TW202111805A - Microstructure manufacturing method and microstructure manufacturing device performing etching by introducing a reactive gas to the plasma source (7) in the chamber (2) of the IAD device (1) - Google Patents

Abstract

A subject of the present invention is to provide a method of manufacturing a microstructure and a device for manufacturing the microstructure, which are excellent in etching rate and can increase throughput. The method of manufacturing a microstructure of the present invention is a method of manufacturing a microstructure by etching, which uses an IAD (Ion Assisted Deposition) device (1) to introduce a reactive gas to the plasma source (7) in the chamber (2) of the IAD device (1) to perform etching.

Description

Microstructure manufacturing method and microstructure manufacturing device

The present invention relates to a method for manufacturing a microstructure and a device for manufacturing a microstructure, and more particularly to a method for manufacturing a microstructure that is excellent in etching rate and can increase throughput.

Conventionally, a plasma generation source is installed in an etching device, and in order to increase the processing area, it is necessary to increase the matching box and the coil required to generate the plasma. However, it is actually impossible to enlarge the matching box, etc., and the processing area is about 8 inches, which makes it difficult to increase the processing volume. Specifically, in the device described in Patent Document 1, it is necessary to increase the size of the target material as the electrode as a plasma source. Therefore, in order to cope with the increase in the size of the wafer, a plasma source is required in addition to the chamber The large-scale and pluralized ones. However, in terms of increasing the size and number of plasma sources, it is necessary to increase the size of the matching box required to generate plasma. In addition, the conventional etching apparatus only has an etching function, so when film formation is required, it is necessary to prepare a film formation apparatus separately, which also leads to a reduction in throughput. On the other hand, in the vapor deposition equipment through the IAD (Ion Assisted Deposition) method, generally only argon (Ar) or oxygen (O ₂ ) can be used, so such argon (Ar) or oxygen (O ₂ ) gas is used for etching In the case of, the etching rate is very small, and the etching process cannot be performed. [Prior Technical Document] [Patent Document]

[Patent Document 1] JP 2000-226649 A

[The problem to be solved by the invention]

The present invention was created in view of the above-mentioned problems and conditions. The problem to be solved by the present invention is to provide a method for manufacturing a microstructure and a manufacturing device for the microstructure, without the need to increase the size and number of plasma sources, and is excellent in terms of etching rate. And can increase the processing capacity. [Technical means to solve the problem]

In the course of reviewing the causes of the above-mentioned problems in order to solve the above-mentioned problems, the inventors found that etching by introducing a reactive gas into the plasma source in the chamber of the IAD device can provide excellent etching rate and can provide The present invention is completed by a method of manufacturing a microstructure that improves the throughput. That is, the above-mentioned problems related to the present invention are solved by the following means.

1. A method of manufacturing a microstructure by etching, Using an IAD (Ion Assisted Deposition) device, a reactive gas is introduced into the plasma source in the chamber of the IAD device to perform etching.

2. The method for producing a microstructure according to item 1, wherein a gas containing a Freon-based gas or a hydrogen fluoride gas is introduced as the reactive gas.

3. The method for manufacturing a microstructure according to item 1 or 2, wherein the IAD device is provided with a means for detoxifying the harmful gas from the reactive gas.

4. The method for manufacturing a microstructure according to item 3, wherein, as a means of detoxification, 10% or more of the surface area of the inner wall of the chamber and the member arranged in the chamber is used to reduce the harmful Cover with harmless materials or polytetrafluoroethylene (registered trademark).

5. The method for manufacturing a microstructure according to item 3, wherein, as the detoxification means, a neutralizing material that neutralizes the harmful gas is provided in the chamber.

6. The method of manufacturing a microstructure according to item 3, wherein, as a means of detoxification, the inner wall of the chamber and the members arranged in the chamber are formed by coating or vapor deposition to neutralize the Neutralizing material for harmful gases.

7. The method for manufacturing a microstructure according to item 6, wherein, before the atmosphere of the chamber is released, the inner wall of the chamber and the members arranged in the chamber are vapor-deposited to form the neutralizing material.

8. The method of manufacturing a microstructure according to item 6 or 7, wherein: The aforementioned neutralizing material can be peeled off, It includes a procedure of peeling off the neutralizing material attached to the microstructure.

9. The method of manufacturing a microstructure according to any one of items 1 to 8, wherein: Install a detector that can detect hydrogen fluoride gas or Freon-based gas in the aforementioned chamber, Before the chamber is released, the concentration of the hydrogen fluoride gas or the freon-based gas is detected by the detector, and after the concentration of the hydrogen fluoride gas or the freon-based gas in the chamber becomes below a predetermined reference value, the chamber is opened The door of the room.

10. The method of manufacturing a microstructure according to any one of items 1 to 9, wherein: In the aforementioned IAD device, a film forming source formed by electron beam or resistance heating is installed in the same chamber as the aforementioned chamber, The IAD device has a procedure for forming a film using the aforementioned film forming source and a procedure for performing the aforementioned etching using the aforementioned plasma source.

11. The method of manufacturing a microstructure according to any one of items 1 to 10, wherein: The aforementioned microstructure has two or more multilayer films, At least one layer of the aforementioned multilayer film contains silicon dioxide.

12. The method for manufacturing a microstructure according to any one of items 1 to 11, wherein, during the aforementioned etching, the selection ratio of the metal mask to the etched layer (etching rate of the etched layer/metal mask Etching rate) becomes 2 times or more, adjust the distance from the grid of the plasma source of the IAD device to the layer to be etched, or the acceleration voltage and pressurized current of the IAD device, or the amount of etching gas introduced, or the vacuum Degree, or the amount of argon introduced.

13. The method for manufacturing a microstructure according to any one of items 1 to 12, wherein during the etching, the distance from the grid of the plasma source of the IAD device to the layer to be etched is 40 cm or more.

14. The method for manufacturing a microstructure according to any one of items 1 to 13, wherein the setting value of the IAD device during the etching is set at an accelerating voltage in the range of 300 to 1200V and an accelerating current in the range of 300 to 1200V. Within the range of 1200mA.

15. The method for manufacturing a microstructure according to any one of items 1 to 14, wherein when the volume of the chamber is 2700L, the amount of Freon-based gas or hydrogen fluoride gas introduced in the chamber during the etching is Above 20sccm.

16. The method of manufacturing a micro structure 15 to any one of 1, wherein the volume of the chamber is 2700L, the degree of vacuum during etching is ^{5.0 × 10 -3 ~ 5.0 × 10} - Within the range of ^{1 Pa.}

17. The method of manufacturing a microstructure according to any one of items 1 to 16, wherein when the volume of the chamber is 2700 L, the amount of argon gas introduced into the chamber during the etching is 20 sccm or less.

18. The method for manufacturing a microstructure according to any one of items 1 to 17, wherein the gas exhaust mechanism in the chamber is exhausted to the chamber with a gas exhaust volume of 250L/min or less in the chamber The pressure in the room becomes 3.0×10 ⁴ Pa.

19. A device for manufacturing a microstructure, which is a user of the method for manufacturing a microstructure according to any one of items 1 to 18, A reactive gas is introduced into the plasma source in the chamber of the IAD device to perform etching. [Compared with the effect of the previous technology]

Through the above-mentioned means of the present invention, there is no need to increase the size and multiples of the plasma source, and provide a method for manufacturing a microstructure and a manufacturing device for the microstructure, which has excellent etching rate and can increase the throughput. Regarding the performance mechanism or action mechanism of the efficacy of the present invention, although it is not clear, it is speculated as follows. Since the IAD device is used to introduce the reactive gas into the plasma source to perform etching, by installing the plasma source in a large vacuum chamber such as a vapor deposition machine, the device can be substantially enlarged and the processing area can be increased , So the processing capacity is increased. In addition, not only the etching function but also the film forming source is used, so film forming and etching can be performed with the same equipment, which also leads to an increase in throughput. Furthermore, the use of reactive gas increases the etching rate.

The manufacturing method of the microstructure of the present invention is a method of manufacturing the microstructure by etching, using an IAD (Ion Assisted Deposition) device to introduce a reactive plasma source in the chamber of the IAD device The gas is used for etching. This feature is a common or corresponding technical feature of the following embodiments.

In an embodiment of the present invention, as the reactive gas, it is preferable to introduce a gas containing a Freon-based gas or a hydrogen fluoride gas from the viewpoint that the desired microstructure can be produced through etching.

The IAD device is preferably provided with a means for detoxifying the harmful gas from the reactive gas, and as the means for detoxifying, the harmful gas is detoxified and the harmful gas can be prevented from adhering to the chamber. From the viewpoint of the inner wall and the members arranged in the chamber, it is preferable that 10% or more of the surface area of the inner wall of the chamber and the members arranged in the chamber be made to harmless the aforementioned harmful gas. Cover with vinyl fluoride.

In addition, as the aforementioned detoxification means, it is preferable to provide a neutralizing material that neutralizes the aforementioned harmful gas in the aforementioned chamber. Furthermore, as the aforementioned means of detoxification, from the viewpoint of low cost and detoxification, it is preferable to neutralize the inner wall of the chamber and the members arranged in the chamber by coating or vapor deposition. Neutralizing material for the aforementioned harmful gases. In particular, from the viewpoint of being able to be easily and reliably detoxified, it is preferable to form the neutralizing material by the vapor deposition before the atmosphere of the chamber is opened.

From the viewpoint that the neutralizing material can be peeled off even if it is attached to the microstructure to produce the desired microstructure, it is preferable that the neutralizing material formed above is peelable, including the neutralizing material attached to the microstructure. The procedure of stripping.

From the viewpoint of preventing harmful gases from being discharged to the outside of the chamber, it is preferable to install a detector capable of detecting hydrogen fluoride gas or Freon-based gas in the chamber, and to detect it through the detector before the chamber is released. After the concentration of the hydrogen fluoride gas or the freon-based gas in the chamber becomes below a predetermined reference value, the door of the chamber is opened.

From the viewpoint of forming a film after etching and etching after forming a film so that the desired microstructure can be manufactured, it is preferable that the IAD device be installed in the same chamber as the chamber made by electron beam or resistance heating. The film forming source of the IAD device has a process of forming a film using the foregoing film forming source and a process of performing the foregoing etching using the foregoing plasma source.

From the viewpoint of improving the etching rate, it is preferable that the microstructure has two or more multilayer films, and at least one of the multilayer films contains silicon dioxide.

In the aforementioned etching, from the viewpoint of improving the etching rate, it is preferable to adjust the selection ratio of the metal mask to the etched layer (etching rate of the etched layer/etching rate of the metal mask) to be 2 times or more. The distance from the grid of the plasma source of the IAD device to the layer to be etched, or the acceleration voltage and pressurized current of the IAD device, or the amount of etching gas introduced, the degree of vacuum, or the amount of argon introduced. In particular, at the time of the aforementioned etching, it is preferable that the distance from the grid of the plasma source of the aforementioned IAD device to the layer to be etched be 40 cm or more.

From the viewpoint of preventing the amount of ions from increasing excessively and increasing the physical etching effect, it is preferable that the setting value of the IAD device during the etching is in the range of 300 to 1200V for acceleration voltage and 300 to 1200mA for acceleration current. In the range.

When the volume of the chamber is 2700 L, from the viewpoint of improving the etching rate, it is preferable that the introduction amount of the Freon-based gas or hydrogen fluoride gas in the chamber during the etching is 20 sccm or more.

When the volume of the chamber is 2700 L, from the viewpoint of improving the etching rate, it is preferable that the degree of vacuum during the etching is in the range of 5.0×10 ^-3 to 5.0×10 ^-1 Pa.

When the volume of the chamber is 2700L, in terms of preventing the mask used for processing the microstructure from being physically etched by argon gas and disappearing, it is preferable to use the argon gas in the chamber during the etching process. The amount of introduction is less than 20sccm. In the gas exhaust mechanism of the aforementioned chamber, it is preferable that the gas exhaust volume in the upper chamber is exhausted at 250 L/min or less until the pressure in the chamber becomes 3.0×10 ⁴ Pa. The purpose of controlling the exhaust volume in this way is that when there is gas in the chamber, the amount of gas discharged from the gas exhaust mechanism is about 1000L/min. To deal with this exhaust volume, it is necessary to increase the size of the decontamination machine. Need to match the detoxification ability of the exhaust volume. Therefore, control is directed to reduce the gas exhaust rate to 250L/min or less, so that even an IAD device with a large chamber can be made to always connect the chamber to the detoxifier, which can prevent harmful effects. The gas is exhausted to the atmosphere.

The microstructure manufacturing device used in the microstructure manufacturing method of the present invention introduces a reactive gas into the plasma source in the chamber of the IAD device to perform etching. As a result, there is no need to increase the size and multiple of the plasma source, the etching rate is also excellent, and the throughput can be increased.

Hereinafter, the present invention, its constituent elements, and embodiments and aspects of the present invention will be described. In addition, in this case, "-" is used to include the numerical value described before and after it as the lower limit and the upper limit.

[Outline of the manufacturing method of the microstructure of the present invention] The manufacturing method of the microstructure of the present invention is a method of manufacturing the microstructure by etching. An IAD (Ion Assisted Deposition) device is used to introduce a reactive gas into the plasma source of the IAD device to perform the aforementioned etching.

Regarding the aforementioned IAD device, a vapor deposition device using a general IAD method can be used. Preferably, a film-forming source formed by electron beam or resistance heating is installed in the same chamber as the device, and the aforementioned film-forming source is used. Film formation by vapor deposition is performed, and etching is performed using the plasma source described above. The order of film formation and etching is not particularly limited.

The aforementioned microstructure may have a single-layer film of one layer, or a multilayer film of two or more layers, but it is preferable to have a multilayer film in the present invention. Furthermore, from the viewpoint of improving the etching rate, it is preferable that at least one layer of the aforementioned multilayer film contains silicon dioxide. In addition, the surface of the single-layer film or the multi-layer film disposed on the IAD device is etched using the plasma source to form pores on the surface. In the case of a multilayer film, this etching forms pores that partially expose the surface of the layer adjacent to the uppermost layer. Specifically, the microstructure related to the present invention is preferably a dielectric multilayer film described later.

When performing etching using the aforementioned IAD device, a reactive gas is introduced into a plasma source (IAD ion source described later). As the reactive gas, it is preferable to introduce a gas containing a Freon-based gas or a hydrogen fluoride gas from the viewpoint that the desired microstructure can be manufactured through etching.

In addition, the reactive gas is introduced into the IAD device to perform etching, which results in the generation of harmful gas from the reactive gas. Therefore, it is preferable to install a means (described later) for detoxifying the harmful gas to make the harmful gas harmless.化.

Hereinafter, although the IAD device used in the manufacturing method of the microstructure of the present invention will be described in detail, it is not limited to this.

[IAD device] FIG. 1 is a schematic diagram showing an example of an IAD device. The IAD device 1 related to the present invention includes a dome chamber 3 in the chamber 2, and the substrate 4 is arranged along the dome chamber 3. At the bottom of the chamber 2, a vapor deposition source (film formation source) 5 and an IAD ion source (plasma source) 7 are arranged. In addition, in the chamber 2, a gas supply unit 91 is connected via a port 91 a, and the gas from the gas supply unit 91 is supplied to the IAD ion source 7. In addition, the chamber 2 communicates with the gas discharge portion 92 via the port 92a. In addition, the gas exhaust unit 92, the port 92a, and the like constitute the gas exhaust mechanism according to the present invention.

＜Evaporation source＞ The vapor deposition source 5 includes an electron gun or a resistance heating device that evaporates the vapor deposition material, and the vapor deposition material 6 is scattered from the vapor deposition source 5 toward the substrate 4 and condenses and solidifies on the substrate 4. At this time, the ion beam 8 is irradiated from the IAD ion source 7 to the substrate 4, and the high kinetic energy of the ions is applied during film formation to form a dense film, improve the adhesion of the film, and the like. In addition, the IAD ion source 7 ionizes the supplied reactive gas, and emits ionized gas molecules (ion beam) into the chamber 2. The emitted ion beam does not form a shield on the film formed on the substrate 4. The exposed part of the mask is etched.

Examples of the substrate 4 used in the present invention herein include resins such as glass, polycarbonate resin, cycloolefin resin, and the like, and are preferably a lens for vehicle.

Regarding the aforementioned vapor deposition source 5, although one vapor deposition source is shown in FIG. 1, the number of vapor deposition sources 5 may be plural. The film-forming material (evaporation material) of the vapor deposition source 5 is passed through the electron gun and resistance heating to generate the vapor-deposited substance 6, and the film-forming material is scattered and adhered to the substrate 4 (for example, lens) provided in the chamber 2, so that A layer made of a film-forming material (for example, SiO ₂ , MgF ₂ , or Al ₂ O ₃ , which is a low-refractive index material described later, and Ta ₂ O ₅ , TiO ₂ , which is a high-refractive index material described later) On the substrate 4.

In addition, as described later, when forming _{the uppermost layer containing SiO 2} in the dielectric multilayer film of the present invention, it is preferable to arrange an SiO ₂ target on the vapor deposition source 5 to form a _{layer containing SiO 2} as a main component. Furthermore, to further improve the hydrophilic function, it is preferable to mix an element with a smaller electronegativity than Si in the aforementioned SiO ₂ , and the element with a smaller electronegativity than Si is exemplified by sodium element, magnesium element, potassium element, calcium element, and lithium. Wait.

In the case of adding sodium element, a sodium-containing SiO ₂ target can be prepared, and this target can be placed in a vapor deposition source and directly vapor deposited. As an alternative method, the SiO ₂ target and the sodium target _{may be separately arranged, and the SiO 2} and sodium can be vapor-deposited through co-evaporation. In the present invention, in order to improve the accuracy of sodium content, it is preferable to prepare a sodium-containing SiO ₂ target, arrange this target in a vapor deposition source, and directly vaporize it.

_{Na 2} O is preferred for sodium, MgO is preferred for magnesium, K ₂ O is preferred for potassium, CaO is preferred for calcium, and Li ₂ O is preferred for lithium. All commercially available ones can be used.

<IAD ion source> The IAD ion source 7 is a device that ionizes the argon and oxygen supplied from the gas supply unit 91 when forming a film on the substrate 4, and ionizes the ionized gas molecules (ion beam 8 ) The substrate 4 is irradiated to ionize the reactive gas supplied from the gas supply unit 91 during the etching of _{the film (for example, the uppermost layer containing SiO 2) formed on the substrate 4 to ionize the ionized ions} The beam 8 irradiates the film to perform etching. The aforementioned argon gas and oxygen gas are also used as neutralizers to prevent the positive charge accumulated on the substrate due to the phenomenon (so-called charging) that the positive ions irradiated from the ion gun accumulate on the substrate and make the entire substrate positively charged. Electric neutralizer. The condition of the neutralizer is preferably 1000 mA or less in terms of the prevention of charging and the effect of reducing damage to the metal shield used to make the structure. It is preferably in the range of 250 to 500 mA.

For IAD ion source 7, Kaufman type (filament), hollow cathode type, RF type, bucket type, double plasma tube type, etc. can be applied. The above-mentioned gas molecules are irradiated to the substrate 4 from the IAD ion source 7, so that, for example, molecules of the film-forming material evaporated from a plurality of evaporation sources can be pressed on the substrate 4, and a film with high adhesion and density can be formed on the substrate 4. On the substrate 4. Although the IAD ion source 7 is arranged at the bottom of the chamber 2 to face the substrate 4, it may be arranged at a position deviated from the opposite axis.

At the time of etching, from the viewpoint of increasing the etching rate, it is preferable that the selection ratio between the metal mask and the layer to be etched (for example, the uppermost layer) described later (etching rate of the layer to be etched/etching rate of the metal mask) is 2 Adjust the distance from the grid of the plasma source of the IAD device to the layer to be etched, or the acceleration voltage and pressurized current of the IAD device, or the amount of etching gas introduced, or the degree of vacuum, or the introduction of argon the amount. In particular, during etching, it is preferable that the distance from the grid of the plasma source of the IAD device to the layer to be etched be 40 cm or more. In addition, the set value of the ion beam during etching is preferably in the range of 300 to 1200V for acceleration voltage and 300 to 1200mA for acceleration current. Within this range, it is possible to prevent the amount of ions from increasing excessively and the physical etching action to become stronger, leading to the disappearance of the mask used for the etching described later. In the etching process, the irradiation time of the ion beam can be set to 15 minutes when the distance from the grid of the plasma source of the IAD device to the etched layer is 40 cm, and the time from the grid of the plasma source of the IAD device to the etched layer is 15 minutes. When the distance to the etched layer is 100 cm, it is 50 minutes. In addition, in the film formation process, the irradiation time of the ion beam can be, for example, 1 to 800 seconds, and the number of particles irradiated by the ion beam can be, for example, 1×10 ¹³ to 5×10 ¹⁷ particles/cm ² .

The ion beam used in the etching process may be an ion beam of a Freon-based gas or a hydrogen fluoride gas as a reactive gas. For example, when the volume of the chamber is 2700L, the introduction amount of the Freon-based gas or hydrogen fluoride gas is preferably 20 sccm or more. In addition, from the viewpoint of preventing the mask used for etching from being physically etched by the argon gas, it is preferable to set the amount of argon gas introduced during etching to be 20 sccm or less.

In addition, the ion beam used for the film forming process may be an ion beam of oxygen, an ion beam of argon, or an ion beam of a mixed gas of oxygen and argon. For example, it is preferable that the amount of oxygen introduced is 30 to 60 sccm, and the amount of argon introduced is 0 to 10 sccm. In the present invention, "sccm" is an abbreviation of standard cc/min, and is a unit that indicates how many ccs flow per minute at ^{1 atmospheric pressure (atmospheric pressure of 10 13 hPa).}

＜Dome room＞ The dome chamber 3 holds at least one holder 3a that holds the substrate 4, which is also called a vapor deposition umbrella. This dome chamber 3 has a circular arc shape in cross section, and is a rotationally symmetrical shape that passes through the center of the chord connecting both ends of the circular arc and is perpendicular to the chord as a rotationally symmetrical axis. The dome chamber 3 rotates at a constant speed, for example, about an axis, so that the substrate 4 held by the dome chamber 3 via the holder 3a revolves at a constant speed around the axis.

In the dome chamber 3, a plurality of holders 3a can be arranged and held in the rotation radius direction (revolution radius direction) and the rotation direction (revolution direction). Thereby, it is possible to simultaneously perform etching or film formation on the plurality of substrates 4 held by the plurality of holders 3a, and the production efficiency of the device can be improved.

<Gas Supply Unit> The gas supply unit 91 is for supplying gas to the IAD ion source 7. As for the gas supplied by the gas supply unit 91, reactive gas and inert gas are exemplified. The reactive gas includes, for example, carbon tetrafluoride (CF ₄ ), sulfur hexafluoride (SF ₆ ), and trifluoromethane (CHF ₃ ). Among these, it is particularly preferable to contain a Freon-based gas or hydrogen fluoride gas. The inert gas includes, for example, argon (Ar), nitrogen (N ₂ ), helium (He), krypton (Kr), neon (Ne), and mixed gases of these.

<Gas discharge part> The gas discharge part 92 is used to exhaust the inside of the chamber 2. The permeated gas exhaust unit 92 exhausts the inside of the chamber 2 to a predetermined degree of vacuum. When the volume of the chamber 2 is 2700 L, it is preferable that the degree of vacuum during the upper etching is in the range of 5.0×10 ^-3 to 5.0×10 ^-1 Pa. In addition, in the gas exhaust mechanism composed of the gas discharge portion 92 and the port 92a, it is preferable that the gas exhaust volume in the upper chamber 2 is exhausted at 250 L/min or less until the pressure in the chamber 2 becomes 3.0×10 Up to ^{4 Pa.} The purpose of controlling the exhaust volume in this way is that when there is gas in the chamber 2, the amount of gas discharged from the gas exhaust mechanism is about 1000 L/min. For this exhaust volume, it is necessary to increase the size of the detoxification machine. It needs to match the detoxification ability of the exhaust gas. Therefore, control is directed to reduce the gas exhaust rate to 250L/min or less, so that even an IAD device with a large chamber can be made to always connect the chamber to the detoxifier, which can prevent harmful effects. The gas is exhausted to the atmosphere. Specifically, the diameter of the piping connected to the gas discharge portion 92 and the port 92a is narrowed so that the gas exhaust volume can be reduced to 250 L/min or less. For example, the generally used piping of φ25mm is piping of φ10mm or less, so that control can be performed in the direction of reducing the exhaust gas volume. In addition, it is preferable to use an orifice plate provided with a hole having a thickness of 1 mm and a diameter of 10 mm or less in terms of a method for making a pipe diameter of 10 mm or less.

＜Means of harmlessness＞ In terms of means to detoxify harmful gases generated by etching (for example, gases containing Freon-based gas and hydrogen fluoride gas), for example, 10% of the surface area of the inner wall of the chamber 2 and the members arranged in the chamber The above-mentioned harmful gas is harmless material or polytetrafluoroethylene to cover. The components arranged in the aforementioned chamber 2 include, for example, the dome chamber 3, the vapor deposition source 5, the IAD ion source 7, and the like. Examples of materials that detoxify the aforementioned harmful gas include calcium carbonate and calcium oxide. In addition, when covering with polytetrafluoroethylene, a polytetrafluoroethylene sheet (product name: PTFE sheet, model number: 638-17-97-01, manufactured by Tokyo Glass Instruments Co., Ltd.) can be used. The inner wall of the chamber 2 and the components arranged in the chamber 2 are covered with materials or polytetrafluoroethylene that harmless gases are harmless, so that the harmful gases generated during the etching process are harmless, or harmful The gas adheres to the inner wall of the chamber 2 and the aforementioned members. For example, when the surface (upper surface and lower surface) of the dome chamber 3 is covered with polytetrafluoroethylene, it is preferable to place the remaining holder 3a (not including the holder 3a) other than the holder 3a holding the vapor-deposited or etched substrate. The holder used) covers the polytetrafluoroethylene sheet 3b. Figure 2 (a) is a schematic diagram of the dome chamber covering the polytetrafluoroethylene sheet, (b) is a cross-sectional view of (a), and (c) is a schematic diagram of the dome chamber before covering the polytetrafluoroethylene sheet. In addition, FIG. 1 shows an example in which the polytetrafluoroethylene sheet is not covered.

In addition, as the aforementioned detoxification means, a neutralizing material that neutralizes the aforementioned harmful gas may be provided in the chamber 2. Specifically, for example, calcium carbonate and calcium oxide are arranged in a position in the chamber 2 that does not affect vapor deposition and etching. In this way, the harmful gas is neutralized and rendered harmless. Furthermore, in terms of other detoxification means, from the viewpoint of low cost and detoxification, it is preferable that the inner wall of the chamber 2 and the components arranged in the chamber 2 be coated or vapor-deposited to form a neutralization Neutralizing material for the aforementioned harmful gases. Examples of the neutralizing material used when forming a film by coating include calcium carbonate and calcium oxide, and examples of neutralizing materials used when forming a film by vapor deposition include calcium carbonate and calcium oxide.

In the case of forming the neutralizing material by vapor deposition, it is preferable to arrange the inner wall of the chamber and the inner wall of the chamber before the atmosphere of the chamber is released from the viewpoint of being effective in detoxifying harmful gases after etching. The member is formed into a film by vapor deposition.

In addition, even if the neutralizing material is attached to the microstructure during film formation, the neutralizing material can be removed and the desired microstructure can be manufactured. Preferably, the neutralizing material formed by coating or vapor deposition is It can be peeled off, and the process of peeling off the neutralizing material attached to the microstructure is performed. The peeling method includes, for example, a peeling method through etching liquid, organic solvent, and dry etching. In addition, it is preferable that the aforementioned detoxification means is further provided in the gas discharge portion 92 as the detoxification device 93. It is preferable to use, for example, a dry etching exhaust gas treatment device (manufactured by Ube Industries Co., Ltd.) as the pest removal machine 93.

In addition, the chamber 2 is provided with a detector 11 capable of detecting hydrogen fluoride gas or Freon-based gas. The hydrogen fluoride gas generated in the chamber 2 may exceed the safety standard because the detector 11 is installed in order to ensure the safety of the working environment. The aforementioned detector 11 is preferably configured such that the gas suction port faces downward. Thereby, the detection accuracy of gas concentration is improved. In the figure, the dotted arrow extending toward the detector indicates the direction of gas inhalation. The detector 11 detects the concentration of hydrogen fluoride gas or Freon-based gas in the chamber 2 before the door of the chamber 2 is released, and after it becomes a predetermined reference value or less, the control unit described later controls the door of the chamber 2 to open. Thereby, harmful gas can be prevented from being discharged to the outside of the chamber 2. As for the aforementioned detector 11, for example, Riken Keiki GD-70D or the like can be used. In addition, not only hydrogen fluoride gas and Freon-based gas, but also a detector that can detect other harmful gases.

In addition, the IAD device 1 related to the present invention includes a monitor system 10. The monitor system 10 is a system that monitors the layer that evaporates from each vapor deposition source 5 and adheres to itself during vacuum film formation, thereby monitoring the wavelength characteristics of the layer formed on the substrate 4. Through this monitor system, the optical characteristics of the layer formed on the substrate 4 (such as spectral transmittance, light reflectance, optical layer thickness, etc.) can be grasped. In addition, the monitor system 10 includes a crystal layer thickness monitor, and can also monitor the physical layer thickness of the layer formed on the substrate 4. The monitor system 10 also functions as a control unit, which controls the ON/OFF switching of a plurality of evaporation sources 5, the ON/OFF switching of the IAD ion source 7, and the gas supply unit 91 and The operation of the gas discharge unit 92, the opening and closing operation of the door (not shown) of the chamber 2, and the like.

[Dielectric multilayer film] The microstructure manufactured by the method of manufacturing the microstructure of the present invention preferably has two or more multilayer films, and preferably at least one layer contains silicon dioxide. Preferably, the aforementioned multilayer film is formed on the substrate. Specifically, regarding the microstructure of the present invention, it is preferably a dielectric multilayer film. The dielectric multilayer film has at least one low refractive index layer and at least one high refractive index layer, the uppermost layer furthest from the substrate is the low refractive index layer, and the uppermost layer is arranged on the substrate side. The high refractive index layer is a functional layer containing a metal oxide with a photocatalyst function, and the uppermost layer is a layer containing the aforementioned silicon dioxide, that is, a hydrophilic layer containing a metal oxide with a hydrophilic function, and has the aforementioned function The pores partially exposed on the surface of the layer are preferable.

Here, the "low refractive index layer" refers to a layer with a refractive index lower than 1.7 under d-rays. The high refractive index layer refers to a layer having a refractive index of 1.7 or more under d-rays. The substrate is an optical member formed of resin or glass regardless of shape. The transmittance at a light wavelength of 550 nm is preferably 90% or more. Here, the "photocatalyst function" in the present invention refers to the decomposition effect of organic matter through the photocatalyst. This is when the photocatalytic TiO _{2 is} irradiated with ultraviolet light after the electrons are released, active oxygen is generated, and the hydroxyl group (·OH radical) decomposes organic matter due to its strong oxidizing ability. _{The addition of a functional layer containing TiO 2 to} the multilayer film according to the present invention makes it possible to prevent the organic matter attached to the optical member from contaminating the optical system as contaminants.

Whether it has a photocatalyst effect, for example, in an environment of 20°C and 80%, a sample colored with a pen can be irradiated with UV and a light amount of 20 J is accumulated, and the color change of the pen can be evaluated step by step to determine. The pen evaluation method is based on the information described in ISO-TC206.

In addition, the "hydrophilic function" means that the contact angle between the standard liquid (pure water) and the uppermost surface is measured according to the method defined by JIS R3257. A water contact angle of 30° or less is called "hydrophilicity". Preferably it is 15 degrees or less. In particular, the case of 15° or less is defined as the so-called "super-hydrophilicity" in the present invention.

The specific measurement conditions are at a temperature of 23°C and a humidity of 50%RH. About 10μL of pure water, which is the aforementioned standard liquid, is dropped on the sample, and 5 places on the sample are measured through a G-1 device manufactured by Elma Co., Ltd., and the measured value is Get the average contact angle on average. The time until the contact angle is measured is measured within 1 minute after dropping the standard liquid.

3 is a cross-sectional view illustrating an example of the structure of a dielectric multilayer film. Among them, the number of layers of the low refractive index layer and the high refractive index layer is an example, and is not limited to this. In addition, other films may be formed between the uppermost layer and the uppermost layer, and between the functional layer and the uppermost layer, within a range that does not hinder the effect of the present invention.

The dielectric multilayer film 100 includes, for example, a high refractive index layer 103 having a refractive index higher than that of a glass substrate 101 constituting a lens, and a low refractive index layer 102 having a refractive index lower than the aforementioned high refractive index layer. , 104. Furthermore, the uppermost layer 106 furthest from the substrate 101 is a low refractive index layer, and the high refractive index layer adjacent to the uppermost layer is a functional layer 105 mainly composed of a metal oxide having a photocatalyst function, and the uppermost layer 106 is The upper layer has pores 30 that partially expose the surface of the aforementioned functional layer and microstructures 31 other than the pores, and constitute a multilayer film 107. With this structure, the photocatalyst function (self-cleaning property) possessed by the functional layer 105 can be expressed on the surface of the multilayer film via the uppermost layer 106. Here, the microstructures 31 other than the pores are etched through the IAD device 1 according to the present invention with the uppermost layer containing a metal oxide having a hydrophilic function using a metal mask described later to form pores and remain structural parts.

The aforementioned dielectric multilayer film preferably has a multilayer structure in which such a high refractive index layer and a low refractive index layer are alternately laminated. Although the number of layers to be laminated is not particularly limited, from the viewpoint of maintaining high productivity and obtaining an anti-reflection layer, it is preferably within 12 layers. In other words, although the number of layers depends on the required optical performance, approximately 3 to 8 layers are laminated, so that the reflectance of the entire visible range can be reduced, and the stress of the film can be prevented from increasing and the film peeling off. From a viewpoint, the upper limit number is preferably 12 layers or less. From the viewpoint of improving the recognizability of images captured as an automotive lens, the dielectric multilayer film related to the present invention is preferably higher than the light reflectivity for light incident from the normal direction in the light wavelength range of 450 to 780 nm It is less than 1% on average. In the present invention, a multilayer film is formed on the substrate 101 to constitute an optical member. The light reflectance can be measured with a reflectance measuring machine (USPM-RUIII) (manufactured by Olympus Co., Ltd.).

In terms of materials used for the high refractive index layer and low refractive index layer of the present invention, oxides such as Ti, Ta, Nb, Zr, Ce, La, Al, Si, and Hf are preferred, or combinations thereof The oxidizing compound and MgF ₂ are suitable. In addition, by stacking multiple layers of different dielectric materials, it is possible to add the function of reducing the reflectance of the entire visible range.

The aforementioned low refractive index layer is composed of a material having a refractive index smaller than 1.7, and in the present invention, it is preferably _{a layer containing SiO 2} as a main component. Among them, it is also preferable to contain other metal oxides, and from the viewpoint of light reflectivity, a mixture _{of SiO 2} and a part of Al ₂ O _{3 , MgF 2} and the like are also preferable.

The high refractive index layer is preferably composed of a material with a refractive index of 1.7 or higher, for example, a mixture of Ta oxide and Ti oxide, in addition to Ti oxide, Ta oxide, La oxide and Ti oxide Mixture and so on. The metal oxide used for the high refractive index layer preferably has a refractive index of 1.9 or more. In the present invention, Ta ₂ O ₅ and TiO ₂ are preferred, and Ta ₂ O _{5 is} more preferred.

Although the overall thickness of the dielectric multilayer film is not particularly limited, it is preferably 500 nm or less from the viewpoint of anti-reflection performance, and more preferably in the range of 50 to 500 nm. When the thickness is 50 nm or more, the anti-reflection optical properties can be exerted, and when the thickness is 500 nm or less, the error sensitivity is reduced, and the yield of the spectral characteristics of the lens can be improved.

The uppermost layer 106 is preferably _{a layer containing SiO 2} as a main component, and it is preferable that the uppermost layer contains an element having a smaller electronegativity than Si, and it is particularly preferable to contain sodium in a range of 0.5 to 10% by mass. The more preferable range of the content is the range of 1.0 to 5.0% by mass. Containing this element makes it possible to maintain super-hydrophilicity for a long time.

Here, the “main component” means that 51% by mass or more of the total mass of the uppermost layer is SiO ₂ , and means that it is preferably 70% by mass or more, and particularly preferably 90% by mass or more.

The composition analysis of the uppermost layer can be measured using the following X-ray photoelectron spectrometer (XPS).

(XPS composition analysis) ・Device name: X-ray photoelectron spectroscopic analysis device (XPS) ・Device type: Quantera SXM ・Device manufacturer: ULVAC-PHI ・Measurement conditions: X-ray source: Monochromatic AlKα rays 25W-15kV ・Vacuum Degree: 5.0×10 ^-8 Pa. Depth analysis is performed through argon ion etching. Data processing uses MultiPak manufactured by ULVAC-PHI.

Furthermore, the film density of the uppermost layer is preferably 98% or more, and the range of 98 to 100% is preferable from the viewpoint of salt water resistance and superhydrophilicity. In particular, from the viewpoint of further increasing the film density, it is preferable that the uppermost layer be formed by ion-assisted vapor deposition using the aforementioned IAD device 1 related to the present invention. In this case, it is more preferable to add heat of 300° C. or more.

With this configuration, the uppermost layer of the multilayer film has a high film density, so it is possible to provide a multilayer film that is excellent in salt water resistance on the surface and can maintain a low water contact angle over a long period of time in a high-temperature and high-humidity environment.

<Method of measuring film density> Here, in the present invention, "film density" means space filling density, and is defined as the value p represented by the following formula (1). In addition, the film density was measured before etching.

Space filling density p=(the volume of the solid part of the membrane)/(the total volume of the membrane)...(1) Here, the total volume of the membrane is the sum of the volume of the solid part of the membrane and the volume of the minute pore part of the membrane.

The film density can be measured by the following method.

(i) On a substrate made of white board glass BK7 (manufactured by SCHOTT) (φ (diameter) = 30 mm, t (thickness) = 2 mm), only a layer containing SiO ₂ and sodium is formed (this is considered to be related to the present invention). The uppermost layer) to measure the light reflectivity of the uppermost layer. On the other hand, (ii) using thin film calculation software (Essential Macleod) (SIGMA KOKI Co., Ltd.), the theoretical value of the light reflectance of the layer made of the same material as the uppermost layer is calculated. In addition, by comparing the theoretical value of the light reflectance calculated in (ii) with the light reflectance measured in (i), the film density of the uppermost layer is specified. The light reflectance can be measured by a reflectance measuring machine (USPM-RUIII) (manufactured by Olympus Co., Ltd.).

As shown in FIG. 3, a functional layer 105 mainly composed of a metal oxide having a photocatalyst function is arranged on the adjacent layer of the uppermost layer 106 to effectively perform the photocatalyst function. The use of a metal oxide having a photocatalyst effect and a photosensitive effect makes it possible to remove it as The surface organic matter of the main body of the dirt contributes to the maintenance of the super-hydrophilicity of the uppermost layer 106, so it is a preferred embodiment.

The metal oxide having a photocatalyst function is TiO _{2 which} has a high refractive index and can reduce the light reflectance of the dielectric multilayer film, which is preferable.

In addition, the dielectric multilayer film related to the present invention shown in FIG. 3 is a multilayer film formed by laminating a low refractive index layer, a high refractive index layer, and the uppermost layer 106 on a substrate 101, but it may also be on both sides of the substrate 101 Form the top layer. That is, although the uppermost layer is preferably on the side exposed to the external environment, the uppermost layer may be formed on the non-exposed side, for example, on the inner side opposite to the exposed side in order to prevent the influence of the internal environment. In addition, the dielectric multilayer film related to the present invention can also be applied to optical members such as anti-reflection members and heat shielding members in addition to lenses. In addition, the uppermost layer 106 is preferably etched using the aforementioned IAD device 1 related to the present invention to have pores having a specific shape.

[Method for manufacturing dielectric multilayer film] Preferably, the manufacturing method of the dielectric multilayer film related to the present invention includes a process of forming at least one low refractive index layer and at least one high refractive index layer on a substrate, and forming the high refractive index layer as the high refractive index layer to have a photocatalyst The procedure of a functional layer mainly composed of a functional metal oxide, a procedure of forming a hydrophilic layer containing a metal oxide having a hydrophilic function from the uppermost layer furthest from the aforementioned substrate, and a procedure of forming the aforementioned functional layer on the uppermost layer. Procedures for local exposure of pores on the surface.

In the process of forming the low refractive index layer and the high refractive index layer on the substrate, a thin film of metal oxide used in the high refractive index layer and the low refractive index layer is formed. Regarding the method of forming the high refractive index layer and the low refractive index layer, although the vacuum evaporation method, ion beam evaporation method, ion plating method, etc. are known in the evaporation system, the sputtering method, ion plating method, etc. are known in the sputtering system. The beam sputtering method, the magnetron sputtering method, etc., are particularly preferred in the present invention. The ion-assisted evaporation method (IAD method) or the sputtering method is preferred.

In the process of forming the aforementioned uppermost layer, a hydrophilic layer containing a metal oxide having a hydrophilic function is formed as the uppermost layer. Regarding the method of forming the uppermost layer, it is preferable to use the IAD method to form a high-density film. It is preferable that any one of the layers of the multilayer film of the present invention is formed by the IAD method, and it is more preferable that the entire layer is formed by the IAD method. The film formation through the IAD method can further improve the overall scratch resistance of the microstructure.

In the process of forming pores in the uppermost layer, pores that partially expose the surface of the functional layer are formed in the uppermost layer. The method for forming pores on the uppermost surface is shown below. As shown in FIG. 3, the uppermost layer 106 has a plurality of pores 30 for expressing the photocatalyst function in the adjacent functional layer 105 that becomes the high refractive index layer. The pores 30 are formed by etching through the aforementioned IAD device.

Hereinafter, the procedure of forming pores in the uppermost layer will be described. FIG. 4 is a flowchart of the procedure of forming pores in the uppermost layer, and FIG. 5 is a conceptual diagram explaining the procedure of forming a particle-like metal mask to form pores in the uppermost layer.

In FIG. 4, a low-refractive-index layer and a high-refractive-index layer as a multilayer film are alternately laminated on, for example, a glass substrate (glass substrate) (multilayer film formation procedure: step S11). Wherein, in step S11, layers other than the uppermost layer 106 and the functional layer 105 in the multilayer film are formed. That is, the low refractive index layer adjacent to the lower side of the functional layer 105 is formed. The multilayer film is formed using various vapor deposition methods, IAD methods, sputtering methods, and the like. In addition, depending on the configuration of the dielectric multilayer film 100, the formation of the multilayer film in step S11 may be omitted.

Next, in step 12, the functional layer 105 is formed, and then in step 13, the uppermost layer 106 is formed. The formation method is preferably the IAD method or the sputtering method for film formation, and it is more preferable to use the IAD method.

After the uppermost layer forming process, a metal mask 50 is formed on the surface of the uppermost layer 106 (mask forming process: step S14). As shown in FIG. 5(A), the metal mask 50 is formed in a particle shape on the surface of the uppermost layer 106. In this way, a nano-sized metal mask 50 can be formed on the uppermost layer 106. In addition, as shown in FIG. 5(D), the metal mask 50 may be formed into a vein shape. In addition, as shown in FIG. 5(E), the metal mask 50 may be formed into a porous shape.

The metal mask 50 is composed of a metal part 50a and an exposed part 50b. The film thickness of the metal mask 50 is in the range of 1 to 30 nm. Although it depends on the film forming conditions, when the metal mask 50 is formed so that the film thickness becomes 2 nm using, for example, a vapor deposition method, the metal mask 50 tends to be in the form of particles. Moreover, when the metal mask 50 is formed so that the film thickness may become 12-15 nm using a vapor deposition method, for example, the metal mask 50 will become a leaf vein shape easily. Furthermore, for example, when a sputtering method is used to form a film so that the film thickness becomes 10 nm, the metal mask 50 is likely to become porous. The metal film is formed into a thickness in the above-mentioned range, so that the optimal metal mask 50 in the form of particles, veins, or porous can be easily formed. The metal mask 50 is formed of, for example, Ag, Al, etc., and Ag is preferable from the viewpoint of controlling the shape of the pores.

Next, a plurality of pores 30 are formed in the uppermost layer 106 (pore formation procedure: step S15). As shown in FIG. 5(B), etching is performed by introducing a reactive gas into the IAD device (IAD ion source) of the present invention. The film formation of the above-mentioned multilayer film and the film formation of the metal mask 50 can also use the IAD device of the present invention. In the pore formation process, a reactive gas that reacts with the material of the uppermost layer 106, specifically, SiO ₂ is used to form a plurality of pores. _{In this case, the SiO 2 of} the uppermost layer 106 can be removed without causing damage to the metal mask 50. The reactive gas includes the aforementioned Freon-based gas or hydrogen fluoride-based gas. Thereby, a plurality of pores 30 that expose the surface of the functional layer 105 are formed in the uppermost layer 106. That is, the uppermost layer 106 corresponding to the exposed portion 50b of the metal mask 50 is etched to form the pores 30 and the SiO ₂ microstructure 31 which is the uppermost layer forming material, and the surface of the functional layer 105 is partially exposed.

After the pore formation process, as shown in FIG. 5(C), the metal mask 50 is removed (mask removal process: step S16). Specifically, the metal mask 50 is removed by wet etching using acetic acid or the like. In addition, in the IAD device of the present invention, the metal mask 50 can also be _{removed by dry etching using, for example, Ar and O 2} as an etching gas. When the metal mask 50 is etched using the aforementioned IAD device, a series of processes including formation of a multilayer film, formation of pores, and etching of the metal mask 50 can be performed in the same IAD device. Through the above procedure, a dielectric multilayer film 100 having a plurality of pores 30 in the uppermost layer 106 can be obtained. [Example]

Hereinafter, although the present invention will be specifically described with examples, the present invention is not limited to these. In addition, in the following examples, unless otherwise specified, the operation was performed at room temperature (25°C). In addition, as long as there is no special description, "%" and "parts" mean "mass %" and "parts by mass", respectively.

・Example 1 [Production of dielectric multilayer film (microstructure) 1] A glass substrate TAFD5G (manufactured by HOYA Co., Ltd.: refractive index 1.835) was used with _{a low refractive index of SiO 2} (manufactured by Merck Co., Ltd.) Layer, the high refractive index layer using OA600 (Material made by CANON OPTRON: _{a mixture of Ta 2} O ₅ , TiO, and Ti ₂ O ₅ ) until the layer numbers 1 to 3 in Table I. Use the IAD method under the following conditions to A predetermined film thickness is laminated. Next, as _{the functional layer (layer number 4) and the uppermost layer (layer number 5) using TiO 2} were deposited by the IAD method so that the sodium content became 5% by mass to form the uppermost layer. The results are described in Table I The number of layers 5 is a dielectric multilayer film before pores are formed.

<Film-forming conditions> (Conditions in the chamber) Heating temperature 370℃ Initial vacuum 1.33×10 ^-3 Pa (evaporation source of film-forming material) Electron gun

<Formation of the low refractive index layer, the high refractive index layer, the functional layer and the uppermost layer> The film-forming material of the low refractive index layer: SiO ₂ (Canon Optron's trade name SiO ₂ ) The above-mentioned substrate is placed on IAD vacuum deposition In the device, the first evaporation source was filled with the aforementioned film-forming material, and the film-forming rate was 3Å/sec to vaporize the substrate to form low-refractive-index layers (layer 1 and layer 3) with thicknesses of 31.7 nm and 34.6 nm on the substrate.

The IAD method uses an accelerating voltage of 1200V, an accelerating current of 1000mA, and a neutralizing current of 1500mA, using OPTORUN’s RF ion source "OIS One". The IAD introduction gas was performed under the conditions of O ₂ being 50 sccm, Ar gas being 10 sccm, and neutral gas Ar being 10 sccm.

The film-forming material of the high refractive index layer: Ta ₂ O ₅ (CANON OPTRON's trade name OA-600) The second evaporation source is filled with the film-forming material, and the film-forming speed is 3Å/sec. A high refractive index layer (layer 2) with a thickness of 30 nm was formed on the layer. The formation of the high refractive index layer was similarly performed by the IAD method under heating conditions of 370°C.

Functional layer film-forming material: TiO ₂ (Fuji Titanium Industry Co., Ltd. trade name TOP (Ti ₃ O ₅ )) The above-mentioned substrate is set in a vacuum evaporation device, and the third evaporation source is filled with the film-forming material to form The film speed was 3Å/sec for vapor deposition, and a functional layer (layer 4) with a thickness of 113 nm was formed on the low refractive index layer. The formation of this functional layer was similarly performed by the IAD method under heating conditions of 370°C.

The film-forming material of the top layer: SiO ₂ and Na ₂ O (trade name SiO ₂ -Na ₂ O of Toyojima Manufacturing Co., Ltd.) were mixed into particles with a mass ratio of 95:5.

The above-mentioned substrate is set in a vacuum evaporation device, the above-mentioned film-forming material is filled in the fourth evaporation source, and the film-forming speed is 3Å/sec. The uppermost layer (layer 5) with a thickness of 88nm is formed on the above-mentioned functional layer. . The formation of this functional layer was similarly performed by the IAD method under heating conditions of 370°C.

In addition, the layer thickness (film thickness) of each layer was measured by the following method.

(Measurement of layer thickness) The above-mentioned layer thickness is measured by the following method.

_{(1) TiO 2} and SiO ₂ are formed into a film with a thickness of 1/4λ (λ=550 nm) on a white board glass substrate in advance, and the spectral reflectance is measured.

_{(2) The respective layers are formed on the TiO 2} and SiO ₂ films formed in (1) under the above-mentioned film forming conditions, the spectral reflectance is measured, and the refractive index and layer thickness of the layer are calculated from the amount of change.

In addition, the composition analysis of the uppermost layer was measured using the following X-ray photoelectron spectrometer (XPS).

(XPS composition analysis) ・Device name: X-ray photoelectron spectroscopic analysis device (XPS) ・Device type: Quantera SXM ・Device manufacturer: ULVAC-PHI ・Measurement conditions: X-ray source: Monochromatic AlKα rays 25W-15kV ・Vacuum Degree: 5.0×10 ^-8 Pa. Depth analysis is performed through argon ion etching. Data processing uses MultiPak manufactured by ULVAC-PHI.

The light reflectance was measured with the UV-visible-near-infrared spectrophotometer V-670 manufactured by JASCO, and the light wavelength was 587.56 nm (d-ray).

(Measurement of refractive index under d-ray) The refractive index described in Table I is calculated by forming each layer of the multilayer film as a single layer and measuring the light reflectance under d-ray using a spectrophotometer U-4100 manufactured by HITACHI HIGH-TECHNOLOGIES. Using thin film calculation software (Essential Macleod) (SIGMA KOKI Co., Ltd.), the refractive index of the layer obtained by adjusting the refractive index in a manner that conforms to the measured light reflectance data is specified.

<Formation of pores in the uppermost layer> After forming the uppermost layer (layer 5), follow the pore formation method shown in Figures 3 and 4, with regard to the mask material, Ag, the deposition method of the mask, and the thickness of the metal mask. (E.g., Ag) 39nm, and on top of the metal mask Substance H4 (Merck, _{a mixture of Ta 2} O ₅ and La ₂ O ₅ ) 0.5nm, the shape of the mask, leaf veins, and the following etching conditions, Form pores. (Etching conditions) IAD device: NIS-175 (manufactured by Shincron) Chamber size: 2700L Etching gas: CHF ₃ Etching gas introduction amount: 100sccm Etching time: 10 minutes Accelerating voltage of IAD device: 500V Accelerating current of IAD device: 500mA Vacuum degree of the chamber: 7.0×10 ^-2 Pa gas introduction Ar gas introduction amount: 0sccm Distance from the grid of the plasma source of the IAD device to the etched layer: 40cm (the uppermost layer of the etched layer and the metal mask The selection ratio (etching rate of the etched layer/etching rate of the metal mask) is 2 times or more.)

<Peeling of the mask> After forming the pores, the aforementioned IAD device was used to irradiate O ₂ plasma to peel off the mask material Ag, and the dielectric multilayer film 1 was produced. The peeling was performed under peeling condition 1 described below. (Mask stripping condition 1) IAD device: NIS-175 (manufactured by Shincron) Chamber size: 2700L Etching gas: O ₂ , Ar Etching gas introduction amount: 50 sccm (O ₂ ), 10 sccm (Ar) Etching time: 10 Accelerating voltage of sub-IAD device: 1000V Accelerating current of IAD device: 1000mA Chamber vacuum: 3.0×10 ^-2 Pa Ar gas introduction amount: 10sccm

In addition, when peeling of the mask is performed under the following peeling condition 2, the Ag can be peeled off as in the case of performing the peeling condition 1 described above, and the dielectric multilayer film 1 can be produced. (Mask peeling condition 2) The mask material Ag was peeled off by immersing in the following chemicals for 1 minute. Medicine: Model SEA-5 (manufactured by HAYASHI PURE CHEMICAL IND.)

[Production of Dielectric Multilayer Film 2] In the formation of the pores in the uppermost layer in the production of the dielectric multilayer film 1, as the etching conditions, the distance from the grid of the plasma source of the IAD device to the etched layer is other than 100 cm, and the dielectric is similarly produced. Electrical multilayer film 2.

[Production of Dielectric Multilayer Film 3] In the production of the aforementioned dielectric multilayer film 1, in terms of detoxification means for detoxifying harmful gases, the inner wall of the chamber of the IAD device and the surface area of the members arranged in the chamber are made of polytetrafluoroethylene. Except for covering a vinyl sheet (product name: PTFE sheet, model number: 638-17-97-01, manufactured by Tokyo Glass Instruments Co., Ltd.), a dielectric multilayer film 3 was produced in the same manner.

[Production of Dielectric Multilayer Film 4] In the production of the dielectric multilayer film 3, in terms of the harmlessness means, in addition to the cover of the polytetrafluoroethylene sheet, a neutralizing material (product name: Except for calcium carbonate (manufactured by SHIRAISHI CALCIUM KAISHA), a dielectric multilayer film 4 was produced in the same manner.

[Production of Dielectric Multilayer Film 5] In the production of the dielectric multilayer film 4, the harmlessness means, in addition to the cover of the polytetrafluoroethylene sheet and the arrangement of the neutralizing material, the inner wall of the chamber and the members arranged in the chamber are The dielectric multilayer film 5 was produced in the same manner except that the neutralization material (product name: calcium carbonate, manufactured by SHIRAISHI CALCIUM KAISHA) was coated and formed.

After etching, using an HF gas concentration meter (GD-70D, manufactured by Riken Keiki Co., Ltd.), in the production of the dielectric multilayer film 5, it can be confirmed that the HF gas concentration in the etching chamber is 1.0 ppm or less, so open the chamber The door of the chamber to take out the sample.

[Production of Dielectric Multilayer Films 6-16] In the production of the aforementioned dielectric multilayer film 1, except that the etching conditions and detoxification means were changed as shown in Table II below, the dielectric multilayer films 6 to 16 were produced in the same manner.

[Evaluation] ＜Etching rate＞ The etching rate is an etching procedure (pore formation in the uppermost layer) during the production of each dielectric multilayer film, and the etching rate is calculated from the difference in film thickness before and after etching. The film thickness difference is calculated from the film thickness simulation of the transmission spectroscopic reflectance measuring machine. Spectroscopic reflectance measuring machine: USPM-RUIII manufactured by OLYMPUS (Evaluation criteria) ◎: 10nm/min or more ○: 3nm/min or more and less than 10nm/min △: 1nm/min or more and less than 3nm/min ×: less than 1nm/min

＜Damage to the mask＞ The damage of the mask was evaluated by the residual film thickness of the metal mask through etching when the pores in the uppermost layer were formed. The film thickness is evaluated as good when the film thickness state at the initial stage of etching can be maintained. The remaining amount of the mask is simulated by a spectroscopic reflectance measuring machine to calculate the film thickness. ○: The residual film thickness of the mask is 10nm or more △: The residual film thickness of the mask is 3nm or more and less than 10nm ×: The residual film thickness of the mask is less than 3nm

＜Processing state of pores of microstructure＞ The microstructure is evaluated through the processing state of the pores of the specific concave-convex shape constituting the uppermost layer. The processing state is to rank the uneven shapes processed by the pores based on the following criteria. (Evaluation criteria) ○: The root mean square height Sq of the pores of the microstructure is 10 nm or more △: The root mean square height Sq of the pores of the microstructure is 1 nm or more and less than 10 nm ×: The root mean square height Sq of the pores of the microstructure is less than 1 nm Regarding the height of the pores of the aforementioned microstructure, the root mean square height Sq was measured using the following atomic force microscope (AFM). Device: Dimension Icon made by BRUKER Detector: Silicon probe Model RTESPA-150 made by BRUKER Measurement mode: Peak Force Tapping Measurement site: the pores of the uppermost layer Analysis: The root mean square height Sq(nm) of the photographed image is measured using software made by BRUKER

<Concentration of HF gas in the chamber> After the pressure in the chamber after the mask is peeled off becomes 1.0×10 ^-5 Pa, the following HF gas detector is used to start measuring the concentration of HF gas. The measurement starts from the measurement. The concentration value after 2 minutes from the time. Device: Riken Keiki Co., Ltd. GD-70D

As shown in the above results, it can be seen that by using the manufacturing method of the microstructure of the present invention, compared with the manufacturing method of the comparative example, the etching rate can be improved and the damage to the mask can be reduced, and the desired microstructure can be manufactured. body. In addition, it can be seen that in the case of using detoxification means (dielectric multilayer film 3 to 5), compared with the case of not using detoxification means (dielectric multilayer film 1), the concentration of HF gas in the chamber Obviously low, effective for harmlessness.

1: IAD device 2: chamber 3: dome room 3a: retainer 3b: PTFE sheet 4: substrate 5: Evaporation source (film forming source) 7: IAD ion source (plasma source) 10: Monitor system (control department) 11: detector 91: Gas Supply Department 92: Gas discharge part 93: Pest Control 30: pores 31: Microstructure other than pores 50: metal mask 50a: Metal Department 50b: Exposure Department 100: Dielectric multilayer film (microstructure) 101: substrate 102, 104: Low refractive index layer 103: High refractive index layer 105: functional layer 106: top layer

[Figure 1] A schematic diagram of an example of an IAD device. [Fig. 2] (a) is a schematic diagram of a dome chamber covering a polytetrafluoroethylene sheet, (b) is a cross-sectional view of (a), and (c) is a schematic diagram of a dome chamber before covering the polytetrafluoroethylene sheet. [Fig. 3] A cross-sectional view showing an example of the structure of a dielectric multilayer film. [Fig. 4] A flowchart of the procedure for forming pores in the uppermost layer. [Fig. 5] A conceptual diagram explaining the procedure of forming a particle-like metal mask to form pores in the uppermost layer.

1: IAD device

2: chamber

3: dome room

3a: retainer

4: substrate

5: Evaporation source (film forming source)

6: Evaporated substance

7: IAD ion source (plasma source)

8: ion beam

10: Monitor system (control department)

11: detector

91: Gas Supply Department

91a: Port

92: Gas discharge part

92a: Port

93: Pest Control

Claims (19)

A method of manufacturing a microstructure by etching, Using an IAD (Ion Assisted Deposition) device, a reactive gas is introduced into the plasma source in the chamber of the IAD device to perform etching. The method for manufacturing a microstructure according to claim 1, wherein, as the reactive gas, a gas containing a Freon-based gas or a hydrogen fluoride gas is introduced. The method for manufacturing a microstructure according to claim 1 or 2, wherein the IAD device is provided with a means for detoxifying the harmful gas from the reactive gas. The method for manufacturing a microstructure according to claim 3, wherein, as a means of detoxification, 10% or more of the surface area of the inner wall of the chamber and the member arranged in the chamber is used to make the harmful gas harmless Covered with modified materials or polytetrafluoroethylene (registered trademark), The method for manufacturing a microstructure according to claim 3, wherein, as the detoxification means, a neutralizing material that neutralizes the harmful gas is provided in the chamber. The method of manufacturing a microstructure according to claim 3, wherein, as a means of detoxification, the inner wall of the chamber and the members arranged in the chamber are formed by coating or vapor deposition to neutralize the harmful Neutralizing material for gas. The method of manufacturing a microstructure according to claim 6, wherein, before the atmosphere of the chamber is released, the inner wall of the chamber and the members arranged in the chamber are vapor-deposited to form the neutralizing material. Such as the manufacturing method of the microstructure of claim 6 or 7, wherein: The aforementioned neutralizing material can be peeled off, It includes a procedure of peeling off the neutralizing material attached to the microstructure. The method for manufacturing a microstructure according to any one of claims 1 to 8, wherein: Install a detector that can detect hydrogen fluoride gas or Freon-based gas in the aforementioned chamber, Before the chamber is released, the concentration of the hydrogen fluoride gas or the freon-based gas is detected by the detector, and after the concentration of the hydrogen fluoride gas or the freon-based gas in the chamber becomes below a predetermined reference value, the chamber is opened The door of the room. The method for manufacturing a microstructure according to any one of claims 1 to 9, wherein: In the aforementioned IAD device, a film forming source formed by electron beam or resistance heating is installed in the same chamber as the aforementioned chamber, The IAD device has a procedure for forming a film using the aforementioned film forming source and a procedure for performing the aforementioned etching using the aforementioned plasma source. The method for manufacturing a microstructure according to any one of claims 1 to 10, wherein: The aforementioned microstructure has two or more multilayer films, At least one of the aforementioned multilayer films should contain silicon dioxide. The method for manufacturing a microstructure according to any one of claims 1 to 11, wherein, in the aforementioned etching, the selection ratio of the metal mask to the etched layer (etching rate of the etched layer/etching rate of the metal mask ) To double or more, adjust the distance from the grid of the plasma source of the IAD device to the layer to be etched, or the acceleration voltage and pressurized current of the IAD device, or the amount of etching gas introduced, or the degree of vacuum, Or the amount of argon introduced. The method for manufacturing a microstructure according to any one of claims 1 to 12, wherein, during the etching, the distance from the grid of the plasma source of the IAD device to the layer to be etched is 40 cm or more. The method of manufacturing a microstructure according to any one of claims 1 to 13, wherein the setting value of the IAD device during the etching is such that the acceleration voltage is in the range of 300 to 1200V and the acceleration current is in the range of 300 to 1200mA Within range. The method for manufacturing a microstructure according to any one of claims 1 to 14, wherein when the volume of the chamber is 2700L, the introduction amount of the Freon-based gas or hydrogen fluoride gas in the chamber during the etching is 20 sccm the above. The method for manufacturing a microstructure according to any one of claims 1 to 15, wherein when the volume of the chamber is 2700L, the degree of vacuum during the etching is 5.0×10 ^-3 to 5.0×10 ^-1 Pa In the range. The method for manufacturing a microstructure according to any one of claims 1 to 16, wherein when the volume of the chamber is 2700 L, the amount of argon gas introduced into the chamber during the etching is 20 sccm or less. The method for manufacturing a microstructure according to any one of claims 1 to 17, wherein the gas exhaust mechanism in the chamber is exhausted with a gas exhaust volume of 250L/min or less in the chamber until the gas exhaust in the chamber The pressure becomes 3.0×10 ⁴ Pa. A device for manufacturing a microstructure, which is used by the user in the method for manufacturing a microstructure according to any one of claims 1-18, A reactive gas is introduced into the plasma source in the chamber of the IAD device to perform etching.

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