CN104932054B - A kind of triple clad thulium doped fiber and preparation method thereof - Google Patents
A kind of triple clad thulium doped fiber and preparation method thereof Download PDFInfo
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- CN104932054B CN104932054B CN201510424997.8A CN201510424997A CN104932054B CN 104932054 B CN104932054 B CN 104932054B CN 201510424997 A CN201510424997 A CN 201510424997A CN 104932054 B CN104932054 B CN 104932054B
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- thulium
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- oxide
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- 239000000835 fiber Substances 0.000 title claims abstract description 179
- 229910052775 Thulium Inorganic materials 0.000 title claims abstract description 98
- FRNOGLGSGLTDKL-UHFFFAOYSA-N thulium atom Chemical compound [Tm] FRNOGLGSGLTDKL-UHFFFAOYSA-N 0.000 title claims abstract description 86
- 238000002360 preparation method Methods 0.000 title claims abstract description 17
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims abstract description 103
- ZIKATJAYWZUJPY-UHFFFAOYSA-N thulium(iii) oxide Chemical compound [O-2].[O-2].[O-2].[Tm+3].[Tm+3] ZIKATJAYWZUJPY-UHFFFAOYSA-N 0.000 claims abstract description 88
- 238000005253 cladding Methods 0.000 claims abstract description 85
- DLYUQMMRRRQYAE-UHFFFAOYSA-N tetraphosphorus decaoxide Chemical compound O1P(O2)(=O)OP3(=O)OP1(=O)OP2(=O)O3 DLYUQMMRRRQYAE-UHFFFAOYSA-N 0.000 claims abstract description 56
- 239000011347 resin Substances 0.000 claims abstract description 46
- 229920005989 resin Polymers 0.000 claims abstract description 46
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 claims abstract description 37
- 239000000377 silicon dioxide Substances 0.000 claims abstract description 32
- 239000002019 doping agent Substances 0.000 claims abstract description 20
- 238000012946 outsourcing Methods 0.000 claims abstract description 7
- 239000010410 layer Substances 0.000 claims description 74
- 238000000151 deposition Methods 0.000 claims description 60
- 230000008021 deposition Effects 0.000 claims description 50
- 239000010453 quartz Substances 0.000 claims description 39
- 239000012792 core layer Substances 0.000 claims description 33
- -1 aluminum ions Chemical class 0.000 claims description 14
- 239000000463 material Substances 0.000 claims description 13
- VXEGSRKPIUDPQT-UHFFFAOYSA-N 4-[4-(4-methoxyphenyl)piperazin-1-yl]aniline Chemical compound C1=CC(OC)=CC=C1N1CCN(C=2C=CC(N)=CC=2)CC1 VXEGSRKPIUDPQT-UHFFFAOYSA-N 0.000 claims description 11
- 239000005049 silicon tetrachloride Substances 0.000 claims description 11
- XHXFXVLFKHQFAL-UHFFFAOYSA-N phosphoryl trichloride Chemical compound ClP(Cl)(Cl)=O XHXFXVLFKHQFAL-UHFFFAOYSA-N 0.000 claims description 10
- 238000005245 sintering Methods 0.000 claims description 9
- 238000007654 immersion Methods 0.000 claims description 8
- 229910019213 POCl3 Inorganic materials 0.000 claims description 5
- 229910052782 aluminium Inorganic materials 0.000 claims description 5
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 claims description 4
- YBMRDBCBODYGJE-UHFFFAOYSA-N germanium oxide Inorganic materials O=[Ge]=O YBMRDBCBODYGJE-UHFFFAOYSA-N 0.000 claims description 4
- PVADDRMAFCOOPC-UHFFFAOYSA-N oxogermanium Chemical compound [Ge]=O PVADDRMAFCOOPC-UHFFFAOYSA-N 0.000 claims description 4
- 229910052698 phosphorus Inorganic materials 0.000 claims description 4
- 239000011574 phosphorus Substances 0.000 claims description 4
- 230000003647 oxidation Effects 0.000 claims description 3
- 238000007254 oxidation reaction Methods 0.000 claims description 3
- 238000000034 method Methods 0.000 description 22
- 239000011241 protective layer Substances 0.000 description 21
- VSCWAEJMTAWNJL-UHFFFAOYSA-K aluminium trichloride Chemical compound Cl[Al](Cl)Cl VSCWAEJMTAWNJL-UHFFFAOYSA-K 0.000 description 16
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 15
- 239000001301 oxygen Substances 0.000 description 15
- 229910052760 oxygen Inorganic materials 0.000 description 15
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 10
- 239000013307 optical fiber Substances 0.000 description 10
- 239000000243 solution Substances 0.000 description 10
- 230000008569 process Effects 0.000 description 8
- 238000012360 testing method Methods 0.000 description 8
- 238000001035 drying Methods 0.000 description 6
- 238000010521 absorption reaction Methods 0.000 description 5
- 239000007864 aqueous solution Substances 0.000 description 5
- 238000005336 cracking Methods 0.000 description 5
- 238000005516 engineering process Methods 0.000 description 5
- 239000007789 gas Substances 0.000 description 5
- 239000001307 helium Substances 0.000 description 5
- 229910052734 helium Inorganic materials 0.000 description 5
- SWQJXJOGLNCZEY-UHFFFAOYSA-N helium atom Chemical compound [He] SWQJXJOGLNCZEY-UHFFFAOYSA-N 0.000 description 5
- 229910052757 nitrogen Inorganic materials 0.000 description 5
- 239000000306 component Substances 0.000 description 4
- 239000004925 Acrylic resin Substances 0.000 description 3
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 3
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 3
- 239000000460 chlorine Substances 0.000 description 3
- 229910052801 chlorine Inorganic materials 0.000 description 3
- 238000013461 design Methods 0.000 description 3
- 239000011521 glass Substances 0.000 description 3
- 230000006872 improvement Effects 0.000 description 3
- 238000004519 manufacturing process Methods 0.000 description 3
- VDGJOQCBCPGFFD-UHFFFAOYSA-N oxygen(2-) silicon(4+) titanium(4+) Chemical compound [Si+4].[O-2].[O-2].[Ti+4] VDGJOQCBCPGFFD-UHFFFAOYSA-N 0.000 description 3
- 239000000523 sample Substances 0.000 description 3
- 239000000758 substrate Substances 0.000 description 3
- 229920000178 Acrylic resin Polymers 0.000 description 2
- 241000790917 Dioxys <bee> Species 0.000 description 2
- 229910003978 SiClx Inorganic materials 0.000 description 2
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 2
- AFCIMSXHQSIHQW-UHFFFAOYSA-N [O].[P] Chemical compound [O].[P] AFCIMSXHQSIHQW-UHFFFAOYSA-N 0.000 description 2
- 239000004411 aluminium Substances 0.000 description 2
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 2
- 238000006243 chemical reaction Methods 0.000 description 2
- 238000005660 chlorination reaction Methods 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
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- 229910052710 silicon Inorganic materials 0.000 description 2
- 239000010703 silicon Substances 0.000 description 2
- 239000007787 solid Substances 0.000 description 2
- IEXRMSFAVATTJX-UHFFFAOYSA-N tetrachlorogermane Chemical compound Cl[Ge](Cl)(Cl)Cl IEXRMSFAVATTJX-UHFFFAOYSA-N 0.000 description 2
- 238000012546 transfer Methods 0.000 description 2
- KZBUYRJDOAKODT-UHFFFAOYSA-N Chlorine Chemical compound ClCl KZBUYRJDOAKODT-UHFFFAOYSA-N 0.000 description 1
- KRHYYFGTRYWZRS-UHFFFAOYSA-M Fluoride anion Chemical compound [F-] KRHYYFGTRYWZRS-UHFFFAOYSA-M 0.000 description 1
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 description 1
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- 235000021197 fiber intake Nutrition 0.000 description 1
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- 239000009719 polyimide resin Substances 0.000 description 1
- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 description 1
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 description 1
- 229910052761 rare earth metal Inorganic materials 0.000 description 1
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- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
Classifications
-
- G—PHYSICS
- G02—OPTICS
- G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
- G02B6/00—Light guides; Structural details of arrangements comprising light guides and other optical elements, e.g. couplings
- G02B6/02—Optical fibres with cladding with or without a coating
- G02B6/036—Optical fibres with cladding with or without a coating core or cladding comprising multiple layers
Landscapes
- Physics & Mathematics (AREA)
- General Physics & Mathematics (AREA)
- Optics & Photonics (AREA)
- Lasers (AREA)
- Glass Compositions (AREA)
Abstract
The invention provides a kind of triple clad thulium doped fiber and preparation method thereof, the thulium doped fiber includes fibre core；The fibre core includes silica, thulium oxide, aluminum oxide and phosphorus pentoxide, and the molar content of thulium oxide is 0.2~0.8%, and the molar content of phosphorus pentoxide is 0.5~1.0%, mol ratio >=8 of aluminum oxide and thulium oxide；The diameter d1 of the fibre core is 10~30 μm；The inner cladding on the fibre core surface is set in, inner cladding includes dopant and silica；A diameter of d2 of inner cladding, 2.5d1≤d2≤4d1；The surrounding layer on the inner cladding surface is set in, the surrounding layer includes silica；With the resin bed for being set in the outsourcing layer surface.Triple clad thulium doped fiber provided by the invention reduces the numerical aperture of fibre core, improves the slope efficiency and beam quality of output laser by controlling the diameter of the content of component, fibre core and inner cladding in component and the fibre core in inner cladding.
Description
Technical field
The present invention relates to thulium doped fiber field, more particularly to a kind of triple clad thulium doped fiber and preparation method thereof.
Background technology
Optical fiber laser with its efficiency high, good beam quality, reliability is high, compact-sized and thermal diffusivity is good the advantages that, extensively
It is general to be applied to the fields such as medical treatment, military, optic communication and industrial processes.Thulium doped optical fiber laser swashs as a kind of new high power
Light, it is by the use of thulium-doped silica fib as gain media, and operation wavelength is at 2 μm, in eye-safe wave-length coverage.With optical fiber
Design and the improvement of preparation technology and the development of semiconductor laser pumping technology, 2 mu m waveband thulium-doped fiber lasers obtain
It is fast-developing.Thulium-doped fiber laser is connected due to that can provide wavelength in 2 μm or so of long wave laser generation with the absworption peak of water
Closely, have it is fabulous to tissue cutting and coagulating effectiveness, can be transmitted with ordinary optic fibre, be preferable surgical laser light source.
Thulium-doped fiber laser also result in the extensive concern of people as the efficient pumping source for producing 3~5 μm of mid-infrared lasers simultaneously.
At present, the core component of thulium-doped fiber laser is double clad thulium doped fiber, the structure one of double clad thulium doped fiber
As include mixing fibre core, numerical aperture and the cross section of thulium element than fibre core is much bigger and titanium dioxide silicon substrate that refractive index is lower than fibre core
The protective layer of covering, the coat lower than titanium dioxide silicon substrate cladding index and high index of refraction.It is of the prior art to mix thulium light
The fibre core of fibre laser includes thulium oxide and aluminum oxide, aluminum oxide (Al2O3) solubility of thulium ion can be increased, improve thulium
The dispersiveness of ion, reduce Energy upconversion.But the refractive index of core layer is larger in the thulium-doped fiber laser, makes fibre core
Numerical aperture greatly increases, so that the beam quality of output laser reduces.
The content of the invention
In view of this, it is an object of the invention to provide a kind of triple clad thulium doped fiber and preparation method thereof, the present invention carries
The fibre core numerical aperture of the triple clad thulium doped fiber of confession is smaller, improves the beam quality of output laser.
The invention provides a kind of triple clad thulium doped fiber, including：
Fibre core；
The fibre core includes silica, thulium oxide, aluminum oxide and phosphorus pentoxide, and the molar content of thulium oxide is
0.2~0.8%, the molar content of phosphorus pentoxide is 0.5~1.0%, mol ratio >=8 of aluminum oxide and thulium oxide；The fibre
The diameter d1 of core is 10~30 μm；
The inner cladding on the fibre core surface is set in, the inner cladding includes dopant and silica；The interior bag
The a diameter of d2,2.5d1≤d2≤4d1 of layer；
The surrounding layer on the inner cladding surface is set in, the surrounding layer includes silica；
With the resin bed for being set in the outsourcing layer surface.
Preferably, the molar content 0.4~0.7% of the thulium oxide of the fibre core.
Preferably, mol ratio >=10 of the aluminum oxide and thulium oxide.
Preferably, the outer cladding cross section be shaped as it is non-circular.
Preferably, it is described it is non-circular be rectangle, D types, hexagon or octagon.
Preferably, the dopant in the inner cladding includes germanium oxide or aluminum oxide.
The invention provides a kind of preparation method of triple clad thulium doped fiber described in above-mentioned technical proposal, including following step
Suddenly：
1) inner surface of quartz deposition pipe is sequentially depositing inner cladding and porous core layer；
2) there is the quartz deposition pipe of inner cladding and porous core layer to be immersed in the inner surface deposition that the step 1) obtains to contain
In thulium ion and aluminum ions solution；
3) the quartz deposition pipe after the step 2) is soaked is dried, sintered and collapsing successively, obtains thulium doped fiber
Prefabricated rods, the thulium doped fiber prefabricated rods include fibre core and are sheathed on the inner cladding and surrounding layer on fibre core surface successively；It is described
Fibre core includes silica, thulium oxide, aluminum oxide and phosphorus pentoxide, and the molar content of thulium oxide is 0.2~0.8%, five
The molar content for aoxidizing two phosphorus is 0.5~1.0%, mol ratio >=8 of aluminum oxide and thulium oxide；The inner cladding includes doping
Agent and silica, the inner cladding include silica；
4) the thulium doped fiber preform for obtaining the step 3), is then coated with resin bed, obtains triple clad and mixes thulium
Optical fiber；The diameter d1 of the fibre core of the triple clad thulium doped fiber is 10~30 μm；A diameter of d2 of the inner cladding, 2.5d1≤
d2≤4d1。
Preferably, the step 1) is specially：
Dopant material and silicon tetrachloride are passed into quartz deposition pipe internal surface sedimentary inner envoloping layer, then pass to trichlorine oxygen
Phosphorus and silicon tetrachloride deposition porous core layer.
Preferably, the time of immersion is more than or equal to 0.5 hour in the step 2).
Preferably, the temperature of sintering is 1800 DEG C~2000 DEG C in the step 3).
The invention provides a kind of triple clad thulium doped fiber, including fibre core；The fibre core includes silica, oxidation
Thulium, aluminum oxide and phosphorus pentoxide, the molar content of thulium oxide is 0.2~0.8%, and the molar content of phosphorus pentoxide is 0.5
~1.0%, mol ratio >=8 of aluminum oxide and thulium oxide；The diameter d1 of the fibre core is 10~30 μm；It is set in the fibre core table
The inner cladding in face, the inner cladding include silica and dopant；A diameter of d2 of the inner cladding, 2.5d1≤d2≤
4d1；The surrounding layer on the inner cladding surface is set in, the surrounding layer includes silica；Be set in the surrounding layer table
The resin bed in face.Triple clad thulium doped fiber provided by the invention by control the component of inner cladding and the content of component in fibre core,
The diameter of fibre core and inner cladding, the numerical aperture of fibre core is reduced, improve the slope efficiency and beam quality of output laser.Experiment
As a result show：Fibre core numerical aperture≤0.15；The absorption coefficient of triple clad thulium doped fiber >=2dB/m@793nm；Laser slope is imitated
Rate >=40%.
Brief description of the drawings
Fig. 1 is structure of the triple clad thulium doped fiber edge perpendicular to the cross section of fibre core axis of the preparation of the embodiment of the present invention 1
Schematic diagram；
Fig. 2 is the refractive index profile figure corresponding to the triple clad thulium doped fiber shown in Fig. 1；
Fig. 3 is structure of the triple clad thulium doped fiber edge perpendicular to the cross section of fibre core axis of the preparation of the embodiment of the present invention 2
Schematic diagram；
Fig. 4 is the refractive index profile figure corresponding to the triple clad thulium doped fiber shown in Fig. 3.
Embodiment
The invention provides a kind of triple clad thulium doped fiber, including：
Fibre core；
The fibre core includes silica, thulium oxide, aluminum oxide and phosphorus pentoxide, and the molar content of thulium oxide is
0.2~0.8%, the molar content of phosphorus pentoxide is 0.5~1.0%, mol ratio >=8 of aluminum oxide and thulium oxide；The fibre
A diameter of 10~30 μm of core；
The inner cladding on the fibre core surface is set in, the inner cladding includes dopant and silica；The interior bag
The a diameter of d2,2.5d1≤d2≤4d1 of layer；
The surrounding layer on the inner cladding surface is set in, the surrounding layer includes silica；
With the resin bed for being set in the outsourcing layer surface.
Triple clad thulium doped fiber provided by the invention includes fibre core；The fibre core includes silica, thulium oxide, oxidation
Aluminium and phosphorus pentoxide.In the present invention, the thulium oxide is main dopant；The aluminum oxide and phosphorus pentoxide are codope
Agent.Aluminum oxide (Al is mixed in silica fibre2O3) solubility of thulium ion can be increased, the dispersiveness of thulium ion is improved, reduces energy
Changed in amount.In the present invention, in order to improve the cross-relaxation between adjacent thulium ion (3H4,3H6-3F4,3F4), it usually needs doping
The thulium oxide of high concentration, when the molar content of thulium oxide is more than 0.2%, thulium doped fiber can break through the limit of Stokes efficiency
System.In addition, increase Tm3+Concentration, reaching the fiber lengths needed for certain gain can shorten, and reduce nonlinear effect,
Reduce the background losses of total background losses especially laser work wave band.But work as Tm3+Excessive concentration when, its cluster it is several
Rate greatly increases, and causes the generation of energy transfer up-conversion process, so as to cause the decline of lasing efficiency.This process both wasted
Pump energy, adds threshold power, while also increase the difficulty of heat management.In order to avoid cluster causes unwanted biography
The generation of energy process, can be realized by adulterating the aluminum oxide of high concentration.When the mol ratio of aluminum oxide and thulium oxide >=8, Tm3+
Preferable dispersion effect can be realized, so as to suppress energy transfer up-conversion process.In the present invention, mole of the thulium oxide
Content is 0.2~0.8%, mol ratio >=8 of aluminum oxide and thulium oxide.In the present invention, doping is appropriate when preparing fibre core five
Two phosphorus are aoxidized, the porosity and uniformity of fibre core can be improved, so as to increase adsorption capacity of the fibre core to Doped ions in solution；This
Outside because phosphorus pentoxide sintering temperature is relatively low, pre-sintered process can increase the intensity of fibre core, so as to reduce the several of fibre core cracking
Rate.But then, the phonon energy of phosphorus pentoxide increase glass ingredient, improves the probability of nonradiative transition, easily causes
The reduction of the quantum efficiency of thulium doped fiber；The incorporation of phosphorus pentoxide makes 1.5~1.7 μm of decay increase (P-OH) simultaneously.Cause
This, the doping concentration of phosphorus pentoxide can not be too high.In the present invention, the molar content of doping phosphorus pentoxide is in fibre core
0.5~1.0%.The present invention adulterates a small amount of phosphorus pentoxide in core layer, it is possible to increase the porosity and uniformity of fibre core,
Reduce the probability of porous core layer cracking.
In order to reduce power density, large mode field diameter optical fiber need to be used.In the present invention, the diameter d1 of the fibre core is 10
~30 μm.In the present invention, the high-concentration dopant of aluminum oxide easily causes the refractive index of core layer to increase in fibre core, so that fine
The numerical aperture (NA) of core greatly increases, so that the beam quality of output laser reduces.Therefore, thulium doped fiber is needed using increasing
The method for increasing refractive index inner cladding reduces the numerical aperture of core layer.
Triple clad thulium doped fiber provided by the invention includes being set in the inner cladding on the fibre core surface, in the inner cladding
Including dopant and silica；A diameter of d2 of the inner cladding, 2.5d1≤d2≤4d1；In the specific embodiment of the present invention
In, a diameter of 30 μm of the inner cladding or 80 μm.The present invention doped aluminium or germanium oxide preferably in inner cladding, more preferably
For aluminum oxide.In order to improve the refractive index of inner cladding, inner cladding reaches refractive index same during with mixing germanium oxide during alumina doped
When, the thermal coefficient of expansion of inner cladding is minimum.The diameter and refractive index of usual inner cladding need to choose suitable value, diameter it is too small or
Person's refractive index is too low, then can not effectively reduce the NA of fibre core.And diameter is too big, refractive index is too high, can increase the bending damage of optical fiber
Consumption, it is larger to also result in inner cladding stress, easily causes prefabricated rods cracking during surrounding layer attrition process.In the present invention, triple clad
After thulium doped fiber increase inner cladding, pump light is easily limited in inner cladding, due to inner cladding along the axle perpendicular to the fibre core
The cross section of line is circle, adds spiral light, causes absorption coefficient to reduce.
Triple clad thulium doped fiber provided by the invention includes the surrounding layer for being set in the inner cladding surface, the surrounding layer
Include silica.In the present invention, the shape of cross section of the surrounding layer is non-circular；I.e. the surrounding layer along perpendicular to
The outer shroud of the cross section of the fibre core axis is shaped as non-circular；In the present invention, non-circular preferably rectangular, the D types, six
Side shape or octagon.In a particular embodiment of the present invention, the surrounding layer is along perpendicular to the cross section of the fibre core axis
Outer shroud is shaped as hexagon or octagon.In a particular embodiment of the present invention, it is described non-circular when being hexagon, surrounding layer
Side-back gauge is 250 μm；Described non-circular when being octagon, side-back gauge of surrounding layer is 130 μm.
Triple clad thulium doped fiber provided by the invention includes the resin bed for being set in the outsourcing layer surface.The present invention is to institute
The material for stating resin bed is not particularly limited, using the material of the resin bed well known to those skilled in the art for thulium doped fiber
.In the present invention, the resin bed includes low refractive index resin layer and high refractive index resins protective layer, the low-refraction
Resin bed is set in the outsourcing layer surface；The high refractive index resins protective layer is set in the low refractive index resin layer table
Face.In the present invention, the thickness of the low refractive index resin layer is 20~150 μm；In a particular embodiment of the present invention, it is described
The euphotic refractive index of resin is 1.39~1.40.In the present invention, the material of the low refractive index resin layer preferably includes to mix
One kind in perfluoroalkyl acrylate resin, silicon rubber and polytetrafluoroethylene (PTFE).
In the specific embodiment of the invention, the refractive index of the high refractive index resins protective layer is 1.53~1.55；It is described
The thickness of high refractive index resins protective layer is preferably 20~150 μm.Material of the present invention to the high refractive index resins protective layer
There is no special limitation, using the material of the high refractive index resins protective layer well known to those skilled in the art for thulium doped fiber
.In the present invention, the material of the high refractive index resins protective layer preferably includes the ultraviolet light solidification propylene of high index of refraction
Acid resin or polyimides.
The invention provides a kind of preparation method of triple clad thulium doped fiber described in above-mentioned technical proposal, including following step
Suddenly：
1) quartz deposition pipe internal surface is sequentially depositing inner cladding and porous core layer；
2) there is the quartz deposition pipe of inner cladding and porous core layer to be immersed in the inner surface deposition that the step 1) obtains to contain
In thulium ion and aluminum ions solution；
3) the quartz deposition pipe after the step 2) is soaked is dried, sintered and collapsing successively, obtains thulium doped fiber
Prefabricated rods, the thulium doped fiber prefabricated rods include fibre core and are sheathed on the inner cladding and surrounding layer on fibre core surface successively；It is described
Fibre core includes silica, thulium oxide, aluminum oxide and phosphorus pentoxide, and the molar content of thulium oxide is 0.2~0.8%, five
The molar content for aoxidizing two phosphorus is 0.5~1.0%, mol ratio >=8 of aluminum oxide and thulium oxide；The inner cladding includes dioxy
SiClx and dopant, the surrounding layer include silica；
4) thulium doped preform is drawn, is then coated with resin bed, obtain triple clad thulium doped fiber；The triple clad
The diameter d1 of the fibre core of thulium doped fiber is 10~30 μm；A diameter of d2 of inner cladding, 2.5d1≤d2≤4d1.
The present invention is manufactured using modified chemical vapor deposition process (MCVD) MCVD binding solns infusion method, can also use Outside Vapor
The use well known to those skilled in the art such as sedimentation OVD, axial vapor deposition method VAD and direct nano-particle sedimentation DND
In the method for manufacture thulium doped fiber.The inner surface of quartz deposition pipe is sequentially depositing inner cladding and porous core layer by the present invention.This hair
The bright source to the quartz deposition pipe does not have special limitation, is using quartz deposition pipe well known to those skilled in the art
Can, it can such as use its commercially available prod.In the present invention, the external diameter of the quartz deposition pipe is 20mm~40mm；The quartz
The pipe thickness of deposited tube is preferably 2.0mm~3.5mm.Redeposition after quartz deposition pipe described in preferred pair of the present invention is polished
Inner cladding and porous core layer.The present invention is preferably passed through fluoride gas at 1900~2100 DEG C and oxygen carries out thermal-flame throwing
Light.In the present invention, cut impurity, surface irregularity and the collapsed cell of deposition pipe surface can be eliminated by polishing.
In the present invention, it is preferably specific to be sequentially depositing inner cladding and porous core layer for the inner surface by quartz deposition pipe
For：
Dopant material and silicon tetrachloride are passed into quartz deposition pipe internal surface sedimentary inner envoloping layer, then pass to trichlorine oxygen
Phosphorus and silicon tetrachloride deposition porous core layer.
Silicon tetrachloride, dopant material and oxygen are preferably passed into quartz deposition pipe internal surface deposition and wrapped by the present invention
Layer, obtains inner cladding.In the present invention, the dopant material preferably includes germanium tetrachloride or aluminium chloride.Of the invention specific
In embodiment, gas raw material aluminium chloride (AlCl3) evaporating temperature more than 200 DEG C, it is necessary to pass through high temperature evaporation tank and height
Warm gas piping realizes doping.In deposition process, blowtorch moves from the arrival end of deposited tube to the port of export, is deposited when blowtorch reaches
During the end of pipe, the gas access end of deposited tube will be returned quickly to.With the movement of blowtorch, the heat general from blowtorch
Grain sinters very thin glassy layer into.Blowtorch periodically moves back and forth, and inner cladding in layer is formed in deposition pipe internal surface.
In the present invention, the temperature of the sedimentary inner envoloping layer is preferably 1900 DEG C~2000 DEG C, more preferably 1950 DEG C~2000 DEG C.
After sedimentary inner envoloping layer, the present invention is redeposited loose after preferably the quartz deposition pipe that deposition has inner cladding is cooled
Sandwich layer.The present invention is preferably pressed into POCl3 and silicon tetrachloride deposition porous core layer.In a particular embodiment, the present invention preferably will
Silicon tetrachloride, POCl3 and oxygen are using reversely deposition porous core layer.Temperature when depositing porous core layer is unsuitable too high, to keep away
Exempt from porous core layer and sinter glassy layer into, cause the porosity of porous core layer too low, can not adsorb enough containing the molten of rare earth element
Liquid；Meanwhile depositing temperature is also unsuitable too low, to ensure that porous core layer has enough intensity, prevents in solution immersion process, dredges
Loose sandwich layer comes off, and therefore, depositing temperature is the key parameter for manufacturing preform.
The present invention preferably closes the tail end for depositing the quartz deposition pipe for having inner cladding and porous core layer.The present invention preferably adopts
Breaking deposited tube with blowtorch rise temperature causes the tail end of deposited tube to close.
The present invention by above-mentioned inner surface deposition have the quartz deposition pipe of inner cladding and porous core layer be immersed in containing thulium ion and
In aluminum ions solution.In the present invention, the thulium ion and aluminum ions solution of containing is preferably TmCl3·6H2The O aqueous solution and
AlCl3·6H2The mixed liquor of the O aqueous solution；The TmCl3·6H2The molar concentration of the O aqueous solution is preferably 0.05~0.15mol/
L, more preferably 0.06~0.08mol/L；The AlCl3·6H2The molar concentration of the O aqueous solution is preferably 0.5~2.0mol/L,
More preferably 1.0~1.5mol/L.The time of the immersion is preferably greater than or equal to 0.5 hour；In the specific embodiment of the present invention
In, the time of the immersion is 1 hour or 1.5 hours.In the present invention, remaining solution after immersion is poured out.
Quartz deposition pipe after above-mentioned immersion is dried, sintered and collapsing by the present invention successively, and it is pre- to obtain thulium doped fiber
Rod processed, the thulium doped fiber prefabricated rods include fibre core and are sheathed on the inner cladding and surrounding layer on fibre core surface successively.The present invention
It is preferred that the effective nitrogen of quartz deposition after immersion is purged, heating, it is passed through oxygen and chlorine is dehydrated.The present invention is to nitrogen
The method that air-blowing is swept does not have special limitation, the technical scheme purged using nitrogen well known to those skilled in the art.
In the present invention, oxygen is passed through again after being preferably warming up to 950 DEG C~1000 DEG C and chlorine is dried.The present invention will be dredged by drying
OH in loose sandwich layer-Remove.In the present invention, the time of the drying is preferably 0.5~3 hour, and more preferably 2~2.5 is small
When.
The present invention is preferably sintered in the presence of oxygen and helium.In the present invention, oxygen and the helium conduct
Auxiliary type gas, ensure pressure-fired in quartz deposition pipe.The present invention does not have special limitation to the method for sintering, using this area
Sintering technology scheme known to technical staff.In the present invention, the temperature of the sintering is preferably 1800 DEG C~2000 DEG C.
Quartz deposition pipe after sintering is carried out collapsing by the present invention.The present invention does not have special limit to the method for the collapsing
System, using collapsing technical scheme well known to those skilled in the art.In the present invention, the temperature of the collapsing is preferably
2200 DEG C~2300 DEG C.
After collapsing, obtained thulium doped fiber prefabricated rods include fibre core, inner cladding and surrounding layer.The present invention uses electron probe
Test the content of thulium oxide, aluminum oxide and phosphorus pentoxide in thulium doped fiber prefabricated rods.In the present invention, the fibre core includes
Thulium oxide, aluminum oxide and phosphorus pentoxide, the molar content of thulium oxide is 0.2~0.8%, and the molar content of phosphorus pentoxide is
0.5~1.0%, mol ratio >=8 of aluminum oxide and thulium oxide；The inner cladding includes dopant and silica；It is described outer
Covering includes silica.
The present invention is in the stress of polarisation Microscopic observation thulium doped fiber prefabricated rods well known to those skilled in the art, test result
For：The stress of thulium doped fiber prefabricated rods is smaller.
Thulium doped fiber preform obtained above is then coated with resin bed, obtains triple clad and mix thulium light by the present invention
It is fine；The diameter d1 of the fibre core of the triple clad thulium doped fiber is 10~30 μm；A diameter of d2 of inner cladding, 2.5d1≤d2≤
4d1.The cross section of the surrounding layer of thulium doped fiber prefabricated rods is preferably processed as non-circular by the present invention, then is drawn.The present invention
Being processed as non-circular method perpendicular to the cross section of the axis of the fibre core to surrounding layer edge does not have special limitation, using this
Machining known to art personnel such as grinding, polishing.In the present invention, the non-circular preferably rectangular, D
Type, hexagon or octagon.
In the present invention, the resin bed includes low refractive index resin layer and high refractive index resins protective layer.The present invention is excellent
Choosing coats low refractive index resin layer and high refractive index resins protective layer successively.The present invention does not have special limit to the method for coating
System, using paint-on technique scheme well known to those skilled in the art.
The present invention does not have special limitation to the method for drawing, and thulium doped fiber is prepared using well known to those skilled in the art
Drawing technology scheme.In the present invention, the temperature of the drawing is preferably 1900~2050 DEG C.
In the present invention, the material of the resin bed and protective layer and source and resin bed and guarantor described in above-mentioned technical proposal
The material of sheath is consistent with source, will not be repeated here.It is special that the present invention does not have to the method for coated with resins layer and protective layer
Limitation, using the technical scheme well known to those skilled in the art for preparing thulium doped fiber coated with resins layer and protective layer.
The present invention is to the absorption coefficient of the triple clad thulium doped fiber of offer and the method for testing of laser slope efficiency without spy
Different limitation, the absorption coefficient of test thulium doped fiber and the test side of laser slope efficiency using those skilled in the art's resin
Method.
In order to further illustrate the present invention, with reference to embodiment to a kind of triple clad thulium doped fiber provided by the invention and
Its preparation method is described in detail, but they can not be interpreted as into limiting the scope of the present invention.
Embodiment 1
After quartz deposition pipe is carried out into thermal-flame polishing, four chlorinations are passed through in quartz deposition pipe internal surface at 1970 DEG C
Silicon, germanium tetrachloride and oxygen sedimentary inner envoloping layer.Temperature is then reduced, is passed through silicon tetrachloride, POCl3 and oxygen using reverse
Deposit porous core layer.Blowtorch is moved to deposited tube tail end again, rise temperature breaks quartz deposition pipe, makes quartz deposition pipe tail end
Closing.
The deposited tube of end-blocking is removed from lathe.By the TmCl containing 0.06mol/L3·6H2O and 1mol/L AlCl3·
6H2The O aqueous solution is slowly added in the deposited tube containing porous core layer, is soaked about 1.5 hours.Remaining solution is poured out, again will
Deposited tube is installed on lathe, is passed through nitrogen purging, is then raised temperature to 1000 DEG C, is passed through oxygen and chlorine dehydrates,
To remove the OH in porous core layer-.Drying time is 2 hours.Porous core layer does not occur cracking situation.After drying and dehydrating, lead to
Enter helium, oxygen is sintered to porous core layer, the temperature of sintering is 1900 DEG C.By deposited tube collapsing into transparent at 2300 DEG C
Solid glass rod.Octagon is processed into the cross section of described prefabricated rods then according to advance design, it is pre- by what is processed
Rod processed is installed on fiber drawing tower, is drawn at 2000 DEG C with 20m/min speed, coats the polytetrafluoro of low-refraction successively
The polyimide resin of vinyl and high index of refraction, obtain triple clad thulium doped fiber.
The structural representation such as Fig. 1 of triple clad thulium doped fiber edge prepared by embodiment 1 perpendicular to the cross section of fibre core axis
Shown, Fig. 1 is structural representation of the triple clad thulium doped fiber edge perpendicular to the cross section of fibre core axis of the preparation of the embodiment of the present invention 1
Figure, wherein 1 is fibre core, 2 be inner cladding, and 3 be surrounding layer, and 4 be low refractive index resin layer, and 5 be high index of refraction protective layer；Fig. 2 is
The refractive index profile figure corresponding to triple clad thulium doped fiber shown in Fig. 1, wherein, d1 is core diameter, and d2 is inner cladding diameter,
D3 is outer cladding diameter, and d4 is low refractive index resin layer diameter, and d5 is high index of refraction protective layer diameter.As seen from Figure 2：It is fine
Core, inner cladding, surrounding layer, the refractive index of low refractive index resin layer and high index of refraction protective layer are respectively 1.4700,1.4663,
1.4571,1.3980 and 1.55.
Thulium doped fiber prefabricated rods sandwich layer prepared by the present embodiment 1 obtains mole containing for phosphorus pentoxide through electron probe test
Measure as 0.5%, the molar content of aluminum oxide is 4.5%, and the molar content of thulium oxide is 0.4%.After being drawn into optical fiber, optical fiber
Core diameter is 10 μm, and a diameter of 30 μm of inner cladding, the diameter (side-back gauge) of surrounding layer is 130 μm, low refractive index resin layer
A diameter of 185 μm, a diameter of 245 μm of high index of refraction protective layer；Fibre core numerical aperture is 0.1.The suction of triple clad thulium doped fiber
Receipts coefficient is 2.4dB/m@793nm, and laser slope efficiency is 41%.
Embodiment 2
Quartz deposition pipe is subjected to thermal-flame polishing, four chlorinations are passed through in quartz deposition pipe internal surface at 1970 DEG C
Silicon, aluminium chloride and oxygen sedimentary inner envoloping layer.Depositing temperature is reduced to 1250 DEG C, silicon tetrachloride, POCl3 and oxygen is passed through and sinks
Product porous core layer.Blowtorch is moved to quartz deposition pipe tail end again, rise temperature breaks quartz deposition pipe, makes quartz deposition pipe tail
End seal is closed.
Quartz deposition pipe is removed from lathe, by the TmCl containing 0.08mol/L3·6H2O and 1.5mol/L AlCl3·
6H2O solution is slowly added in the quartz deposition pipe containing porous core layer, is soaked about 1 hour.Remaining solution is poured out, again will
Quartz deposition pipe, which is installed on lathe, rotates deposited tube, is passed through nitrogen purging, then raises temperature to 950 DEG C, is passed through oxygen, chlorine
Gas and helium dehydrate, to remove the OH in porous core layer-.Drying time is 2.5 hours.Porous core layer does not occur cracking feelings
Condition.After drying and dehydrating, be passed through helium, oxygen is sintered to porous core layer, the temperature of sintering is 1950 DEG C.At 2200 DEG C
By deposited tube collapsing into transparent solid glass bar.The cross section of described prefabricated rods is processed into six then according to advance design
Side shape, the prefabricated rods processed are installed on fiber drawing tower, are drawn with 10m/min speed at 2050 DEG C, applied successively
The fluorine doped acrylic resin of low-refraction and the acrylic resin of high index of refraction are covered, obtains triple clad thulium doped fiber.
The structural representation such as Fig. 3 of triple clad thulium doped fiber edge prepared by embodiment 2 perpendicular to the cross section of fibre core axis
Shown, Fig. 3 is structural representation of the triple clad thulium doped fiber edge perpendicular to the cross section of fibre core axis of the preparation of the embodiment of the present invention 2
Figure, wherein 1 is fibre core, 2 be inner cladding, and 3 be surrounding layer, and 4 be low refractive index resin layer, and 5 be high index of refraction protective layer；Fig. 4 is
The refractive index profile figure corresponding to triple clad thulium doped fiber shown in Fig. 3, wherein, d1 is core diameter, and d2 is inner cladding diameter,
D3 is outer cladding diameter, and d4 is low refractive index resin layer diameter, and d5 is high index of refraction protective layer diameter.As can be seen from Figure 4：
Fibre core, inner cladding, surrounding layer, the refractive index of low refractive index resin layer and high index of refraction protective layer are respectively 1.4750,1.4673,
1.4573,1.3980 and 1.55.
Thulium doped fiber prefabricated rods sandwich layer prepared by the present embodiment 2 obtains mole containing for phosphorus pentoxide through electron probe test
Measure as 0.8%, the molar content of aluminum oxide is 6%, and the molar content of thulium oxide is 0.6%.After being drawn into optical fiber, the fibre of optical fiber
Core diameter is 25 μm, and a diameter of 80 μm of inner cladding, the diameter (side-back gauge) of surrounding layer is 250 μm, and low refractive index resin layer is straight
Footpath is 325 μm, a diameter of 400 μm of high index of refraction protective layer；The numerical aperture of fibre core is 0.15.The suction of triple clad thulium doped fiber
Receipts coefficient is 3.2dB/m@793nm, and laser slope efficiency is 45%.
As seen from the above embodiment, the invention provides a kind of triple clad thulium doped fiber, including fibre core；Wrapped in the fibre core
Silica, thulium oxide, aluminum oxide and phosphorus pentoxide are included, the molar content of thulium oxide is 0.2~0.8%, phosphorus pentoxide
Molar content be 0.5~1.0%, mol ratio >=8 of aluminum oxide and thulium oxide；A diameter of 10~30 μm of the fibre core；Set
The titanium dioxide silicon substrate inner cladding on the fibre core surface is located at, the inner cladding includes silica and dopant；The interior bag
The a diameter of d2,2.5d1≤d2≤4d1 of layer；The surrounding layer on the inner cladding surface is set in, the surrounding layer includes dioxy
SiClx；With the resin bed for being set in the outsourcing layer surface.Triple clad thulium doped fiber provided by the invention is by controlling inner cladding
Component and fibre core in the content of component, fibre core and inner cladding diameter, reduce the numerical aperture of fibre core, improve output laser
Slope efficiency and beam quality.Test result indicates that：Fibre core numerical aperture≤0.15；The absorption coefficient of triple clad thulium doped fiber
≥2dB/m@793nm；Laser slope efficiency >=40%.
Described above is only the preferred embodiment of the present invention, it is noted that for the ordinary skill people of the art
For member, under the premise without departing from the principles of the invention, some improvements and modifications can also be made, these improvements and modifications also should
It is considered as protection scope of the present invention.
Claims (9)
1. a kind of triple clad thulium doped fiber, including：
Fibre core；
The fibre core includes silica, thulium oxide, aluminum oxide and phosphorus pentoxide, the molar content of thulium oxide for 0.2~
0.8%, the molar content of phosphorus pentoxide is 0.5~1.0%, mol ratio >=8 of aluminum oxide and thulium oxide；The fibre core it is straight
Footpath d1 is 10~30 μm；
The inner cladding on the fibre core surface is set in, the inner cladding includes dopant and silica；The inner cladding
A diameter of d2,2.5d1≤d2≤4d1；Dopant in the inner cladding includes germanium oxide or aluminum oxide；
The surrounding layer on the inner cladding surface is set in, the surrounding layer includes silica；
With the resin bed for being set in the outsourcing layer surface.
2. triple clad thulium doped fiber according to claim 1, it is characterised in that the molar content of the thulium oxide of the fibre core
0.4~0.7%.
3. triple clad thulium doped fiber according to claim 1, it is characterised in that the mol ratio of the aluminum oxide and thulium oxide
≥10。
4. triple clad thulium doped fiber according to claim 1, it is characterised in that being shaped as the outer cladding cross section is non-
It is circular.
5. triple clad thulium doped fiber according to claim 4, it is characterised in that described non-circular for rectangle, D types, six sides
Shape or octagon.
6. the preparation method of triple clad thulium doped fiber, comprises the following steps described in a kind of Claims 1 to 5 any one：
1) inner surface of quartz deposition pipe is sequentially depositing inner cladding and porous core layer；
2) by inner surface that the step 1) obtains deposition have the quartz deposition pipe of inner cladding and porous core layer be immersed in containing thulium from
In sub and aluminum ions solution；
3) the quartz deposition pipe after the step 2) is soaked is dried, sintered and collapsing successively, and it is prefabricated to obtain thulium doped fiber
Rod, the thulium doped fiber prefabricated rods include fibre core and are sheathed on the inner cladding and surrounding layer on fibre core surface successively；The fibre core
Include silica, thulium oxide, aluminum oxide and phosphorus pentoxide, the molar content of thulium oxide is 0.2~0.8%, five oxidations
The molar content of two phosphorus is 0.5~1.0%, mol ratio >=8 of aluminum oxide and thulium oxide；The inner cladding include dopant and
Silica, the surrounding layer include silica；
4) the thulium doped fiber preform for obtaining the step 3), is then coated with resin bed, obtains triple clad thulium doped fiber；
The diameter d1 of fibre core is 10~30 μm in the triple clad thulium doped fiber；A diameter of d2 of inner cladding, 2.5d1≤d2≤4d1.
7. preparation method according to claim 6, it is characterised in that the step 1) is specially：
Dopant material and silicon tetrachloride are passed into quartz deposition pipe internal surface sedimentary inner envoloping layer, then pass to POCl3 and
Silicon tetrachloride deposits porous core layer.
8. preparation method according to claim 6, it is characterised in that the time of immersion is more than or equal in the step 2)
0.5 hour.
9. preparation method according to claim 6, it is characterised in that in the step 3) temperature of sintering for 1800 DEG C~
2000℃。
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| CN106396360B (en) * | 2016-08-30 | 2019-01-25 | 武汉睿芯特种光纤有限责任公司 | A kind of gain fibre preparation method of online collapsing wire drawing |
| CN106990475A (en) * | 2017-05-18 | 2017-07-28 | 烽火通信科技股份有限公司 | New wavelength Double Cladding Ytterbium Doped Fiber and preparation method |
| CN108802898B (en) * | 2018-08-29 | 2023-05-02 | 法尔胜泓昇集团有限公司 | Large-mode-field ytterbium-doped active optical fiber and preparation method thereof |
| CN110165531A (en) * | 2019-06-27 | 2019-08-23 | 深圳市创鑫激光股份有限公司 | A kind of large mode field triple clad passive fiber, mode stripper and optical fiber laser |
| CN111562648B (en) * | 2020-04-30 | 2022-12-16 | 江苏永鼎光纤科技有限公司 | Large effective mode area low-loss optical fiber with optimized cladding components |
| CN112505827A (en) * | 2020-11-24 | 2021-03-16 | 法尔胜泓昇集团有限公司 | Active optical fiber for high-power laser and preparation method thereof |
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| CN104692656A (en) * | 2015-02-03 | 2015-06-10 | 中国科学院上海光学精密机械研究所 | 2mu m silica fiber core rod glass and preparation method thereof |
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Effective date of registration: 20200415 Address after: 311400 Building 9, Futong Science Park, No. 1-8, Jinqiu Avenue, Fuchun street, Fuyang District, Hangzhou City, Zhejiang Province Co-patentee after: HANGZHOU FUTONG COMMUNICATION TECHNOLOGY Co.,Ltd. Patentee after: Futong Group Co.,Ltd. Co-patentee after: TIANJIN FUTONG XINMAO SCIENCE & TECHNOLOGY Co.,Ltd. Co-patentee after: SHENZHEN XIN'AOKE CABLE Co.,Ltd. Address before: 311400 Building 9, Futong Science Park, No. 1-8, Jinqiu Avenue, Fuchun street, Fuyang District, Hangzhou City, Zhejiang Province Co-patentee before: HANGZHOU FUTONG COMMUNICATION TECHNOLOGY Co.,Ltd. Patentee before: Futong Group Co.,Ltd. Co-patentee before: TIANJIN FUTONG XINMAO SCIENCE & TECHNOLOGY Co.,Ltd. Co-patentee before: HANGZHOU FUTONG ELECTRIC WIRE & CABLE Co.,Ltd. |
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Address after: 311400 Building 9, Futong Science Park, 1-8 Jinqiu Avenue, Fuchun street, Fuyang District, Hangzhou City, Zhejiang Province Patentee after: Futong Group Co.,Ltd. Patentee after: HANGZHOU FUTONG COMMUNICATION TECHNOLOGY Co.,Ltd. Patentee after: Tianjin Futong Information Technology Co.,Ltd. Patentee after: SHENZHEN XIN'AOKE CABLE Co.,Ltd. Address before: 311400 Building 9, Futong Science Park, 1-8 Jinqiu Avenue, Fuchun street, Fuyang District, Hangzhou City, Zhejiang Province Patentee before: Futong Group Co.,Ltd. Patentee before: HANGZHOU FUTONG COMMUNICATION TECHNOLOGY Co.,Ltd. Patentee before: TIANJIN FUTONG XINMAO SCIENCE & TECHNOLOGY Co.,Ltd. Patentee before: SHENZHEN XIN'AOKE CABLE Co.,Ltd. |
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Effective date of registration: 20210926 Address after: No.2 songpingshan Road, North Science Park, Nanshan District, Shenzhen, Guangdong 518000 Patentee after: SHENZHEN XIN'AOKE CABLE Co.,Ltd. Address before: 311400 Building 9, Futong Science Park, 1-8 Jinqiu Avenue, Fuchun street, Fuyang District, Hangzhou City, Zhejiang Province Patentee before: Futong Group Co.,Ltd. Patentee before: HANGZHOU FUTONG COMMUNICATION TECHNOLOGY Co.,Ltd. Patentee before: Tianjin Futong Information Technology Co.,Ltd. Patentee before: SHENZHEN XIN'AOKE CABLE Co.,Ltd. |
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