type plasma head 22 and the stage 32 can be applied and formed on the entire surface of the substrate 3 by moving relative to each other by a mechanism not shown. Examples of the reactive gas include simple substances such as helium, argon, nitrogen gas, and hydrogen gas, and mixed gases. The same effect can be obtained by a film forming method such as plasma CVD in which the thin film material gas is introduced without using the target 5 or the like.

  Thus, according to the ninth embodiment described above, in order to form the functional film mixed with the functional fine particles 4 under the atmosphere control in the same chamber, in addition to the effects of the seventh embodiment, the functional fine particles. The effect of preventing alteration such as oxidation of 4 can be obtained.

Embodiment 10 FIG.
FIG. 10 is a sectional view showing a schematic configuration of the functional film forming apparatus according to the tenth embodiment of the present invention. In FIG. 10, this functional film forming apparatus includes a coating mechanism for applying a liquid mixed with functional fine particles 4 to the surface of the substrate 3 in a desired atmosphere, and a thin film on the substrate 3 to which the functional fine particles 4 are attached. A film forming mechanism for forming the film 8 in a desired atmosphere using atmospheric pressure plasma is separately provided. Here, the application mechanism of the functional fine particles 4 is the same as the application mechanism of the functional fine particles 4 of FIG. The film forming mechanism of the thin film 8 is the same as the structure in which the spray head 12 is removed from the structure of FIG.

  Next, a method for forming a functional film using this functional film forming apparatus will be described. In the mist jet head 19, when an inert gas such as nitrogen, helium or argon is allowed to flow into the atmosphere control member 10c from the inert gas inflow path 9c, The vibration wave is reflected by the side wall surface of the vibration wave reflector 14 through the insulating material 16 and focused on the discharge hole of the nozzle plate 15, and the liquid mixed with the functional fine particles 4 from the discharge hole is formed as a mist flow 18. It is discharged and applied to the surface of the substrate 3 on the stage 13. Here, the mist jet head 19 and the stage 13 can be applied to the entire surface of the substrate 3 by relative movement by a mechanism (not shown).

  Next, the substrate 3 to which the functional fine particles 4 are attached is placed on the stage 32, and the high-frequency power is supplied via the high-frequency power source 6 while the reaction gas flows into the atmosphere control member 10d from the reaction gas inflow path 21. The thin film 8 is formed by causing the target 5 and the reactive gas to react in the atmospheric pressure plasma by being applied to the ejection type plasma head 22 and ejecting reactive species contributing to the film formation from the ejection type plasma head 22. If the film thickness is insufficient in one process, these processes may be alternately repeated a plurality of times. Alternatively, the functional fine particles 4 and the thin films 8 may be alternately deposited after the thin films 8 are formed on the substrate 3. Specific materials such as the functional fine particles 4 and the thin film 8 are the same as those described in the first embodiment.

  Further, the ejection type plasma head 22 and the stage 32 can be formed on the entire surface of the substrate 3 by relative movement by a mechanism (not shown). Examples of the reactive gas include simple substances such as helium, argon, nitrogen gas, and hydrogen gas, and mixed gases. The same effect can be obtained by a film forming method such as plasma CVD in which the thin film material gas is introduced without using the target 5 or the like.

  As described above, according to the tenth embodiment described above, by using the mist jet head 19, the functional fine particles 4 can be attached to the surface of the substrate 3 as a fine mist flow 18. In addition to the effect, there is an effect that a more uniform functional film can be formed.

Embodiment 11 FIG.
FIG. 11 is a cross-sectional view showing a schematic configuration of the eleventh embodiment of the functional film forming apparatus according to the present invention. In FIG. 11, this functional film forming apparatus includes a coating mechanism for applying a liquid mixed with functional fine particles 4 to the surface of the substrate 3 in a desired atmosphere, and a thin film on the substrate 3 to which the functional fine particles 4 are attached. A film forming mechanism for forming the film 8 in a desired atmosphere using atmospheric pressure plasma is separately provided. Here, in the application mechanism of the functional fine particles 4, a nozzle plate 15a is provided instead of the nozzle plate 15 of FIG. The nozzle plate 15a is provided with a gas inflow passage 9e through which the inert gas 23 flows. Note that the air outlet of the gas inflow passage 9e is arranged around the outlet of the nozzle plate 15a so that the mist flow 18 discharged from the nozzle plate 15a is surrounded by the inert gas 23. The film forming mechanism of the thin film 8 is the same as the configuration of FIG.

  Next, a method for forming a functional film using this functional film forming apparatus will be described. In the mist jet head 19, when an inert gas such as nitrogen, helium, or argon flows out around the mist flow 18 through the gas inflow passage 9e, The vibration wave is reflected by the side wall surface of the vibration wave reflector 14 through the insulating material 16 and focused on the discharge hole of the nozzle plate 15 a, and the liquid mixed with the functional fine particles 4 from the discharge hole is formed as a mist flow 18. It is discharged and applied to the surface of the substrate 3 on the stage 13. Here, the mist jet head 19 and the stage 13 can be applied to the entire surface of the substrate 3 by relative movement by a mechanism (not shown).

  Next, the substrate 3 to which the functional fine particles 4 are attached is placed on the stage 32, and the high-frequency power is supplied via the high-frequency power source 6 while the reaction gas flows into the atmosphere control member 10d from the reaction gas inflow path 21. The thin film 8 is formed by causing the target 5 and the reactive gas to react in the atmospheric pressure plasma by being applied to the ejection type plasma head 22 and ejecting reactive species contributing to the film formation from the ejection type plasma head 22. If the film thickness is insufficient in one process, these processes may be alternately repeated a plurality of times. Alternatively, the functional fine particles 4 and the thin films 8 may be alternately deposited after the thin films 8 are formed on the substrate 3. Specific materials such as the functional fine particles 4 and the thin film 8 are the same as those described in the first embodiment.

  Further, the ejection type plasma head 22 and the stage 32 can be formed on the entire surface of the substrate 3 by relative movement by a mechanism (not shown). Examples of the reactive gas include simple substances such as helium, argon, nitrogen gas, and hydrogen gas, and mixed gases. The same effect can be obtained by a film forming method such as plasma CVD in which the thin film material gas is introduced without using the target 5 or the like.

  As described above, according to the eleventh embodiment described above, by providing the gas inflow passage 9e in the nozzle plate 15a of the mist jet head 19, it is possible to control the atmosphere only in necessary portions. In addition to the effects of the tenth embodiment, There is an effect that a more uniform film can be formed while making the coating mechanism compact.

Embodiment 12 FIG.
12 is a perspective view showing a schematic configuration of a functional film forming apparatus according to a twelfth embodiment of the present invention. FIG. 13 is a cross-sectional view showing a schematic configuration of the functional film forming apparatus according to a twelfth embodiment of the present invention. is there. 12 and 13, the functional film forming apparatus is provided with a head 24 in which a coating mechanism for coating the functional fine particles 4 and an ejection type plasma film forming mechanism are integrated. Here, the head 24 includes a vibration wave reflector 14 formed in a parabolic shape, a piezoelectric vibrator 17 bonded to the upper surface of the vibration wave reflector 14 via an insulating material 16, and the vibration wave reflector 14. Nozzle plate 15a joined to the lower surface of gas, gas inflow passage 9e formed in nozzle plate 15a, atmosphere control member 10e joined to the lower surface of nozzle plate 15a, and exhaust formed in atmosphere control member 10e A path 27 and a gas inflow path 28, a target 5, and a cooling unit 25 that cools the target 5 are provided.

  The nozzle plate 15a is arranged so that the opening of the nozzle plate 15a is located at the focal position of the paraboloid of the vibration wave reflector 14. A liquid (eg, water) containing the functional fine particles 4 (eg, silicon fine particles having a diameter of several tens of nanometers to several μm) is filled in the liquid chamber 20 surrounded by the vibration wave reflector 14 and the insulating material 16. A drive electrode (not shown) is provided on the upper surface of the piezoelectric vibrator 17 and a common electrode (not shown) is provided on the lower surface, and a high frequency voltage can be applied between the drive electrode and the common electrode by a driver. It has become. Further, at the center of the atmosphere control member 10e, a high frequency voltage can be applied to the target 5 by the high frequency power source 6.

  Next, a method for forming a functional film using the head 24 will be described. While an inert gas such as helium, argon, or nitrogen is allowed to flow through the gas inflow passages 9e, 28, exhaust is performed from the exhaust passage 27 to create a clean environment free of oxygen between the substrate 3 and the head 24.

  Next, an ultrasonic wave generated by applying a high-frequency voltage to the piezoelectric vibrator 17 is introduced into the liquid, the ultrasonic wave is reflected by the vibration wave reflector 14, and the acoustic energy of the ultrasonic wave is focused. Further, the nozzle plate 15a To focus on the through hole. As the vibration wave is focused in this manner, the energy density of the vibration wave released into the liquid is increased, and the mist flow 18 containing the functional fine particles 4 is discharged from the discharge hole onto the substrate 3 on the stage 13. The When the mist flow 18 is discharged onto the substrate 3, the liquid mixed with the functional fine particles 4 evaporates, and only the functional fine particles 4 are deposited on the surface of the substrate 3.

Next, an inert gas is allowed to flow from the gas inflow path 28 and exhaust gas is exhausted from the exhaust path 27 while a reaction gas (for example, hydrogen gas, hydrogen / helium mixed gas, hydrogen / argon mixed gas, hydrogen / Nitrogen mixed gas or the like is introduced to create a clean environment free of oxygen between the substrate 3 and the head 24.

  Further, the target 5 (for example, a silicon target) is cooled by the cooling unit 25 to maintain a low temperature. The substrate 3 is heated by a heater (not shown) and maintained at a high temperature. By applying high-frequency power from a high-frequency power source 6 to a silicon target in which hydride is volatile, a hydrogen plasma discharge is caused, and a reactive gas flow flowing from the gas inflow path 9e causes the silicon target and the substrate 3 to be Generation of silicon hydride (SiHx) (x = 1, 2,...) By chemical reaction with atomic hydrogen excited by hydrogen plasma, etching by volatilization, and hydride generated by etching are re-decomposed in plasma. Both processes of silicon target material deposition occur simultaneously.

  This reaction rate is higher for etching and lower for deposition on the surface of the target 5 on the low temperature side. On the other hand, on the surface of the substrate 3 on the high temperature side, the deposition rate is high and the etching rate is low. Accordingly, by appropriately increasing the temperature difference between the two, the difference in etching and deposition rates becomes very large, and relatively high-speed mass transfer from the low-temperature target 5 to the high-temperature substrate 3 occurs. Then, silicon is deposited on the substrate 3. Such mass transfer that is not performed under reduced pressure in a sealed space is called an atmospheric pressure plasma chemical transport method. The low temperature is, for example, 15 ° C., and the high temperature is, for example, 300 ° C., and it is preferable that there is a temperature difference of about 285 ° C. between the target 5 and the substrate 3. Therefore, if the low temperature side is −35 ° C., about 250 ° C. is preferable on the high temperature side, but any combination of temperatures can be used as long as the temperature difference is 100 ° C. or more.

  As described above, according to the twelfth embodiment, the deposition of the functional fine particles 4 (for example, silicon fine particles) by mist ejection and the deposition of the target material (for example, silicon) by the atmospheric pressure plasma chemical transport method are repeated in order. Thus, there is an effect that a silicon film mixed with silicon fine particles can be formed at high speed. Further, by adjusting the size of the functional fine particles 4 mixed in the liquid, there is an effect that a silicon film mixed with silicon fine particles of a desired size can be produced.

  Further, since the local atmosphere control of the peripheral portion is performed using the gas inflow passages 9e and 28 and the exhaust passage 27 provided in the head 24, the peripheral portion is made to be the same as in the ninth, tenth, and eleventh embodiments. The functional film forming apparatus can be made more compact than when covering and controlling the atmosphere. Further, by scanning the head 24 and the substrate 3 relatively, it is possible to easily cope with the substrate 3 having an enlarged area. If the film thickness is insufficient in one process, these processes may be alternately repeated a plurality of times. Alternatively, the functional fine particles 4 and the thin films 8 may be alternately deposited after the thin films 8 are formed on the substrate 3.

Embodiment 13 FIG.
FIG. 14 is a cross-sectional view showing a schematic configuration of the functional film forming apparatus according to the thirteenth embodiment of the present invention. 14, the difference from the head 24 of FIG. 13 is that in the head 24a, the lower surface of the vibration wave reflector 14a is inclined so as to be lowered from the side portion of the head 24a toward the center portion. Is that a substantially inverted C-shaped nozzle plate 15b is disposed. Corresponding to the shape of the nozzle plate 15b, the upper surface of the atmosphere control member 10f is formed to be inclined so as to fall from the side toward the center.

  Here, the nozzle mounting angle θ formed by the direction perpendicular to the mist ejection direction and the nozzle plate 15b is an acute angle (0 ° <θ <90 °). By setting the nozzle attachment angle θ to an acute angle, the meniscus can be retained up to a larger droplet, so that the overflow of the meniscus can be effectively suppressed against a high liquid pressure. That is, the effect of increasing the mist discharge amount can be achieved. For this reason, since the mixing amount of the functional fine particles 4 (for example, silicon fine particles) can be increased, a thick functional film (for example, a silicon film) can be formed at a higher speed. If the film thickness is insufficient in one process, these processes may be alternately repeated a plurality of times. Alternatively, the functional fine particles 4 and the thin films 8 may be alternately deposited after the thin films 8 are formed on the substrate 3.

  As described above, the functional film forming apparatus according to the present invention can stably form a functional film containing functional fine particles on the surface of a substrate while increasing the purity of the functional fine particles. The method is suitable for a method of forming a functional film containing functional fine particles having a large unit size on a substrate surface such as a glass substrate or a plastic substrate.

DESCRIPTION OF SYMBOLS 1 Liquid discharge port 2 Spin mechanism 3 Substrate 4 Functional fine particle 5 Target 6 High frequency power supply 7 Vacuum chamber 8 Thin film 9, 9a-9d Inert gas inflow path 10, 10a-10f Atmosphere control member 11 Atmosphere control vacuum chamber 12 Spray head 13 , 32 Stages 14, 14a Vibration wave reflectors 15, 15a, 15b Nozzle plate 16 Insulating material 17 Piezoelectric vibrator 18 Mist flow 19 Mist jet head 20 Liquid chamber 21 Reactive gas inflow path 22 Jet type plasma head 23 Inert gas 24, 24a Head 25 Cooling part 9e, 28 Gas inflow path 27 Exhaust path 31a Upper electrode 31b Lower electrode

Claims (9)

Attaching functional fine particles mixed in the liquid to the surface of the substrate;
And a step of forming a thin film by plasma on the substrate to which the functional fine particles are attached.   2. The method for forming a functional film according to claim 1, wherein the functional fine particles are adhered to the surface of the substrate in a space in which the atmosphere is controlled.   The method for forming a functional film according to claim 1, wherein the functional fine particles are adhered to a surface of a substrate by spraying a liquid in which the functional fine particles are mixed. Discharging the functional fine particles in the liquid as a mist to the surface of the substrate in a locally controlled atmosphere;
And a step of forming a thin film integrated with the functional fine particles by an atmospheric pressure plasma chemical transport method in a locally controlled atmosphere.   5. The method of forming a functional film according to claim 4, wherein the functional fine particles are silicon fine particles, the liquid is water, and the thin film is a silicon thin film. A substrate;
A functional film forming body, comprising: a functional film provided on the base material and having a thin film that does not include the functional fine particles formed on the functional fine particles.   The functional film forming body according to claim 6, wherein the functional fine particles and the thin film not containing the functional fine particles are alternately deposited on the base material.   The functional film forming body according to claim 6, wherein the thin film is a sputtered film.   The functional film forming body according to claim 6, wherein the thin film is a plasma CVD film.

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