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Mgf2 Optical Thin Film Including Amorphous Silicon Oxide Binder, Optical Element Provided With the Same, and Method for Producing Mgf2 Optical Thin Film

a technology of optical thin film and amorphous silicon oxide, which is applied in the field of single-layer or multi-layer optical thin film, can solve the problems of insufficient refractive index of the film, insufficient environmental resistance, and insufficient film strength and adhesive force with respect to the base material, and achieve excellent environmental resistance (durability), improve mechanical strength of the film and adhesive force between the film and the base material, and improve environmental resistance.

Inactive Publication Date: 2008-01-03
NIKON CORP
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  • Summary
  • Abstract
  • Description
  • Claims
  • Application Information

AI Technical Summary

Benefits of technology

[0028] According to a first aspect of the present invention, there is provided an MgF2 optical thin film, comprising MgF2 minute particles; and an amorphous silicon oxide-based binder which exists between the MgF2 minute particles.
[0029] According to the present invention, the MgF2 minute particles, which are excellent in the environment resistance (durability), are used as the main constitutive substance of the film, and the MgF2 minute particles are bonded or connected to one another by the amorphous silicon oxide-based binder. Therefore, the strong bonding or connection can be provided between the MgF2 minute particles and between the MgF2 minute particles and the base material. The mechanical strength of the film and the adhesive force between the film and the base material are improved. That is, it is considered that the MgF2 optical thin film has such a structure that the voids (gaps) are present between the MgF2 minute particles, and the voids are filled with the amorphous silicon oxide-based binder. SiO2, which is somewhat inferior in the environment resistance, can be used as the amorphous silicon oxide-based binder. However, it is enough to use a small amount of the binder as compared with the MgF2 minute particles. Therefore, it is possible to sufficiently secure the environment resistance as the entire thin film.
[0030] In the MgF2 optical thin film of the present invention, the MgF2 minute particles may be connected by the amorphous silicon oxide-based binder, and the amorphous silicon oxide-based binder, disposed on surfaces of MgF2 minute particles, among the MgF2 minute particles, which exist at an outermost portion of the MgF2 optical thin film, may have a thickness which is not more than 5% of a wavelength of light to be radiated. Further, in the MgF2 optical thin film of the present invention, the amorphous silicon oxide-based binder, which exists between adjacent MgF2 minute particles, among the MgF2 minute particles, may have a thickness which is smaller than a particle diameter of the MgF2 minute particles. When the thickness of the binder is adjusted as described above, it is possible to lower the refractive index. In particular, when the refractive index of the outermost layer of the optical thin film is sufficiently lowered, the antireflection film is obtained, which has the low reflectance in a wide wavelength band or zone and in a wide angle band or zone.
[0031] In the present invention, it is unnecessary that the amorphous silicon oxide-based binder exists in all of the spaces between the MgF2 minute particles. It is enough that the amorphous silicon oxide-based binder exists in a part of the spaces between the MgF2 minute particles to maintain the thin film of the MgF2 minute particles. It is unnecessary that the amorphous silicon oxide-based binder completely exists in the spaces between the MgF2 minute particles and the base material. It is enough that the amorphous silicon oxide-based binder exists in a part of the spaces between the MgF2 minute particles and the base material, and thus the amorphous silicon oxide-based binder reinforces the bonding between the MgF2 minute particles and the base material.
[0032] In the MgF2 optical thin film of the present invention, the MgF2 minute particles may have an average particle diameter of 1 nm to 100 nm (not less than 1 nm and not more than 100 nm). In this case, owing to the high crystallization property of the MgF2 minute particles, the adhesion or agglutination between the MgF2 minute particles can be suppressed to secure the voids between the MgF2 minute particles so that the MgF2 optical thin film having a porous structure may be successfully obtained. When the porous structure is provided, it is possible to obtain the MgF2 optical thin film having the lower refractive index. The porous structure may have a percentage of voids or porosity of not more than 50%, in view of the retention of the film strength.
[0033] In the MgF2 optical thin film of the present invention, the amorphous silicon oxide-based binder may be formed of amorphous silica. In this case, the refractive index of amorphous silica is low, i.e., 1.42. Therefore, it is possible to secure the low refractive index of the entire thin film even when the composite is formed together with the MgF2 minute particles.

Problems solved by technology

However, in the case of the film using MgF2 as described in International Publication No. 02 / 18982A1, the film strength and the adhesive force with respect to the base material are insufficient, although the refractive index of the optical thin film can be lowered to be not more than 1.30.
In the case of the films in which the film strength and the adhesive force with respect to the base material can be secured as described in Japanese Patent No. 3272111, Japanese Patent Application Laid-open No. 11-6902, Japanese Patent Application Laid-open No. 7-48527, Japanese Patent Application Laid-open No. 8-122501 and Japanese Patent Application Laid-open No. 2000-169133, the problem arises such that the refractive index of the film cannot be lowered sufficiently, and the environment resistance is insufficient.
There has been the problem such that it is not possible to obtain any optical thin film which is capable of sufficiently decreasing the refractive index and of securing the mechanical strength of the film, the adhesive force with respect to the base material, and the environment resistance.
However, in the case of the wet process, it is difficult to perform the multilayered coating.

Method used

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  • Mgf2 Optical Thin Film Including Amorphous Silicon Oxide Binder, Optical Element Provided With the Same, and Method for Producing Mgf2 Optical Thin Film
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  • Mgf2 Optical Thin Film Including Amorphous Silicon Oxide Binder, Optical Element Provided With the Same, and Method for Producing Mgf2 Optical Thin Film

Examples

Experimental program
Comparison scheme
Effect test

first embodiment

[0084]FIG. 1 shows an optical element in which an MgF2 optical thin film (MgF2—SiO2 film) of the first embodiment is formed. The optical element 100 includes a base material 10 and the MgF2 optical thin film 11 which is stacked on a flat optical surface of the base material 10. The base material 10 is formed of, for example, glass, plastic or the like having a refractive index of 1.4 to 2.1, and may be a plate member or a lens. The optical surface of the base material 10 may be formed to have a curved surface form.

[0085] The optical thin film 11 is an antireflection film which is stacked on at least one optical surface of the base material 10 onto which the light is radiated. In this embodiment, the optical thin film 11 is a singlelayered MgF2 antireflection film.

[0086] The optical thin film 11 includes MgF2 minute particles 12 and an amorphous silicon oxide-based binder 13. The connection is made by the amorphous silicon oxide-based binder 13 between a large number of the MgF2 mi...

examples 1 to 5

[0168] The hydrofluoric acid methanol solution was mixed with the magnesium acetate methanol solution so that the MgF2 concentration was 1%, and that the hydrofluoric acid / magnesium acetate ratio was 1.95 to prepare an MgF2 sol solution. Subsequently, the sol solution was subjected to the high temperature high pressure treatment at 140° C. for 24 hours. The average particle diameter of MgF2 minute particles contained in the treated MgF2 sol solution was measured by the electron microscopic observation, which was 20 nm. The sol solution was concentrated by using the rotary evaporator, followed by being diluted with 1-propanol to substitute 67% of the methanol solvent. The MgF2 sol solution was allowed to have an MgF2 concentration of 2.5%, with which a silica glass substrate having a thickness of 3 mm was spin-coated at 2,000 rpm to form a porous MgF2 film.

[0169] The substrate was dried at 70° C. for 1 hour, and then the temperature was returned to room temperature. An undiluted sol...

examples 6 to 8

[0172] MgF2—SiO2 films were formed by the double coating method in the same manner as in Examples 1 to 5 except that MgF2 sol solutions were prepared by mixing the hydrofluoric acid methanol solution with the magnesium acetate methanol solution so that the MgF2 concentration was 1%, and the ratio of hydrofluoric acid / magnesium acetate was 1.98, 1.99, and 2.0. Characteristics of the obtained films were measured. Results are shown in Table 1.

[0173] When the results are compared with each other with respect to Example 1, the following fact is appreciated. That is, there is such a tendency that as the ratio of hydrofluoric acid / magnesium acetate is higher, the refractive index of the MgF2—SiO2 film becomes lower. In order to make the refractive index of the MgF2—SiO2 film as low as possible, it is appreciated that the ratio of hydrofluoric acid / magnesium acetate is preferably allowed to approach 2.0. However, if the ratio of hydrofluoric acid / magnesium acetate exceeds 2.0, then the gel...

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Abstract

An MgF2 optical thin film is formed on an optical surface of a base material. The MgF2 optical thin film includes MgF2 particles and an amorphous silicon oxide-based binder which exists on the surfaces of the MgF2 particles and between the MgF2 particles. Owing to this amorphous silicon oxide-based binder, the optical thin film can have high mechanical strength and high adhesion to the base material, while having excellent environment resistance and a lower refractive index.

Description

TECHNICAL FIELD [0001] The present invention relates to a singlelayered or multilayered optical thin film formed of MgF2, a method for producing the same, an optical element having the MgF2 optical thin film, and an optical system for optical instruments such as cameras, microscopes, binoculars, and exposure apparatuses which is provided with the optical element. BACKGROUND ART [0002] Surfaces of individual lenses, which construct an optical system such as a camera lens and an objective lens of a microscope, are coated with an antireflection film in order to reduce the reflection. In general, the optical thin film such as the antireflection film is produced by the dry method (dry process), in which the vacuum vapor deposition method, the sputtering method, the CVD method (Chemical Vapor Deposition) or the like is used. [0003] In order to obtain a high performance optical thin film having a low reflectance in a wide wavelength band or a wide angle band, it is known that a multilayere...

Claims

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Application Information

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IPC IPC(8): G02B1/11C01F5/28C03C17/22C03C17/25B82Y20/00B82Y30/00B82Y40/00C03C17/34G02B1/113G02B1/115G02B1/14
CPCC03C17/007C03C2217/45C03C2217/475C03C2218/113G02B1/105Y10T428/258G02B1/113G02B2207/107G02B2207/109Y10T428/2495G02B1/111G02B1/14C01F5/28C03C17/22C03C17/25G02B1/11G02B1/116G02B1/118
Inventor ISHIZAWA, HITOSHINIISAKA, SHUNSUKEMURATA, TSUYOSHI
Owner NIKON CORP
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