JPH09314716A - Optical part, manufacture thereof, and manufacturing apparatus - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain desired spectroscopic properties without generating a color center by making the first layer film counted from the substrate side contain one kind selected from among SiO2 , BeO, MgO, and MgF2 and forming a film of a thickness not exceeding a specified value. SOLUTION: A lens SA as an optical part is made, for example, by forming a film 101 (undercoat film) not exceeding 30nm in thickness and a reflection preventive film 102 on a substrate 100 containing fluorite as a main component. By forming the undercoat film 101 on the substrate 100, damage of the substrate can be alleviated in the formation of the film 102 on it, and adhesion to the substrate can be improved. Moreover, by the existence of the film 101, a film which is made by a film making apparatus which emits electrons or ions like spattering can be used as a film to be formed on it. At least one kind selected from among SiO2 , BeO, MgO, and MgF2 is used as the film 101 and its thickness is made less than or equal to 30nm.

Description

Detailed Description of the Invention

[0001]

TECHNICAL FIELD The present invention relates to ultraviolet light, especially Kr.
The present invention relates to an optical component that constitutes an optical system such as an F excimer laser beam and an ArF excimer laser beam, a manufacturing method thereof, and a manufacturing apparatus.

In particular, the present invention uses a vapor deposition method in which a coating film (thin film) such as an antireflection film is appropriately set on a substrate containing fluorite as a main component without deteriorating the optical characteristics of the substrate. However, it is suitable for manufacturing an optical component that can easily obtain predetermined optical characteristics.

[0003]

2. Description of the Related Art Conventionally, as an optical device, for example, in a projection exposure apparatus for manufacturing a semiconductor, light in the ultraviolet region has been used.

For example, as a laser having an oscillation wavelength of 250 nm or less, KrF, KrCl, ArF, ArCl, Xe
_{There are 2} , Kr ₂ , Ar ₂ and F ₂ lasers. As one of optical components such as a reflecting mirror, a lens, a beam splitter, and a window member that constitute an optical system used in this projection exposure apparatus, fluorite having a good transmittance in the ultraviolet region is often used.

On the other hand, for example, JP-A-7-261002, JP-A-7-218701, and JP-A-8-220.
Japanese Laid-Open Patent Publication No. 304 discloses a structure of an antireflection film suitable for an optical component. Of these, an optical component for light of a KrF excimer laser is provided with an aluminum oxide film having a high reflectance in contact with the surface of a quartz substrate, and a silicon oxide film having a low refractive index is provided thereon, and a multilayer in which this combination is sequentially repeated is provided. Membranes were used. Then, an attempt has been made to produce a base body of fluorite (calcium fluoride) as an optical component for light of shorter wavelength, for example, ArF excimer laser light.

However, in an optical component in which the above-mentioned multilayer film is formed on a fluorite substrate by sputtering or the like, a color center is generated and it is difficult to obtain desired spectral characteristics.

Further, in JP-A-4-228560 and JP-A-5-188203, a film thickness of 5 is formed on a fluorite substrate.
A 2.0 nm silicon oxide film is formed, and an aluminum oxide film and a silicon oxide film are sequentially laminated thereon, and a 62 nm-thickness silicon oxide film is formed on a fluorite substrate, and magnesium oxide and silicon oxide are formed thereon. It is described that the films are sequentially laminated.

However, color centers are generated also in these optical parts, and it is difficult to obtain desired spectral characteristics.

[0009]

When an antireflection film is formed by using fluorite as a substrate, the conventional sputter film forming method or ion beam film forming method is that the fluorite is directly exposed to electrons, ions or plasma containing electrons. Therefore, there is a problem that so-called color center is generated inside the fluorite and a predetermined spectral characteristic cannot be obtained.

According to the present invention, a substrate containing fluorite as a main component is used, and when a predetermined film is formed on the substrate, by appropriately setting the material and film thickness of the film adjacent to the fluorite, An object of the present invention is to provide an optical component having desired spectral characteristics without generation of color centers.

The present invention also prevents the occurrence of color centers on the fluorite substrate without impairing the optical characteristics of the fluorite substrate by appropriately setting the film formation method on the substrate containing fluorite as the main component. It is an object of the present invention to provide an optical component manufacturing method and an optical component manufacturing apparatus by which an optical component having a desired spectral characteristic can be easily obtained.

Further, in the optical component in which a plurality of films are laminated on the fluoride substrate of the present invention, the film in contact with the substrate contains at least one of silicon oxide, beryllium oxide, magnesium oxide and magnesium fluoride. It is an object of the present invention to provide an exposure apparatus that is a film and has a film thickness of 30 nm or less so that a good optical component can be obtained and a high-resolution pattern can be obtained.

[0013]

The method of manufacturing an optical component according to the present invention comprises: (1-1) forming at least one layer on a substrate containing fluorite as a main component in a film forming apparatus for emitting electrons or ions. In the method of manufacturing an optical component, which comprises forming a film to manufacture an optical component,
Counting from the substrate side, SiO ₂ , BeO, Mg was added to the first layer film.
Contains at least one of O and MgF ₂ and has a film thickness of 30 n
It is characterized by having a step of forming a film of m or less.

In particular, (1-1-1) the thickness of the first layer film is 5 nm or more.

(1-1-2) The first layer film is a film containing SiO ₂ and the method has a step of forming a film containing Al ₂ O ₃ on the second layer film.

(1-1-3) The third and subsequent layers have a step of alternately forming a film containing SiO ₂ and a film containing Al ₂ O ₃ .

(1-1-4) The steps of forming the _third , fifth and seventh layer films with a film containing SiO ₂ and the steps of forming the fourth and sixth layer films with a film containing Al ₂ O _3. In addition, the formed laminated film has an antireflection function.

(1-1-5) The laminated film has an antireflection function at a wavelength of 193 nm.

(1-1-6) The film-forming apparatus that emits electrons or ions uses a vacuum deposition method in which a film material is melted by an electron beam.

(1-1-7) The film forming apparatus that emits electrons or ions uses a sputtering film forming method in which a film material is sputtered. And so on.

(1-2) In a film-forming apparatus that emits electrons or ions, a film is formed on a substrate containing fluorite as a main component to manufacture an optical part. It is characterized in that it comprises a step of previously forming a film containing at least one of SiO ₂ , BeO, MgO, and MgF ₂ on the first layer film by counting from the substrate side by a film forming apparatus which does not emit.

In particular, (1-2-1) the film-forming apparatus that emits electrons or ions,
Utilizing a vacuum evaporation method in which the film material is melted by an electron beam.

(1-2-2) The film forming apparatus that emits electrons or ions uses a sputtering film forming method in which a film material is sputtered.

(1-2-3) The film forming apparatus that does not emit electrons or ions uses a vacuum evaporation method in which a film material is melted by resistance heating. And so on.

(1-3) In a method of manufacturing an optical component, which is a film-forming apparatus for emitting electrons or ions, wherein films are formed at a plurality of locations on a substrate containing fluorite as a main component to manufacture an optical component
The first layer film is counted from the substrate side with a film forming apparatus that does not emit electrons or ions at the plurality of locations, and the first layer film is formed of SiO 2.
_The method is characterized by having a step of forming in advance a film containing at least one of ₂ , BeO, MgO, and MgF ₂ .

The optical component manufacturing apparatus of the present invention comprises (2-1) an optical film forming apparatus that emits electrons or ions and forms films at a plurality of locations on a substrate containing fluorite as a main component. In an optical component manufacturing apparatus for manufacturing a component, when a film is formed at predetermined locations of the plurality of locations, the electrons are prevented from entering the plurality of locations except the predetermined locations. Alternatively, it is characterized by having a shielding means for shielding ions.

In particular, (2-1-1) the film forming apparatus that emits electrons or ions,
Utilizing a vacuum evaporation method in which the film material is melted by an electron beam.

(2-1-2) The film forming apparatus that emits electrons or ions uses a sputtering film forming method in which a film material is sputtered. And so on.

The optical component of the present invention is (3-1) an optical component in which a plurality of films are laminated on a fluoride substrate, and the film in contact with the substrate is silicon oxide, beryllium oxide, magnesium oxide, or fluoride. A film containing at least one of magnesium and having a film thickness of 3
It is characterized by being 0 nm or less.

In particular, (3-1-1) the fluoride is calcium fluoride.

(3-1-2) The plurality of films are aluminum oxide or silicon oxide.

(3-1-3) The film thickness of the film in contact with the substrate is 5 n
m or more. And so on.

(3-2) In an optical component used in a laser optical system having a wavelength of 250 nm or less in which a plurality of films are laminated on a fluoride substrate, the film in contact with the substrate is silicon oxide, beryllium oxide, magnesium oxide, The film is characterized by being a film containing at least one of magnesium fluoride and having a film thickness of 30 nm or less.

In particular, (3-2-1) the fluoride is calcium fluoride.

(3-2-2) The plurality of films are aluminum oxide or silicon oxide.

(3-2-3) The film thickness of the film in contact with the substrate is 5 n
m or more.

(3-2-4) The laser optical system is an optical system for ArF excimer laser. And so on.

The exposure apparatus of the present invention comprises (4-1) an illumination light source and a stage on which an object to be exposed is placed,
In an exposure apparatus having an illumination optical system and / or a projection optical system having a plurality of optical components in which a plurality of films are laminated, a film in contact with a substrate of the optical components is silicon oxide, beryllium oxide, magnesium oxide, magnesium fluoride. It is characterized in that it is a film containing at least one of the above and has a film thickness of 30 nm or less.

In particular, (4-1-1) the fluoride is calcium fluoride.

(4-1-2) The plurality of films should be aluminum oxide or silicon oxide.

(4-1-3) The film thickness of the film in contact with the substrate is 5 n
m or more.

(4-1-4) The illumination light source is an excimer laser light source. And so on.

[0043]

FIG. 1 is a schematic sectional view of Embodiment 1 of an optical component (optical member) of the present invention. In the figure, SA is a lens as an optical component. Reference numeral 100 is a calcium fluoride substrate containing fluorite as a main component, 101
Is a film having a film thickness of 30 nm or less (hereinafter referred to as an undercoat film), and 102 is an antireflection film.

In SB, the antireflection film 102 is a film 1 having a low refractive index.
A lens made of 02L and a film 102H having a high refractive index is shown. SC indicates a lens having an antireflection film 102 in which four films 102L and 102H are alternately laminated.

SD represents a film 102H in contact with the undercoat film 101 in the structure of the lens SC, and a film 1 having an intermediate refractive index.
This is a lens having a configuration replaced with 02M. SE is a lens having an antireflection film 102 in which six low refractive index films 102L and high refractive index films 102H are alternately laminated. SF is a reflection enhancing film 1 in which a film 104H having a high refractive index is provided on the atmosphere side.
04 is a reflecting mirror.

According to the optical component of the present invention, by providing the undercoat film which is a film in contact with the surface of the fluoride substrate, the fluoride substrate is damaged when the films 102 and 104 formed thereon are formed. And the adhesion between the fluoride substrate 100 and the films 102 and 104 can be improved.

Further, due to the presence of the undercoat film 101, a film formed by a film-forming device that emits electrons or ions such as sputtering can be used as a film formed thereon. Since such a film forming method can increase the deposition rate, it has an effect of reducing the cost of the optical component.

As the undercoat film used in the optical component of the present invention, silicon oxide, beryllium oxide, magnesium oxide, and magnesium fluoride are preferable, and the film thickness thereof is preferably as thin as 30 nm or less. More preferably, the film thickness is 5 nm or more and 30 nm or less.

FIG. 2 is a schematic view of the essential portions of Embodiment 1 of a film forming apparatus suitable as an optical component manufacturing apparatus of the present invention. In the figure, 200 is a reaction chamber and 201 is an exhaust port. 20
Reference numeral 3 denotes a resistance heating evaporation source, in which a raw material to be film-formed is put in a crucible therein, and resistance heating is performed to evaporate the raw material.

Reference numeral 204 denotes an electron beam evaporation source, which evaporates the raw material using an electron beam. Reference numeral 205 denotes a substrate holder, which holds the fluoride substrate S. A film thickness monitor 206 can optically measure the film thickness during film formation.

In the film forming apparatus according to the present invention, the raw material of the undercoat film is put into the crucible of the resistance heating evaporation source 203, and resistance heating is performed to deposit silicon oxide, beryllium oxide or magnesium oxide on the surface of the upper substrate S. A film of magnesium fluoride is formed.

At this time, the value detected by the film thickness monitor is 50n.
The film formation is stopped at a point not exceeding m, and the thickness of the undercoat film is set to 50 nm or less. After that, thin films are laminated by electron beam evaporation.

In this embodiment, the film adjacent to the fluorite substrate is made of S.
By forming a film containing at least one of iO ₂ , BeO, MgO and MgF ₂ , generation of color centers on the fluorite substrate is suppressed.

In particular, in this embodiment, the optical characteristics are largely changed by selecting the SiO ₂ or MgF ₂ film having a relatively small difference in refractive index from the fluorite substrate as the film to be brought close to the fluorite substrate. It is possible to deposit a film without using it.

FIG. 3 is a schematic diagram of the optical member 21 (Sample A) of Embodiment 2 in which a MgF ₂ film and a Ta ₂ O ₅ film are deposited on a fluorite substrate by using the film forming apparatus shown in FIG. FIG. 4 is a schematic diagram of the optical member 31 (Sample B) when only the Ta ₂ O ₅ film is deposited on the fluorite substrate for reference.

In FIG. 3, the MgF ₂ film is deposited by heating MgF ₂ on a fluorite substrate using a resistance heating evaporation source RH, and the Ta ₂ O ₅ film is an electron beam evaporation source from which electrons are emitted. Ta ₂ O ₅ was heated and deposited with EB. Then, in these two types of optical members 21 and 31, the presence or absence of a color center and the adhesion between the substrate and the film were examined. Table 1 shows the results.

The presence or absence of a color center in fluorite was determined by the presence or absence of absorptance near a wavelength of 500 nm, and the adhesiveness was determined by whether or not the film was strongly wiped and peeled off. As is clear from Table 1, the optical member of FIG. 2 formed by the method according to the present invention is superior to the optical member of FIG. 3 in both optical properties and mechanical properties.

[0058]

[Table 1] In the present invention, it has been confirmed that the same effect can be obtained by using a SiO ₂ , BeO or MgO film instead of the MgF ₂ film formed directly on the fluorite substrate.

FIG. 5 shows a SiO ₂ film and Al ₂ O ₃ on a fluorite substrate.
FIG. 6 is a schematic diagram of an optical member 41 (Sample C) of Embodiment 3 according to the present invention in which films are sequentially deposited by a sputtering method.
For reference, is a schematic diagram of a conventional optical member 51 (Sample D) in which an Al ₂ O ₃ film is directly deposited on a fluorite substrate. In these two types of optical members 41 and 51, the wavelength 1
The absorptance at 93 nm, the presence / absence of a color center, and the adhesion between the substrate and the film were examined. The results are shown in Table 2.

The absorptance at a wavelength of 193 nm is calculated by subtracting the sum of the transmittance and the reflectance from 100% by spectroscopic measurement.
Judgment was made based on the presence / absence of absorptance in the vicinity of nm, and adhesion was judged based on whether or not the film was strongly wiped and the film peeled off.

[0061]

[Table 2] FIG. 5 shows a film formed by the method according to the present invention as apparent from Table 2.
The optical member 41 is superior to the optical member 51 of FIG. 6 in both optical properties and mechanical properties.

FIGS. 7 and 8 show Si on the fluorite substrate in FIG.
O ₂ film 10 nm, the reflection characteristic diagram and the transmission characteristic diagram of a third embodiment of the present invention when an Al ₂ O ₃ film was 270nm deposited, and the Al ₂ O ₃ film in the fluorite substrate 6 270
FIG. 3 is a reflection characteristic diagram and a transmission characteristic diagram when a nm deposition is performed.

As is clear from FIGS. 7 and 8, the optical characteristics of the two are substantially the same. For this reason, Si
If the thickness of the O ₂ film is about this, the SiO ₂ film has optical characteristics.
The existence of the film can be almost ignored.

In this embodiment, even if the SiO ₂ film has this thickness, the absorption coefficient at the wavelength of 193 nm, the color center,
The adhesion between the substrate and the film was the same as in the second embodiment.

Next, an optical member according to the fourth embodiment of the present invention will be described. In Embodiment 4, wavelength 1 of ArF laser
In order to form a film having an antireflection property at 93 nm, a SiO ₂ film, an Al ₂ O ₃ film and an S film are sequentially formed on a fluorite substrate.
iO ₂ film, Al ₂ O ₃ film, SiO ₂ film, Al ₂ O ₃ film, S
The iO ₂ film was deposited with the refractive index and optical thickness of Table 3.

FIG. 9 is a reflection characteristic diagram at this time. still,
The refractive index in Table 3 shows the refractive index at a wavelength of 193 nm, and the optical film thickness is shown by (refractive index of material × mechanical film thickness).

As is apparent from FIG. 9, in this embodiment, an antireflection film having a good antireflection property of 0.1% or less at a wavelength of 193 nm is deposited on the fluorite substrate. Further, this antireflection film did not generate a color center of fluorite and had good adhesion.

[0068]

[Table 3] FIG. 10 is a correlation diagram between the film thickness of the first layer and the band where the reflectance of this antireflection film satisfies 0.1% or less in the present embodiment. From FIG. 10, when the film thickness of the first layer is set to 30 nm or more, the band satisfying the low reflectance of 0.1% or less becomes narrow to 10 nm or less, and it becomes difficult to have a practical antireflection property. Therefore, it is desired that the thickness of the first layer be 30 nm or less. On the other hand, when the thickness of the first layer is 5 nm, the occurrence of color centers of fluorite is not observed, but when it is less than this, the occurrence of color centers is observed. Therefore, the thickness of the first layer should be 5 nm or more. Is desired. Therefore, in this embodiment, the thickness of the first layer is set to 5 nm or more and 30 nm or less.

As described above, in the present embodiment, the SiO ₂ film as the first layer film is preliminarily formed on the fluorite substrate so as to have a thin film thickness of 5 nm or more and 30 nm or less, whereby the film peeling or the fluorite substrate is formed. The color center is suppressed from occurring.

Further, according to this embodiment, since the refractive index of this optical member can be almost the same as that of the fluorite substrate, the optical characteristics of the film further deposited on this optical member can be changed. There are features such as not having to do so.

FIG. 11 is a schematic view of a main part of the film forming apparatus of the present invention. The figure shows a case where a predetermined film is formed on a fluorite substrate by sputtering. In the figure, 1 is a vacuum chamber. The vacuum chamber 1 has an exhaust system 2 for exhausting the inside thereof.
And a gas introduction system 12 for introducing various gases into the inside,
A shutter drive system 17 for driving the shutter plate 16 provided therein is attached.
Inside the vacuum chamber 1, a substrate holder 5 having a cathode electrode 3 and a substrate (fluorite substrate) 6 at a position facing the cathode electrode 3 and having a light-shielding member for covering a surface other than the film formation surface of the substrate 6 is provided. It is arranged.

For the cathode electrode 3, aluminum (Al) target 4a and SiO ₂ target 4b, which are target materials, are used.
The target holder 4 is attached so as to be rotatable around the rotation shaft 4d. Target 4
Magnets 4c are provided on a and 4b. The substrate holder 5 has a mechanism capable of heating the attached substrate 6. The shutter plate 16 is arranged below the substrate 6 and adjusts the timing (time) for forming a thin film (SiO ₂ or alumina thin film) on the substrate 6.

A high frequency power source 8 is connected to the cathode electrode 3 via a matching box 7 for matching the discharge impedance. Further, one terminal of a switch 10 is connected to the cathode electrode 3 through a low pass filter 9 that cuts off high frequency components from a high frequency power source 8. The DC power supply 11 is connected to the other terminal of the switch 10.

Oxygen (O ₂ ) which is a reaction gas and Ar which is a sputtering gas are connected to the gas introduction system 12 through mass flows 13 and 14 for adjusting the supply of these gases. A mass flow 14 for adjusting the supply of the argon gas Ar and a control system 15 for controlling the switch 10 are connected.

In this embodiment, first, the SiO ₂ target 4b is set to face the substrate 6.

Next, after the inside of the vacuum chamber 1 is sufficiently evacuated by the exhaust system 2, 100 sccm of oxygen gas (O ₂ ) is first introduced through the mass flow 13 of the gas introduction system 12. 400 W of high frequency power from the high frequency power supply 8 matching box 7
The plasma 18 is generated by supplying the cathode 18 to the cathode electrode 3 and the SiO ₂ target 4b. At this time, the high frequency power is supplied up to the set value while performing the matching adjustment so that the high frequency reflected wave becomes the minimum value. Target 4b
After the pre-sputtering process for the purpose of cleaning the surface and stabilizing the discharge, the shutter plate 16 is opened by the driving force of the shutter drive system 17, and the thin film formation on the substrate 6 is started.

When the film formation of SiO _{2 on} the substrate 6 is completed, the shutter plate 16 is closed. Then, the next target holder 4 is rotated to set the Al target 4a so as to face the substrate 6. Then, in the same manner as the film formation of SiO ₂ , while introducing oxygen gas (O ₂ ) at 150 sccm, high frequency power of 200 W and DC power of 200 W are applied to the Al target 4a.
Then, the Al ₂ O ₃ film is deposited on the substrate 6.

In this embodiment, the fluorite substrate 6 provided with the thin film by the above method was taken out from the vacuum container 1 and the occurrence of color centers was examined. As a result, no color center was observed by covering the back surface of the fluorite substrate 6.

In this embodiment, when depositing a film on a plurality of locations (both sides) on a fluorite substrate by a sputtering method, an ion beam method, or the like, first, SiO _{2 is} deposited on all deposition surfaces by vacuum evaporation by resistance heating shown in FIG. By pre-depositing the film, it is possible to prevent the fluorite substrate from being directly exposed to plasma or the like (electrons, ions) and damaged, thereby suppressing the generation of color centers.

According to the present invention, as described above, when fluorite is used as a substrate and a predetermined film is formed thereon, the material and thickness of the film adjacent to the fluorite are appropriately set, and By properly setting the film formation method on fluorite, the color center of the fluorite substrate can be prevented from occurring without impairing the optical properties of the fluorite substrate, and optical components with desired spectral characteristics can be easily obtained. The optical component manufacturing method and the optical component manufacturing apparatus can be achieved.

Next, an exposure apparatus using the optical component of the present invention will be described.

Examples of the exposure apparatus in this embodiment include a reduction projection exposure apparatus using a lens optical system and a lens type unit magnification projection exposure apparatus.

Particularly, in order to expose the entire surface of the wafer, one small section (field) of the wafer is exposed, the wafer is moved by one step, and the adjacent one field is exposed.
A stepper employing a step-and-repeat method is desirable. Of course, it is also suitably used for a mirror scan type exposure apparatus.

FIG. 12 is a schematic diagram of the structure of the first embodiment of the exposure apparatus of the present invention. In the figure, 121 is an illumination light source unit, 22 is an exposure mechanism unit, and 121 and 22 are configured separately and independently.

That is, the two are physically separated. 23
Is an illumination light source, which is a large light source with high output such as an excimer laser. 24 is a mirror, 25 is a concave lens, 26 is a convex lens, 25 and 26 have a role as a beam expander, and expand the beam diameter of the laser to the size of an optical integrator.

Reference numeral 27 is a mirror, and 28 is an optical integrator for uniformly illuminating the reticle. The illumination light source unit 121 includes the laser 23 to the optical integrator 28. Reference numeral 29 is a mirror, and 30 is a condenser lens for collimating the light flux emitted from the optical integrator 28.

Reference numeral 131 is a reticle on which a circuit pattern is drawn, 131a is a reticle holder for sucking and holding the reticle, and 32 is a projection optical system for projecting the reticle pattern.
Reference numeral 33 is a wafer on which the pattern of the reticle 131 is printed on the projection lens 32. Reference numeral 34 denotes an XY stage, which holds the wafer 33 by suction and moves in the XY directions when printing is performed by step and repeat. 35
Is a surface plate of the exposure apparatus.

The exposure mechanism section 22 is composed of a mirror 29, which is a part of an illumination optical system, and a surface plate 35. 36
Is an alignment means used for TTL alignment. In addition to this, the normal exposure apparatus includes an autofocus mechanism, a wafer transfer mechanism, and the like, which are also included in the exposure mechanism unit 22.

FIG. 13 shows an example of an optical component used in the exposure apparatus of the present invention, which is a lens used in the projection optical system of the exposure apparatus shown in FIG. This lens assembly is configured by combining 11 lenses L1 to L11 without adhering them to each other.

[0090]

As described above, according to the present invention, (a) when a substrate containing fluorite as a main component is used and a predetermined film is formed on the substrate, the material of the film adjacent to the fluorite and By appropriately setting the film thickness and the like, it is possible to achieve an optical component having desired spectral characteristics without the occurrence of color centers.

(B) By appropriately setting the film formation method on the substrate containing fluorite as a main component, it is possible to prevent the occurrence of color centers on the fluorite substrate without impairing the optical characteristics of the fluorite substrate, It is possible to achieve an optical component manufacturing method and an optical component manufacturing apparatus by which an optical component having the spectral characteristic of can be easily obtained.

(C) In an optical component in which a plurality of films are laminated on a fluoride base, the film in contact with the base contains at least one of silicon oxide, beryllium oxide, magnesium oxide, and magnesium fluoride. When the film thickness is 30 nm or less, a good optical component can be obtained, and an exposure apparatus that can obtain a high-resolution pattern can be achieved.

[Brief description of drawings]

FIG. 1 is a schematic sectional view of Embodiment 1 of an optical component of the present invention.

FIG. 2 is a schematic view of a main part of Embodiment 1 of a film forming apparatus according to the present invention.

FIG. 3 is a second embodiment of an optical member provided with a film according to the present invention.
Main part sectional view of

FIG. 4 is a sectional view of an essential part of an optical member provided with a conventional film.

FIG. 5 is a third embodiment of an optical member provided with a film according to the present invention.
Main part sectional view of

FIG. 6 is a sectional view of an essential part of an optical member having a conventional film.

FIG. 7 is a color light reflectance characteristic of the optical member shown in FIGS.

FIG. 8 is a color light transmittance characteristic of the optical member shown in FIGS.

FIG. 9 is a color light reflectance characteristic of the optical member according to the fourth embodiment of the present invention.

FIG. 10 is an explanatory view of the film thickness of the first layer film according to the fifth embodiment of the present invention.

FIG. 11 is a schematic view of the essential portions of Embodiment 2 of the film forming apparatus according to the present invention.

FIG. 12 is a schematic view of a main part of an exposure apparatus of the present invention.

FIG. 13 is an explanatory diagram of an optical system using the optical component of the present invention.

[Explanation of symbols]

1 Vacuum Tank 2 Exhaust System 3 Cathode Electrode 4 Target Holder 4a Al Target 4b SiO ₂ Target 4c Magnet 4d Rotating Shaft 5 Substrate Holder 6 Substrate 7 Matching Box 8 High Frequency Power Supply 9 Low Pass Filter 10 Switch 11 DC Power Supply 12 Gas Introducing System 22 Exposure Mechanism Section SA, SB, SC, SD, SE, SF Optical parts 100 Fluorite substrate 101 Undercoat film 200 Reaction chamber 201 Exhaust port 203 Resistance heating evaporation source 121 Illumination light source section 131 Reticle 23 Illumination light source 32 Projection optical system 33 Wafer 204 Electronics Beam evaporation source 205 Substrate holder 206 Film thickness monitor

Front page continued (72) Inventor Minoru Otani 3-30-2 Shimomaruko, Ota-ku, Tokyo Canon Inc. (72) Hidehiro Kanazawa 3-30-2 Shimomaruko, Ota-ku, Tokyo Canon Inc. Within

Claims (30)

[Claims] 1. A method of manufacturing an optical component, wherein a film of at least one layer is formed on a substrate containing fluorite as a main component by a film-forming device that emits electrons or ions to manufacture an optical component. Counting from the side, the first layer film has SiO ₂ , Be
A method of manufacturing an optical component, comprising the step of forming a film containing at least one of O, MgO, and MgF ₂ and having a film thickness of 30 nm or less. 2. The method of manufacturing an optical component according to claim 1, wherein the film thickness of the first layer film is 5 nm or more. 3. The optical device according to claim 1, wherein the first layer film is a film containing SiO ₂ and there is a step of forming a film containing Al ₂ O ₃ on the second layer film. Manufacturing method of parts. 4. A film containing SiO ₂ and Al after the third layer film.
_The method for manufacturing an optical component according to claim ₃ , further comprising the step of alternately forming films containing ₂ O ₃ . 5. The method comprises the steps of forming the _third , fifth and seventh layer films with a film containing SiO ₂ and forming the fourth and sixth layer films with a film containing Al ₂ O _3. The method for manufacturing an optical component according to claim 3, wherein the laminated film has an antireflection function. 6. The method of manufacturing an optical component according to claim 5, wherein the laminated film has an antireflection function at a wavelength of 193 nm. 7. The film forming apparatus that emits electrons or ions uses a vacuum deposition method in which a film material is melted by an electron beam, according to any one of claims 1 to 5.
A method of manufacturing an optical component according to the item. 8. The optical component according to claim 1, wherein the film forming apparatus for emitting electrons or ions uses a sputtering film forming method for sputtering a film material. Manufacturing method. 9. A method for producing an optical component, which comprises forming a film on a substrate containing fluorite as a main component in a film-forming apparatus for emitting an electron or ion to produce an optical component. A method of manufacturing an optical component, comprising the step of previously forming a film containing at least one of SiO ₂ , BeO, MgO and MgF ₂ on the first layer film by counting from the substrate side by a film device. 10. The method of manufacturing an optical component according to claim 9, wherein the film forming apparatus that emits electrons or ions uses a vacuum evaporation method in which a film material is melted by an electron beam. 11. The method of manufacturing an optical component according to claim 9, wherein the film-forming apparatus that emits electrons or ions uses a sputtering film-forming method of sputtering a film material. 12. The film deposition apparatus that does not emit electrons or ions uses a vacuum deposition method in which a film material is melted by resistance heating, according to any one of claims 9 to 11. Optical component manufacturing method. 13. A method of manufacturing an optical component, wherein a film is formed at a plurality of locations on a substrate containing fluorite as a main component in a film-forming apparatus that emits electrons or ions. , by a film forming apparatus which does not emit electrons, or ions, SiO ₂ in the first layer film counting from the substrate side,
A method of manufacturing an optical component, comprising a step of previously forming a film containing at least one of BeO, MgO, and MgF ₂ . 14. An optical component manufacturing apparatus for manufacturing an optical component using a film-forming apparatus that emits electrons or ions and forms films at a plurality of locations on a substrate containing fluorite as a main component. When a film is formed at a predetermined place of a place, it has a shield means for shielding the electrons or ions so that the electrons or ions do not enter the plurality of places except the predetermined place. Optical component manufacturing equipment. 15. The apparatus for manufacturing an optical component according to claim 14, wherein the film forming apparatus that emits electrons or ions uses a vacuum evaporation method in which a film material is melted by an electron beam. 16. The apparatus for manufacturing an optical component according to claim 14, wherein the film forming apparatus for emitting electrons or ions uses a sputtering film forming method for sputtering a film material. 17. An optical component in which a plurality of films are laminated on a fluoride base, and the film in contact with the base is a film containing at least one of silicon oxide, beryllium oxide, magnesium oxide and magnesium fluoride. An optical component having a thickness of 30 nm or less. 18. The optical component according to claim 17, wherein the fluoride is calcium fluoride. 19. The optical component according to claim 17, wherein the plurality of films are aluminum oxide or silicon oxide. 20. The optical component according to claim 17, wherein the film in contact with the substrate has a film thickness of 5 nm or more. 21. In an optical component used in a laser optical system having a wavelength of 250 nm or less, in which a plurality of films are laminated on a fluoride substrate, the film in contact with the substrate is silicon oxide.
An optical component comprising a film containing at least one of beryllium oxide, magnesium oxide, and magnesium fluoride, and having a film thickness of 30 nm or less. 22. The optical component according to claim 21, wherein the fluoride is calcium fluoride. 23. The optical component according to claim 21, wherein the plurality of films are aluminum oxide or silicon oxide. 24. The optical component according to claim 21, wherein the film in contact with the substrate has a film thickness of 5 nm or more. 25. The laser optical system is an optical system for an ArF excimer laser.
Optical components. 26. An exposure apparatus comprising an illumination light source and a stage on which an object to be exposed is mounted, and comprising a plurality of optical components having a plurality of films laminated in an illumination optical system and / or a projection optical system, An exposure apparatus, wherein the film in contact with the substrate is a film containing at least one of silicon oxide, beryllium oxide, magnesium oxide, and magnesium fluoride, and has a film thickness of 30 nm or less. 27. The exposure apparatus according to claim 26, wherein the fluoride is calcium fluoride. 28. The exposure apparatus according to claim 26, wherein the plurality of films are aluminum oxide or silicon oxide. 29. The exposure apparatus according to claim 26, wherein the film in contact with the substrate has a film thickness of 5 nm or more. 30. The exposure apparatus according to claim 26, wherein the illumination light source is an excimer laser light source.