Patent Grant
10941072
This application is a national phase application of PCT Application No. PCT/KR2018/005756, filed on 19 May 2018, which claims the benefit and priority to Korean Patent Application Nos. 10-2017-0061909, filed on 19 May 2017 and 10-2018-0056420, filed on 17 May 2018. The entire disclosures of the applications identified in this paragraph are incorporated herein by references.
The present disclosure relates to fluorophosphate glasses for an active device and, more particularly, to the composition of fluorophosphate glasses for an active device, the fluorophosphate glasses having thermal and mechanical properties to be able to be used as a glass base material for an optical fiber laser, having a high emission cross-section characteristic, having a reinforced upconversion and downconversion emission characteristic, and having high sensitiveness S in a cryogenic environment.
This section provides background information related to the present disclosure which is not necessarily prior art.
In general, an erbium-doped fiber amplifier (EDFA), which is an optical fiber amplifier device that is used as an important device in not only a wavelength division multiplexing (WDM) communication system, but most optical networks, amplifies light having a wavelength between 1530 and 1610 nm by doping an optical fiber made of glass with erbium.
Fluorophosphate (FP) glass produced by mixing fluoride glass with phosphate has excellent thermal stability and chemical durability, low phonon energy, and excellent linearity of a light transmittance characteristic and a refractive index in a wide spectrum region from the ultraviolet ray to the near infrared ray, as compared with fluoride glass. Further, when a rare earth (RE) element is used as a dopant, high dopant concentration can be achieved by providing multiple energy levels, so the fluorophosphate glass is a glass base material that can achieve high efficiency even using a short cavity.
Meanwhile, ytterbium (Yb) provides a considerably high absorption cross section in the region of 980 nm, and is used as a sensitizer of laser excitation by being co-doped with erbium (Er) because overlap of the energy level of a donor (2F5/2, Yb3+) and the energy level of an acceptor (4I11/2, Er3+).
The application range of the fluorophosphate glass co-doped with Er/Yb having these excellent characteristics, in order to use the excellent characteristics described above, has been increased recently up to not only existing applications such as a visible light or infrared laser, an optical fiber amplifier, an optical storage device, and a submarine optical communication network, but a 3D space observation system that requires high output, an eye-safe light source (1550 nm), and light weight such as LiDAR (Light Detection and Ranging).
Further, a green color having a wavelength of 500 nm band and a red color having a wavelength of 600 nm band are used in fields such as a biotechnology and data storage.
In order to be used in this wide application field, it is required to develop a fluorophosphate glass base material that can achieve high pulse output even if the size of a device is reduced. Further, it is required to use an upconversion phenomenon in order to emit a wavelength of 500 to 600 nm using a laser excitation system of 980 nm.
An object of the present disclosure is to provide fluorophosphate glasses for an active device, the fluorophosphate glasses having thermal and mechanical properties to be able to be used as a glass base material for an active device (e.g., an optical fiber laser), having a high emission cross-section characteristic, having a reinforced upconversion and downconversion emission characteristic, and having high sensitivity S in a cryogenic environment.
This section provides a general summary of the disclosure and is not a comprehensive disclosure of its full scope or all of its features.
In order to achieve the objects, fluorophosphate glasses for an active device according to an aspect of the present disclosure includes: a metaphosphate composition including Al(PO3)3; a fluoride composition including BaF2 and SrF2; and a dopant composed of ErF3 and YbF3.
In the fluorophosphate glasses for an active device according to an aspect of the present disclosure, the YbF3 may be about 3 mol % to about 5 mol %.
In the fluorophosphate glasses for an active device according to an aspect of the present disclosure, the ErF3 may be about 3 mol % and YbF3 may be about 3 mol % to about 5 mol %.
In the fluorophosphate glasses for an active device according to an aspect of the present disclosure, the Al(PO3)3 may be about 20 mol % to about 30 mol %, the BaF2 may be about 10 mol % to about 60 mol %, and the SrF2 may be about 10 mol % to about 70 mol %.
In the fluorophosphate glasses for an active device according to an aspect of the present disclosure, the Al(PO3)3 may be about 20 mol %, the BaF2 may be about 40 mol % to about 60 mol %, and the SrF2 may be about 20 mol % to about 40 mol %.
In the fluorophosphate glasses for an active device according to an aspect of the present disclosure, the ErF3 may be about 3 mol % and YbF3 may be about 3 mol % to about 5 mol %.
In the fluorophosphate glasses for an active device according to an aspect of the present disclosure, the Al(PO3)3 may be about 20 mol %, the BaF2 may be about 60 mol %, and the SrF2 may be about 20 mol %.
In the fluorophosphate glasses for an active device according to an aspect of the present disclosure, the ErF3 may be about 3 mol % and YbF3 may be about 3 mol % to about 5 mol %.
In the fluorophosphate glasses for an active device according to an aspect of the present disclosure, the Al(PO3)3 may be about 20 mol %, the BaF2 may be about 50 mol %, and the SrF2 may be about 30 mol %.
In the fluorophosphate glasses for an active device according to an aspect of the present disclosure, the ErF3 may be about 3 mol % and YbF3 may be about 3 mol % to about 5 mol %.
In the fluorophosphate glasses for an active device according to an aspect of the present disclosure, the Al(PO3)3 may be about 20 mol %, the BaF2 may be about 40 mol %, and the SrF2 may be about 40 mol %.
According to the present disclosure, thermal properties including glass transition temperature (tg) and peak temperature (tp), thermomechanical properties including coefficient of thermal expansion (CTE), and mechanical properties including Knop hardness are improved, so there is provided an advantage in the process of manufacturing an active device including an optical fiber laser.
According to the present disclosure, there is an effect of being able to achieve high pulse output even if the size of a device decreases by achieving a high emission cross-section characteristic.
According to the present disclosure, there is an effect of increasing the lifetime of carriers at a metastable state energy level that is stimulated-emitted due to an effective energy transfer phenomenon by the composition optimization of dopants (e.g., Er and Yb).
According to the present disclosure, there is an effect of reinforcing downconversion and upconversion emission characteristics by the composition optimization of dopants (e.g., Er and Yb).
According to the present disclosure, it is possible to obtain a glass base material for an active device which has excellent sensitivity at cryogenic temperature. Therefore, it is possible to provide an active device that can be used in a cryogenic environment.
Hereafter, embodiments of achieving fluorophosphate glasses for an active device according to the present disclosure are described in detail with reference to the drawings.
However, it should be understood that the spirit of the present disclosure is not considered as being limited to the embodiments described below and those skilled in the art may easily propose various embodiments included in the same spirit as the present disclosure through changing and modifying, but the changes and modification are included in the spirit of the present disclosure.
Further, the terms to be used hereafter are selected for the convenience of description and should be appropriately construed as meanings coinciding with the spirit of the present disclosure, not being limited to the meanings in dictionaries when finding out the spirit of the present disclosure.
Fluorophosphate glasses according to the present embodiment have Al(PO3)3—BaF2—(Sr, Ca, Mg)F2 as a base material. In detail, the inventor(s) proposes the composition of fluorophosphate glasses composed of ErF3—YbF3—Al(PO3)3—BaF2—SrF2 or has these compositions as a base material as characteristic of the present disclosure.
Accordingly, as for Al(PO3)3—BaF2—(Sr, Ca, Mg)F2-based glass, by satisfying thermal and mechanical property conditions that can be applied to glass for an active device (e.g., an optical fiber laser) and optimizing the composition ratio (mol %) of a dopant composed of Er3+ and Yb3+, a high emission cross-section characteristic is achieved such that an effect that can achieve high pulse output even if the size of devices is reduced can be derived.
Referring to
In
An optical fiber is manufactured by reheating and drawing a glass base material manufactured in an ingot shape at predetermined temperature and at a predetermined speed.
Accordingly, glass transition temperature Tg and peak temperature Tp are important factors that determine difficulty and yield of a process of glass base materials for manufacturing optical fibers.
Referring to
Further, as the content of SrF2 increases from 0.2 mol % to 0.7 mol % instead of BaF2 from the sample composition 8 to the sample composition 14 in a Al(PO3)3—BaF2—SrF2-based glass composition candidate, there is no thermal property displacement behavior tendency, so it is determined as relatively slight.
Accordingly, in Al(PO3)3—BaF2—(Sr, Ca, Mg)F2-based glass, a change in the composition has low influence on the difficulty and yield of a drawing process in manufacturing of an optical fiber, so there is the advantage that the composition optimization for adjusting other characteristics is possible.
Meanwhile, it can be seen that the content of Al(PO3)3 that is a network former increases from 0.2 mol % to 0.3 mol %, the structure of rigidity relatively increases and the glass transition temperature increases, so there is a limit in a composition change range of the content of Al(PO3)3.
Referring to
In general, when rare earth ions are added, a phenomenon that is opposite to the phenomenon that glass transition temperature relatively increases is shown.
Further, it is shown that as ErF3 increases in ErF3—Al(PO3)3—BaF2—MgF2-based glass of (0.01, 0.02) mol %, the glass transition temperature linearly decreases and it can be seen that the same tendency can be also seen in ErF3—Al(PO3)3—BaF2—CaF2-based glass of (0.01, 0.02) mol % and ErF3—Al(PO3)3—BaF2—SrF2-based glass of (0.01, 0.02) mol %.
When an optical fiber expands or contracts in accordance with external temperature, the transmission characteristic of a communication system is obviously deteriorated and a change of a gain characteristic is caused in an optical fiber laser or an optical fiber amplifier, so it is preferable that a coefficient of thermal expansion is small.
Referring to
Referring to
Meanwhile, the hardness is relatively low in the sample composition 4, which is determined because the composition ratio of Al(PO3)3 decreased to 0.1.
Accordingly, it can be seen that as the composition ratio of Al(PO3)3 increases in the Al(PO3)3—BaF2—MgF2-based glass, the hardness linearly increases.
Next, as for a hardness change of the Al(PO3)3—BaF2—CaF2-based glass, it can be seen that as BaF2 mol % decreases from 0.7 to 0.4, that is, CaF2 mol % increases from 0.1 to 0.4 in 0.2Al(PO3)3, the hardness linearly increases and the same hardness increase is shown in 0.3Al(PO3)3.
Further, when Al(PO3)3 increases, the hardness relatively increases, so it can be seen in this test that when the composition changes from the number 6 to the number 14, the hardness also linearly increases.
Next, as for a hardness change of Al(PO3)3—BaF2—SrF2-based glass, first, when the BaF2 composition mole ratio is relatively large as 0.6 mol %, as in the composition samples 8 and 14, the hardness is very small.
In particular, it could be seen that there is little influence even though mol % of Al(PO3)3 increases in the Al(PO3)3—BaF2—SrF2-based glass.
Meanwhile, as SrF2 mol % increases from 0.4 to 0.7, that is, from the composition 9 to composition 13 with 0.2Al(PO3)3 fixed, the hardness linearly increases, which means that, according to the change tendency of hardness of Al(PO3)3—BaF2—(Ca, Mg, Sr)F2 fluorophosphate glass, the hardness is small in the region with a large composition ratio of BaF2 and the hardness generally increases with an increase in CaF2, MgF2, or SrF2 composition ratio to BaF2. Further, an increase of phosphate with high melting temperature results in improvement of hardness.
Meanwhile, referring to
When it is added up to 0.01 mol % ErF3 concentration, as a test, it is expected that ligand and covalent bonding around Er ions increase, so, relatively, the glass transition temperature increases and hardness is improved when rare earth ions are relatively added even in consideration of non-uniform distribution of Er3+ ions in glass crystals due to volatility.
Referring to
Meanwhile, the absorption spectrum of
Referring to
Referring to
Referring to
Further, a full width at half maximum (FWHM) increases from 67 nm to 78 nm when YbF3 increases from 1.0 mol % to 4.0 mol % and decreases when the YbF3 concentration is 5.0 mol %. When the YbF3 concentration is 5.0 mol %, the emission intensity and FWHM are decreased by a non-radiative process due to cluster formation.
Referring to
Referring to
When the population inversion ratio γ is 0.4 or more, the laser emission wavelength moves to a short wavelength. Further, when the population inversion ratio γ is 0.4 or more, the bandwidth is 74 nm, which is very wide in comparison to the bandwidth of a common silicated erbium-doped fiber amplifier.
When population inversion ratio γ is 0.4 or more, a flat gain characteristic is shown in the range of 1490 nm to 1620 nm including C(1530-1565 nm) and L(1565-1625 nm) bands of an optical communication window. Accordingly, it is possible to receive more channels in wavelength division multiplex networks.
Referring to
The increase of τexp with an increase from 1.0 mol % to 4.0 mol % of the concentration of YbF3 is because excitation through energy conversion according to the increase in concentration of YbF3 and dispersion by ErF3 increase. Further, the decrease of τexp due to the increase to 5.0 mol % of the concentration of YbF3 is because a non-radiative loss is increased due to cluster formation. Accordingly, τexp when x is 0.02 to 0.05 in Al(PO3)3-(40−x)BaF2—SrF2-(0.03)ErF3/(x)YbF3 is longer than that of fluorophosphate glasses or fluorophosphate glasses based on Al(PO3)3 in the related art.
Next, an emission cross-section characteristic of fluorophosphate glasses for an active device according to the present embodiment is described.
Referring to
Referring to
Referring to
In other words, these results are considered as being caused by a relatively small ratio of quenching effect, such as energy transition and multiphonon relaxation of rare earth elements.
Further, when the content of SrF2 increases instead of BaF2 with a composition change of a base material, that is, the sample composition increases from sample composition ABS-8 to sample composition ABS-10, the relatively highest emission cross-section is shown at the ratio of ErF3:YbF3=0.03:0.03 to 0.03:0.05, so a high emission cross-section may be achieved at a relatively very lower content of YbF3 than 1:3 that is the ratio studied up to now.
Downconversion is described first with reference to
In this case, it can be seen that an energy transition phenomenon occurs between 4I15/24I11/2 transition of erbium (Er) and 2F7/22F5/2 transition of ytterbium (Yb) and a non-radiative transmission phenomenon to 4I11/24I13/2 of erbium (Er) is complexly shown, thereby influencing the carrier lifetime at 4I13/2.
When the concentration of ytterbium (Yb) increases, 2F7/22F5/2 transition of ytterbium (Yb) and 4I15/24I11/2 transition of erbium (Er) overlap, so an energy transfer phenomenon from ytterbium (Yb) to erbium (Er) increases. Further, as described above, the effect of ytterbium (Yb) ions reducing the non-radiative process of the erbium (Er) ions increases, so the carrier lifetime at the energy level of 4I13/2 increases.
Next, upconversion is described.
Upconversion occurs in very (imitative situations and is almost not observed in the natural world.
The upconversion phenomenon is a phenomenon of excitation to an energy level higher than the energy of one photon due to not a single photon, but two or more photons. This is also called anti-Stokes-emission.
According to the upconversion phenomenon, an electron primarily is excited to a high energy level by absorbing a photon and then it should absorb another photon before dropping to the ground state. Accordingly, the electron primarily excited by absorbing a photon should exist at the primarily excited energy level until it secondarily absorbs a photon.
Referring to
Another carrier remaining at 4I11/2 is up-converted by an exited-state absorption phenomenon of excitation to 4F7/2 or 4F9/2 by another energy transfer of 4I15/2→4I11/2.
The carriers up-converted to 4F7/2 or 4F9/2 drop to 2H11/2, 4S3/2, and 4F9/2 through non-radiative re-bonding. The carriers dropped to 2H11/2, 4S3/2, and 4F9/2 drop again to 4I15/2 and re-bonding, thereby emitting photons of 523 nm and 545 nm and a photon of 651 nm.
Referring to
Accordingly, it can be seen that it is possible to analyze influence of temperature on thermally coupled levels of Al(PO3)3-(1−x)BaF2—SrF2-(0.03)ErF3/(x)YbF3-based glass through a fluorescence temperature sensing method.
The sensitivity S is a rate according to time of fluorescence intensity ratio (FIR, hereafter, referred to as R).
Referring to
Accordingly, as it can be seen from
S and maximum sensor sensitivity Tmax calculated on the basis of
Referring to Table 1, the fluorophosphate glasses for an active device according to the present embodiment (particularly, Al(PO3)3-(1−x)BaF2—SrF2-(0.03)ErF3/(x)YbF3 glass (x=0.05)) have S of 22.4×10−4 and Tmax of 123 K.
Accordingly, it can be seen that the fluorophosphate glasses for an active device according to the present embodiment have high sensitivity S at cryogenic temperature (123 K) that has not been shown in any glass base materials.
| Number | Date | Country | Kind |
|---|---|---|---|
| 10-2017-0061909 | May 2017 | KR | national |
| 10-2018-0056420 | May 2018 | KR | national |
| Filing Document | Filing Date | Country | Kind |
|---|---|---|---|
| PCT/KR2018/005756 | 5/19/2018 | WO | 00 |
| Publishing Document | Publishing Date | Country | Kind |
|---|---|---|---|
| WO2018/212631 | 11/22/2018 | WO | A |
| Number | Date | Country |
|---|---|---|
| 106186679 | Dec 2016 | CN |
| 06-157068 | Jun 1994 | JP |
| 2014-091650 | May 2014 | JP |
| 10-2016-0048962 | May 2016 | KR |
| Entry |
|---|
| Goncalves et al. Structure-property relations in newfluorophosphate glasses singly-and co-doped with Er3+ and Yb3+. Materials Chemistry and Physics 157 (2015), pp. 45-55. |
| International Search Report from corresponding PCT Application No. PCT/KR2018/005756, dated Jan. 2, 2019. |
| Number | Date | Country | |
|---|---|---|---|
| 20200002218 A1 | Jan 2020 | US |
