Patent Application
20220064051
The present invention relates to an optical glass, an optical element composed of the optical glass, an optical system, an interchangeable lens, and an optical device. The present invention claims priority to Japanese Patent Application No. 2017-181028, filed on Sep. 21, 2017, the contents of which are incorporated by reference herein in its entirety in designated states where the incorporation of documents by reference is approved.
An optical glass is used in various optical elements and optical devices. For example, Patent Literature 1 discloses a halide glass used for an ultraviolet region to an infrared region. In order to improve a degree of freedom in design of an optical system used for an optical device, development of an optical glass having a high refractive index has been demanded. However, when a composition is adjusted so as to obtain a high refractive index of the optical glass, vitrification tends to be difficult.
PTL 1: JP H07-081973 A
A first aspect according to the present invention is an optical glass including, in terms of mol % of cations, a total amount of La3+, Y3+, and Gd3+ components falling within a range of from 5% to 65% and a total amount of Zr4+, Hf4+, and Ta5+ components falling within a range of from 5% to 65%, and a relationship expressed in Expression (1) given below is satisfied;
(La3++Y3++Gd3+)×(Zr4++Hf4++Ta5+)≥400(%)2 (1).
A second aspect according to the present invention is an optical element composed of the optical glass according to the first aspect.
A third aspect according to the present invention is an optical system using the optical element according to the second aspect.
A fourth aspect according to the present invention is an interchangeable lens including the optical system according to the third aspect.
A fifth aspect according to the present invention is an optical device including the optical element according to the second aspect.
Hereinafter, description is made on an embodiment of the present invention (hereinafter, referred to as the “present embodiment”). The present embodiment described below is an example for describing the present invention, and is not intended to limit the present invention to the contents described below.
Description is made below on a component composition, physical properties, and the like of an optical glass according to the present embodiment. Note that, in the present specification, a content amount of each of all the components is expressed by mol % in terms of cations unless otherwise stated.
An optical glass according to the present embodiment is an optical glass including, in terms of mol % of cations a total amount of La3+, Y3+, and Gd3+ components falling within a range of from 5% to 65% and a total amount of Zr4+, Hf4+, and Ta5+ components falling within a range of from 5% to 65%, and a relationship expressed in Expression (1) given below is satisfied.
(La3++Y3++Gd3+)×(Zr4++Hf4++Ta5+)≥400 (%)2 (1)
A mode of each cation is not particularly limited, and a cation is contained in the optical glass in a mode of an oxide described later, for example. The optical glass according to the present embodiment is a novel optical glass that enables vitrification even when a content amount of cations forming a network former oxide such as SiO2 and B2O3 and the like is low. Further, an optical glass having a high refractive index and low wavelength dependency of a refractive index can be obtained. In general, regarding the optical glass, it is difficult to obtain both a high refractive index and low dispersibility (wavelength dependency of a refractive index) in a compatible manner, and there is a problem in that those factors tend to have a trade-off relationship. In view of this, it is also difficult to achieve an optical glass having a high refractive index and low dispersibility. In this respect, the optical glass according to the present embodiment contains the component composition described above, and hence such properties can be provided.
La3+, Y3+, and Gd3+ being rear earth components are components capable of increasing a refractive index without losing low dispersibility, and are respectively contained as La2O3, Y2O3, and Gd2O3 in terms of an oxide-converted composition, for example. When a total amount of La3+, Y3+, and Gd3+(La3++Y3++Gd3+) is small, the effect described above is not sufficient. When the total amount exceeds 65%, the glass is more likely to be devitrificated. In view of this, La3++Y3++Gd3+ falls within a range of from 5% to 65%, more preferably from 30% to 60%, further more preferably from 40% to 55%.
La3+ is a component contained as La2O3 in terms of an oxide-converted composition, for example. La3+ has an effect of increasing a refractive index without losing low dispersibility, and is capable of maintaining glass-devitrification resistance. In view of this, the content amount preferably falls within a range of from 0% to 65%, more preferably from 20% to 60%, further more preferably from 30% to 55%.
Y3+ is a component contained as Y2O3 in terms of an oxide-converted composition, for example. Y3+ is a component capable of increasing a refractive index without losing low dispersibility, and particularly is capable of further improving devitrification resistance by coexisting with La3+ in the glass. In view of this, the content amount preferably falls within a range of from 0% to 10%, more preferably from 0% to 7%, further more preferably from 0% to 5%. Further, both La+ and Y3+are preferably contained.
Gd3+ is a component contained as Gd2O3 in terms of an oxide-converted composition, for example. Gd3+ is a component capable of increasing a refractive index without losing low dispersibility, and particularly is capable of further improving glass-devitrification resistance by coexisting with La3+ in the glass. In view of this, the content amount preferably falls within a range of from 0% to 20%, more preferably from 0% to 15%, further more preferably from 0% to 10%. Further, both La+ and Gd+ are preferably contained.
Similarly to the rear earth components described above, Zr4+, Hf4+, Ta5+ being transition metal components are components having an effect of increasing a refractive index of the glass without losing low dispersibility greatly, and has an effect of further increasing a refractive index more than the rear earth components. Zr4+, Hf4+, and Ta5+ are respectively contained as ZrO2, HfO2, and Ta2O5 in terms of an oxide-converted composition, for example. When a total amount of Zr4+, Hf4+, and Ta5+ (Zr4++Hf4++Ta5+) is small, the effect described above is not sufficient. When the total amount of those components exceeds 60%, the glass is more likely to be devitrificated. In view of this, (Zr4++Hf4++Ta5+) falls within a range of from 5% to 65%, preferably from 20% to 60%, more preferably from 30% to 60%.
Zr4+ is a component contained as ZrO2 in terms of an oxide-converted composition, for example. Zr4+ exerts an effect of increasing a refractive index of the glass while maintaining low dispersibility. In view of a refractive index and glass-devitrification resistance, the content amount preferably falls within a range of from 0% to 15%, more preferably from 0% to 10%, further more preferably from 0% to 8%.
Hf4+ is a component contained as HfO2 in terms of an oxide-converted composition, for example. Hf4+ exerts an effect of increasing a refractive index of the glass while maintaining low dispersibility. In view of a refractive index and glass-devitrification resistance, the content amount preferably falls within a range of from 0% to 10%, more preferably from 0% to 7%, further more preferably from 0% to 5%.
Ta5+ is a component contained as Ta2O5 in terms of an oxide-converted composition, for example. Ta5+ has an effect of increasing a refractive index of the glass while maintaining low dispersibility and an effect of improving glass-devitrification resistance. In view of this, the content amount preferably falls within a range of from 5% to 65%, more preferably from 10% to 50%, further more preferably from 15% to 40%.
The optical glass according to the present embodiment satisfies a relationship expressed in Expression (1) given below. In addition to the rare earth oxides described above, specific transition metal components such as Zr4+, Hf4+, and Ta5+ are combined to satisfy a relationship expressed in Expression (1). With this, a high refractive index and low dispersibility can be achieved in a compatible manner at a high level.
(La3++Y3++Gd+)×(Zr4++Hf4++Ta5+)≥400(%)2 (1)
Further, Expression (1) preferably satisfies Expression (1a) given below, more preferably satisfies Expression (1b) given below. When such condition is satisfied, both a high refractive index and low dispersibility can be achieved in a compatible manner at a higher level as compared to a case where an optical glass contains either one of rear earth components and transition metal components.
(La3++Y3++Gd+)×(Zr4++Hf4++Ta5+)≥800(%)2 (1a)
(La3++Y3++Gd3+)×(Zr4++Hf4++Ta5+)≥1200(%)2 (1b)
The upper limit value of Expression (1) is not particularly limited. In view of maintaining glass-devitrification resistance, the upper limit value is preferably 2,400(%)2 or less (see Expression ((1c) given below), more preferably 2,000(%)2 or less (see Expression (1d) given below).
2400(%)2≥(La3++Y3++Gd3+)×(Zr4++Hf4++Ta5+)≥400(%)2 (1c)
2000(%)2≥(La3++Y3++Gd3+)×(Zr4++Hf4++Ta5+)≥400(%)2 (1d)
Further, the optical glass according to the present embodiment preferably contains at least one component selected from a group consisting of Ga3+, Al3+, Si4+, B3+, Mg2+, Ca2+, Sr2+, Ba2+, Ti4+, Nb5+, and W6+. In place of one of those, two or more components may be used. A mode of each cation is not particularly limited, and a cation may be contained in the optical glass in a mode of an oxide described later, for example. When such component is further contained, glass formability at the time of manufacturing the optical glass can be improved.
Ga3+ is a component contained as Ga2O3 in terms of an oxide-converted composition, for example. Ga3+ can further improve glass stability while maintaining a high refractive index and low dispersibility. In view of such effects and the content amounts of rear earth components and transition metal components, the content amount preferably falls within a range of from 0% to 60%, more preferably exceeds 0% up to 30% (exceeding 0% and equal to or less than 30%), further more preferably exceeds 0% up to 15% (exceeding 0% and equal to or less than 15%).
Al3+ is a component contained as Al203 in terms of an oxide-converted composition, for example. Al3+ can improve glass stability and ultraviolet transmittance. In view of such effects and the refractive index, the content amount preferably falls within a range of from 0% to 200, more preferably from 0% to 100, further preferably from 0% to 50, still further preferably 00.
Si4+ is a component contained as SiO2 in terms of an oxide-converted composition, for example, and is a component forming a network former oxide. Due to Si+, glass formability can be more likely to be improved. In view of such effects and the refractive index, the content amount preferably falls within a range of from 0% to 300, more preferably from 0% to 200, further more preferably from 0% to 100, further more preferably 00. The optical glass according to the present embodiment enables vitrification even when a content amount of Si4+ forming a network former oxide is reduced, and excellent physical properties can be provided.
B3+is a component contained as B2O3 in terms of an oxide-converted composition, for example, and is a component forming a network former oxide. Due to B3+, glass formability can be more likely to be improved. Meanwhile, B3+ is a component with high volatility. Thus, when B3+ is excessively introduced, a glass composition is changed, which may degrade striae quality in some cases. Further, when B3+ is excessively introduced, a refractive index may be reduced in some cases. In view of this, the content amount preferably falls within a range of from 0% to 10%, more preferably from 0% to 5%, further more preferably from 0% to 3%, further more preferably 0%. The optical glass according to the present embodiment enables vitrification even when a content amount of B3+ forming a network former oxide is reduced, and excellent physical properties can be provided.
Ti4+ and Nb5+ are components contained as TiO2 and Nb2O5, respectively, in terms of an oxide-converted composition, for example. Ti4+ and Nb5+ can further improve a refractive index of the glass. In view of such effects and dispersibility, the content amounts each preferably fall within a range of from 0% to 20%, more preferably from 0% to 10%, further more preferably from 0% to 5%.
W6+ is a component contained as WO3 in terms of an oxide-converted composition, for example. W6+ is capable of increasing a refractive index. In view of such effects and dispersibility, the content amount preferably falls within a range of from 0% to 10%, more preferably from 0% to 5%, further more preferably from 0%.
An alkali earth metal oxide R2+ (R referrers to one or more selected from Mg, Ca, Sr, and Ba) is a component contained as RO in terms of an oxide-converted composition, for example. R2+ has an effect similar to that of the rear earth components described above. However, when R2+ is excessively introduced, high refractivity may be degraded in some cases. In view of this, the total amount of the R2+ component preferably falls within a range of from 0% to 10%, more preferably from 0% to 5%, further more preferably from 0% to 3%.
In view of further improving physical properties of the optical glass according to the present embodiment, a suitable combination of the components described above includes, for example, Ga3+ component falling within a range of from 0% to 60%, Al3+ component falling within a range of from 0% to 20%, Si4+ component falling within a range of from 0% to 30%, and B3+ component falling within a range of from 0% to 10%. Further, a Ti4+ component falling within a range of from 0% to 20%, a Nb5+ component falling within a range of from 0% to 20%; a W6+ component falling within a range of from 0% to 10%, and an R2+ (R referrers to one or more selected from a group consisting of Mg, Ca, Sr, and Ba) component falling within a range of from 0% to 10% are exemplified.
Further, the optical glass according to the present embodiment enables vitrification even when a component forming a network former oxide is not contained, and excellent physical properties can be provided. In view of this, the optical glass according to the present embodiment can be an optical glass that does not contain a B3+ component and a Si4+ component substantially, and can be an optical glass containing a total amount of the two components being 0%.
The optical glass according to the present embodiment may further contain other freely selected components as long as the components cause no particular obstruction to achieve the object.
Next, description is made on physical property value of the optical glass according to the present embodiment.
The optical glass according to the present embodiment can be used suitably as a glass regarding a high refractive index region. In view of this, a refractive index (nd) with respect to a d-line (wavelength: 587.562 nm) of the optical glass according to the present embodiment preferably falls within a range of from 1.93 to 2.15, more preferably from 1.95 to 2.12, further more preferably from 1.98 to 2.10.
The optical glass according to the present embodiment is glass having low dispersibility (a high abbe number (vd)). The abbe number (vd) of the optical glass according to the present embodiment preferably falls within a range of from 25 to 40, more preferably from 27 to 37, further more preferably from 29 to 35.
The optical glass according to the present embodiment preferably has Δnd, which is expressed by Δnd=nd-0.01023vd+2.2988, of 0.02 or more, more preferably 0.04 or more, further more preferably 0.06 or more.
Here, Δnd indicates a deviation amount from a reference line connecting two points obtained by plotting an abbe number on a horizontal axis and a refractive index on a vertical axis with respect to two glass types of “J-LASF08” and “J-LASFH16” (both are glass type names produced by HIKARI GLASS Co., Ltd.). Δnd indicates a relationship between low dispersibility (vd) and a high refractive index (nd) of the optical glass according to the present embodiment, and also indicates that the optical glass according to the present embodiment is capable of achieving low dispersibility and a high refractive index in a compatible manner at a high level. When La3+, Y3+, Gd3+, Zr4+, Hf4+, and Ta5+ are introduced, Δnd tends to be high. When Si4+, B3+, Al3+, Ti4+, Nb5+, and W6+ are introduced, Δnd tends to be low.
The optical glass according to the present embodiment is suitable for an optical element such as a lens and the like included in an optical device such as a camera, a microscope, and binocular glasses and the like, and an optical element such as a lens and the like included in an interchangeable camera lens. Among optical devices, a multi-photon microscope is especially suitable.
A pulse laser device 101 emits ultrashort pulse light having, for example, a near infrared wavelength (approximately 1,000 nm) and a pulse width of a femtosecond unit (for example, 100 femtoseconds). In general, ultrashort pulse light immediately after being emitted from the pulse laser device 101 is linearly polarized light that is polarized in a predetermined direction.
A pulse division device 102 divides the ultrashort pulse light, increases a repetition frequency of the ultrashort pulse light, and emits the ultrashort pulse light.
A beam adjustment unit 103 has a function of adjusting a beam diameter of the ultrashort pulse light, which enters from the pulse division device 102, to a pupil diameter of the objective lens 106, a function of adjusting convergence and divergence angles of the ultrashort pulse light in order to correct chromatic aberration (a focus difference) on an axis of a wavelength of multi-photon excitation light emitted from a sample S and the wavelength of the ultrashort pulse light, a pre-chirp function (group velocity dispersion compensation function) providing inverse group velocity dispersion to the ultrashort pulse light in order to correct the pulse width of the ultrashort pulse light, which is increased due to group velocity dispersion at the time of passing through the optical system, and the like.
The ultrashort pulse light emitted from the pulse laser device 101 have a repetition frequency increased by the pulse division device 102, and is subjected to the above-mentioned adjustments by the beam adjustment unit 103. Furthermore, the ultrashort pulse light emitted from the beam adjustment unit 103 is reflected on a dichroic mirror 104 in a direction toward a dichroic mirror 105, passes through the dichroic mirror 105, is converged by the objective lens 106, and is radiated to the sample S. At this time, an observation surface of the sample S may be scanned with the ultrashort pulse light through use of scanning means (not illustrated).
For example, when the sample S is subjected to fluorescence imaging, a fluorescent pigment by which the sample S is dyed is subjected to multi-photon excitation in an irradiated region with the ultrashort pulse light and the vicinity thereof on the sample S, and fluorescence having a wavelength shorter than an infrared wavelength of the ultrashort pulse light (hereinafter, also referred to “observation light”) is emitted.
The observation light emitted from the sample S in a direction toward the objective lens 106 is collimated by the objective lens 106, and is reflected on the dichroic mirror 105 or passes through the dichroic mirror 105 depending on the wavelength.
The observation light reflected on the dichroic mirror 105 enters a fluorescence detection unit 107. For example, the fluorescence detection unit 107 is formed of a barrier filter, a photo multiplier tube (PMT), or the like, receives the observation light reflected on the dichroic mirror 105, and outputs an electronic signal depending on an amount of the light. Further, the fluorescence detection unit 107 detects the observation light over the observation surface of the sample S, in conformity with the ultrashort pulse light scanning on the observation surface of the sample S.
Meanwhile, the observation light passing through the dichroic mirror 105 is de-scanned by scanning means (not illustrated), passes through the dichroic mirror 104, is converged by the condensing lens 108, passes through a pinhole 109 provided at a position substantially conjugate to a focal position of the objective lens 106, passes through the image forming lens 110, and enters a fluorescence detection unit 111. For example, the fluorescence detection unit 111 is formed of a barrier filter, a PMT, or the like, receives the observation light forming an image on a light formed by the image forming lens 110 on the reception surface of the fluorescence detection unit 111, and outputs an electronic signal depending on an amount of the light. Further, the fluorescence detection unit 111 detects the observation light over the observation surface of the sample S, in conformity with the ultrashort pulse light scanning on the observation surface of the sample S.
Note that all the observation light emitted from the sample S in a direction toward the objective lens 106 may be detected by the fluorescence detection unit 111 by excluding the dichroic mirror 105 from the optical path.
Further, the observation light emitted from the sample S in a direction opposite to the objective lens 106 is reflected on a dichroic mirror 112, and enters a fluorescence detection unit 113. The fluorescence detection unit 113 is formed of, for example, a barrier filter, a PMT, or the like, receives the observation light reflected on the dichroic mirror 112, and outputs an electronic signal depending on an amount of the light. Further, the fluorescence detection unit 113 detects the observation light over the observation surface of the sample S, in conformity with the ultrashort pulse light scanning on the observation surface of the sample S.
The electronic signals output from the fluorescence detection units 107, 111, and 113 are input to, for example, a computer (not illustrated). The computer is capable of generating an observation image, displaying the generated observation image, storing data on the observation image, based on the input electronic signals.
The optical element using the optical glass according to the present embodiment can be suitably used in an imaging device.
The imaging device 2 is a so-called digital single lens reflex camera, and a lens barrel 202 is removably attached to a lens mount (not illustrated) of a camera body 201. Further, an image is formed with light, which passes through the lens 203 of the lens barrel 202, on a sensor chip (solid-state imaging elements) 204 of a multi-chip module 206 arranged on a back surface side of the camera body 201. The sensor chip 204 is a so-called a bare chip such as a CMOS image sensor and the like. For example, the multi-chip module 206 is a module of a chip-on-glass (COG) type in which the sensor chip 204 is mounted on a glass substrate 205 as a bare chip.
Note that the optical device is not limited to such imaging device, and includes a wide variety of devices such as a projector and the like. The optical element is not limited to the lens, and includes a wide variety of elements such as a prism and the like.
The optical glass according to the present embodiment can be manufactured through use of, for example, a levitation furnace. Examples of the levitation furnace includes an electrostatic type, an electromagnetic type, a sonic type, a magnetic type, a gas-jet type and the like, and are not particularly limited. However, for levitation melting of oxides, a gas-jet type levitation furnace is preferably used. Now, the manufacturing method through use of a gas-jet type levitation furnace is described as one example.
In the gas-jet type levitation furnace 3, the material M is in a state of levitation due to gas sent to the pedestal (see
It has been difficult to vitrificate the composition of the optical glass according to the present embodiment. For example, in the related art, in a case where an optical glass is manufactured through use of a container such as a crucible and the like that is normally used, it is required to contain a large number of network former oxides such as SiO2, B2O3, P2O5, GeO2 and the like to enhance glass formability. For example, rare earth oxides such as La2O3, Y2O3, Gd2O3 and transition metal oxides such as ZrO2, HfO2, Ta2O5 are not network former oxides. Thus, in a case of a glass composition having a large amount of those components and a small content amount of the network former oxides described above, crystallization starting from a container-melt interface (uneven nucleation) is caused, which prevents vitrification in many cases.
Meanwhile, in the present embodiment, for example, in a case where an optical glass is manufactured by the method through use of the levitation furnace described above, the container and the melt are not held in contact with each other, and hence uneven nucleation is suppressed as much as possible. As a result, glass formation of the melt is largely promoted, and vitrification is enabled even with a composition having a small or no content amount of the network former oxides, which makes it impossible to perform manufacturing by crucible melting. By adopting such manufacturing method, the optical glass according to the present embodiment, which has a composition that cannot be vitrificated in the related art, can be manufactured. The optical glass according to the present embodiment has a high refractive index and a high abbe number. Thus, the present invention is applicable to a glass material having a high refractive index and low dispersibility and a wide-band transmittance material.
Next, description is made on Examples and Comparative Examples given below, and the present invention is not limited at all by Examples given below.
The optical glasses in Examples were produced through use of the gas-jet type levitation furnace 3 illustrated in
The optical glasses in Comparative Examples were produced in accordance with the following procedure. First, raw materials selected from oxides, hydroxides, carbonates, nitrates, sulfates, and the like were weighted to have a predetermined chemical composition. Subsequently, the weighted raw materials were mixed and put into a platinum crucible, melted at a temperature of 1,350° C. for approximately an hour, and uniformed by stirring. After that, the temperature was lowered appropriately, and then casting in a die or the like and annealing were performed. In this manner, each sample was obtained.
A refractive index of each glass was measured through use of a prism coupler (“2010/M” model, produced by Metricon). A glass sample was polished, a polished surface was held in close contact with a single crystal rutile prism, and a total reflection angle when light having a measurement wavelength entered was measured. In this manner, a refractive index was obtained. Measurement was performed five times at each of three wavelengths of 473 nm, 594.1 nm, and 656 nm, and an average value was given as a measurement value. Further, the obtained actual measurement value was subjecting to fitting by the least-squares method through use of Drude-Voigt's dispersion equation given below, and refractive indexes and abbe numbers (vd) on a d-line (587.562 nm), an F-line (486.133 nm), and a C-line (656.273 nm) were calculated. Note that, a value of each refractive index is shown truncating the numbers beyond the fourth decimal point.
(n: a refractive index, m: an electron mass, c: light velocity, e: an elementary charge, N: the number of molecules per unit volume, f: oscillator strength, λ0: an intrinsic resonance wavelength, λ: a wavelength).
Further, an abbe number (vd) is defined in the following expression.
A component composition (in terms of mol % of cations), a refractive index (nd), an abbe number (vd), and Δnd of each of the optical glasses in Examples and Comparative Examples are shown in the tables. Formation of a reference line of Δnd=nd−0.01023vd+2.2988 or the like can be successfully performed in accordance with the method of forming a reference line described above. Two glass types of “J-LASF08” and “J-LASFH16” (both are glass type names produced by HIKARI GLASS Co., Ltd.) having different abbe numbers (vd) and refractive indexes (nd) can be adopted as reference materials, and the reference line can be successfully formed based on those values.
As described above, all the optical glasses in Examples satisfied (La3++Y3++Gd3+)×(Zr4++Hf4++Ta5+)≥400(%)2, and had Δnd of 0.02 or greater. Further, it was confirmed that the optical glasses in Examples achieved both high refractivity and low dispersibility at the same time.
| Number | Date | Country | Kind |
|---|---|---|---|
| 2017-181028 | Sep 2017 | JP | national |
This application is a Continuation of U.S. patent application Ser. No. 16/823,860, filed on Mar. 19, 2020, which is a Continuation of International Patent Application No. PCT/JP2018/014932, filed on Apr. 9, 2018, which claims foreign priority benefit to Japanese Patent Application No. 2017-181028, filed Sep. 21, 2017, the disclosures of which are herein incorporated by reference in their entireties.
| Number | Date | Country | |
|---|---|---|---|
| Parent | 16823860 | Mar 2020 | US |
| Child | 17523515 | US | |
| Parent | PCT/JP2018/014932 | Apr 2018 | US |
| Child | 16823860 | US |
