CN113568244A - Semiconductor quantum dot and rare earth co-doped quartz amplification optical fiber and preparation method thereof - Google Patents
Semiconductor quantum dot and rare earth co-doped quartz amplification optical fiber and preparation method thereof Download PDFInfo
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- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 title claims abstract description 86
- 229910052761 rare earth metal Inorganic materials 0.000 title claims abstract description 66
- 239000013307 optical fiber Substances 0.000 title claims abstract description 58
- 239000004065 semiconductor Substances 0.000 title claims abstract description 58
- 150000002910 rare earth metals Chemical class 0.000 title claims abstract description 56
- 239000002096 quantum dot Substances 0.000 title claims abstract description 54
- 239000010453 quartz Substances 0.000 title claims abstract description 30
- 230000003321 amplification Effects 0.000 title claims abstract description 21
- 238000003199 nucleic acid amplification method Methods 0.000 title claims abstract description 21
- 238000002360 preparation method Methods 0.000 title claims abstract description 11
- 239000000463 material Substances 0.000 claims abstract description 40
- VQCBHWLJZDBHOS-UHFFFAOYSA-N erbium(III) oxide Inorganic materials O=[Er]O[Er]=O VQCBHWLJZDBHOS-UHFFFAOYSA-N 0.000 claims abstract description 14
- 239000000835 fiber Substances 0.000 claims description 48
- 235000012239 silicon dioxide Nutrition 0.000 claims description 39
- 238000000151 deposition Methods 0.000 claims description 31
- 238000005253 cladding Methods 0.000 claims description 28
- 239000000377 silicon dioxide Substances 0.000 claims description 28
- 229910001404 rare earth metal oxide Inorganic materials 0.000 claims description 23
- 230000008021 deposition Effects 0.000 claims description 22
- 239000002243 precursor Substances 0.000 claims description 22
- YBMRDBCBODYGJE-UHFFFAOYSA-N germanium oxide Inorganic materials O=[Ge]=O YBMRDBCBODYGJE-UHFFFAOYSA-N 0.000 claims description 21
- XCAUINMIESBTBL-UHFFFAOYSA-N lead(ii) sulfide Chemical compound [Pb]=S XCAUINMIESBTBL-UHFFFAOYSA-N 0.000 claims description 20
- 238000000034 method Methods 0.000 claims description 20
- 238000010926 purge Methods 0.000 claims description 15
- 238000006243 chemical reaction Methods 0.000 claims description 14
- 150000004706 metal oxides Chemical class 0.000 claims description 13
- 150000002500 ions Chemical class 0.000 claims description 10
- PVADDRMAFCOOPC-UHFFFAOYSA-N oxogermanium Chemical compound [Ge]=O PVADDRMAFCOOPC-UHFFFAOYSA-N 0.000 claims description 10
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims description 9
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical group O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 claims description 8
- 238000010521 absorption reaction Methods 0.000 claims description 7
- 229910052593 corundum Inorganic materials 0.000 claims description 6
- 238000002189 fluorescence spectrum Methods 0.000 claims description 6
- 239000002245 particle Substances 0.000 claims description 6
- 229910001845 yogo sapphire Inorganic materials 0.000 claims description 6
- 238000009826 distribution Methods 0.000 claims description 5
- 229910044991 metal oxide Inorganic materials 0.000 claims description 5
- 238000005229 chemical vapour deposition Methods 0.000 claims description 4
- CBENFWSGALASAD-UHFFFAOYSA-N Ozone Chemical group [O-][O+]=O CBENFWSGALASAD-UHFFFAOYSA-N 0.000 claims description 3
- 239000008367 deionised water Substances 0.000 claims description 3
- 229910021641 deionized water Inorganic materials 0.000 claims description 3
- DVVZFKBUKVTGJB-UHFFFAOYSA-N erbium;2,2,6,6-tetramethylheptane-3,5-dione Chemical compound [Er].CC(C)(C)C(=O)CC(=O)C(C)(C)C.CC(C)(C)C(=O)CC(=O)C(C)(C)C.CC(C)(C)C(=O)CC(=O)C(C)(C)C DVVZFKBUKVTGJB-UHFFFAOYSA-N 0.000 claims description 3
- 239000011521 glass Substances 0.000 claims description 3
- 238000010438 heat treatment Methods 0.000 claims description 3
- 239000000203 mixture Substances 0.000 claims description 3
- JLTRXTDYQLMHGR-UHFFFAOYSA-N trimethylaluminium Chemical group C[Al](C)C JLTRXTDYQLMHGR-UHFFFAOYSA-N 0.000 claims description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 3
- 238000005516 engineering process Methods 0.000 abstract description 20
- 238000000231 atomic layer deposition Methods 0.000 abstract description 16
- -1 rare earth erbium oxide Chemical class 0.000 abstract description 10
- 238000001228 spectrum Methods 0.000 abstract description 3
- 239000012071 phase Substances 0.000 description 9
- 230000009102 absorption Effects 0.000 description 6
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- 238000010586 diagram Methods 0.000 description 3
- 238000011160 research Methods 0.000 description 3
- 238000005491 wire drawing Methods 0.000 description 3
- 229910052691 Erbium Inorganic materials 0.000 description 2
- 229910005793 GeO 2 Inorganic materials 0.000 description 2
- 239000007983 Tris buffer Substances 0.000 description 2
- 230000005540 biological transmission Effects 0.000 description 2
- 125000004122 cyclic group Chemical group 0.000 description 2
- 238000011161 development Methods 0.000 description 2
- UYAHIZSMUZPPFV-UHFFFAOYSA-N erbium Chemical compound [Er] UYAHIZSMUZPPFV-UHFFFAOYSA-N 0.000 description 2
- 230000005284 excitation Effects 0.000 description 2
- 230000003287 optical effect Effects 0.000 description 2
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- 239000000126 substance Substances 0.000 description 2
- 239000010409 thin film Substances 0.000 description 2
- YRAJNWYBUCUFBD-UHFFFAOYSA-N 2,2,6,6-tetramethylheptane-3,5-dione Chemical compound CC(C)(C)C(=O)CC(=O)C(C)(C)C YRAJNWYBUCUFBD-UHFFFAOYSA-N 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 238000005090 crystal field Methods 0.000 description 1
- 239000002019 doping agent Substances 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 239000010408 film Substances 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 238000004020 luminiscence type Methods 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000011159 matrix material Substances 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 150000004767 nitrides Chemical class 0.000 description 1
- 238000005086 pumping Methods 0.000 description 1
- 230000009103 reabsorption Effects 0.000 description 1
- 229920006395 saturated elastomer Polymers 0.000 description 1
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Classifications
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- G—PHYSICS
- G02—OPTICS
- G02F—OPTICAL DEVICES OR ARRANGEMENTS FOR THE CONTROL OF LIGHT BY MODIFICATION OF THE OPTICAL PROPERTIES OF THE MEDIA OF THE ELEMENTS INVOLVED THEREIN; NON-LINEAR OPTICS; FREQUENCY-CHANGING OF LIGHT; OPTICAL LOGIC ELEMENTS; OPTICAL ANALOGUE/DIGITAL CONVERTERS
- G02F1/00—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics
- G02F1/35—Non-linear optics
- G02F1/39—Non-linear optics for parametric generation or amplification of light, infrared or ultraviolet waves
- G02F1/395—Non-linear optics for parametric generation or amplification of light, infrared or ultraviolet waves in optical waveguides
-
- C—CHEMISTRY; METALLURGY
- C03—GLASS; MINERAL OR SLAG WOOL
- C03B—MANUFACTURE, SHAPING, OR SUPPLEMENTARY PROCESSES
- C03B37/00—Manufacture or treatment of flakes, fibres, or filaments from softened glass, minerals, or slags
- C03B37/01—Manufacture of glass fibres or filaments
- C03B37/012—Manufacture of preforms for drawing fibres or filaments
- C03B37/014—Manufacture of preforms for drawing fibres or filaments made entirely or partially by chemical means, e.g. vapour phase deposition of bulk porous glass either by outside vapour deposition [OVD], or by outside vapour phase oxidation [OVPO] or by vapour axial deposition [VAD]
- C03B37/018—Manufacture of preforms for drawing fibres or filaments made entirely or partially by chemical means, e.g. vapour phase deposition of bulk porous glass either by outside vapour deposition [OVD], or by outside vapour phase oxidation [OVPO] or by vapour axial deposition [VAD] by glass deposition on a glass substrate, e.g. by inside-, modified-, plasma-, or plasma modified- chemical vapour deposition [ICVD, MCVD, PCVD, PMCVD], i.e. by thin layer coating on the inside or outside of a glass tube or on a glass rod
-
- 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
- G02B6/02395—Glass optical fibre with a protective coating, e.g. two layer polymer coating deposited directly on a silica cladding surface during fibre manufacture
Abstract
The invention discloses a semiconductor quantum dot and rare earth co-doped quartz amplification optical fiber and a preparation method thereof. The invention combines the semiconductor quantum dots and the rare earth erbium oxide material with the optical fiber preparation by utilizing the advantages of the thermal atomic layer deposition (T-ALD) technology or the advantages of the plasma enhanced atomic layer deposition (PE-ALD) technology, and the semiconductor quantum dots with certain concentration are doped into the rare earth quartz amplification optical fiber, so that the key scientific problems of limited amplification gain bandwidth, large noise coefficient and the like of the rare earth doped optical fiber can be solved, the luminous intensity of the rare earth doped optical fiber can be obviously enhanced, and the rare earth doped optical fiber has application potential in the fields of ultra-wide spectrum, high gain, low loss and low noise quartz optical fiber amplifiers.
Description
Technical Field
The invention relates to an optical fiber structure and a preparation method thereof.
Background
Due to the rapid development of the optical communication industry, erbium (Er) -doped silica fiber has become the most widely used fiber amplifier in the 1.5 μm band as its bandwidth just matches the low loss window of silica. However, with the continuous increase of the transmission signal capacity, the traditional Er-doped fiber is far from meeting the requirement of mass data transmission due to the limitation of the gain bandwidth (35 nm). Because the luminescence of the Er element at the position of 1.5um belongs to 4f inner layer electron transition, and the quartz optical fiber has a single material structure and limited crystal field regulation and control capability, the gain bandwidth of the erbium-doped optical fiber is difficult to be effectively improved. PbS quantum dots have been widely studied as an important nano semiconductor material due to its characteristics of adjustable band gap, high stability, high conversion efficiency, and the like.
The PbS quantum dots are doped into the rare earth doped fiber as a doping medium to prepare the fiber amplifier, the position of a fiber gain window is flexibly adjusted by regulating and controlling the size effect of the PbS quantum dots, and the amplification bandwidth and the gain characteristic of the Er doped fiber can be effectively improved. For high-speed and broadband optical fiber communication systems, research efforts of many research institutes have shown that doping optical fibers with quantum dots exhibits many excellent characteristics, including wide bandwidth, high gain, high saturated output power, low noise, and the like. Therefore, the research on the application of the nano semiconductor and rare earth co-doped material in the optical fiber technology has very important academic significance and application value for the development of optical fiber communication.
Atomic Layer Deposition (ALD) is a chemical vapor deposition technique in which vapor phase precursor pulses of a dopant source are alternately introduced into a heated reactor and then sequentially subjected to a chemisorption process to deposit on a substrate surface. By accurately controlling the deposition cycle period (atomic layer scale) and the reaction temperature, quantum dots with controllable size, uniform particles and certain thickness can be prepared on the surface of the matrix material. Plasma-enhanced atomic layer deposition (PE-ALD) introduces a plasma generating device in the growth. By introducing the plasma, a large number of active free radicals are generated, and the reaction activity of a precursor substance is enhanced, so that the selection range and the application requirement of ALD on a precursor source are expanded, the time of a reaction period is shortened, and the requirement on the deposition temperature of a sample is reduced. In addition, the introduction of the plasma can further remove impurities in the thin film, and lower resistivity and higher compactness of the thin film can be obtained. Compared with a thermal atomic layer deposition (T-ALD) technology, the PE-ALD technology has wider application prospects in the fields of nitride deposition, doping, metal simple substance material preparation and the like.
Disclosure of Invention
The technical problems to be solved by the invention are as follows: the rare earth doped optical fiber has limited amplification gain bandwidth and large noise coefficient.
The technical scheme of the invention is as follows:
a semiconductor quantum dot and rare earth co-doped quartz amplifying fiber comprises a fiber core and a cladding, wherein the fiber core is doped with PbS quantum dots and rare earth.
The fiber core comprises a silica loose layer on the outer layer and a doping layer in the middle, wherein PbS quantum dots, rare earth oxides and metal oxides are doped in the doping layer.
The rare earth oxide is Er2O3The metal oxide is aluminum oxide Al2O3With germanium oxide GeO2。
PbS quantum dots, rare earth oxides and metal oxides are alternately deposited.
The deposition thickness is 10-1000 nm, and the doping concentration range of the nano semiconductor PbS is controlled to be 0.01-3 mol%; the concentration range of rare earth Er ions is controlled to be 0.01-4 mol%; the concentration range of Al ions is controlled to be 0.1-10 mol%, and the concentration range of Ge ions is controlled to be 1-10 mol%.
The diameter of the fiber core is 4.0-100.0 μm, the diameter of the cladding is 125.0-400.0 μm, the difference of the refractive indexes of the fiber core and the cladding is 0.4-3.5%, the absorption wavelength range of the optical fiber is 600-1600 nm, and the fluorescence spectrum range is 900-2000 nm; the gain range is 1000-1700 nm.
A preparation method of a semiconductor quantum dot and rare earth co-doped quartz amplification optical fiber comprises the following steps:
firstly, depositing a cladding (2) and a silicon dioxide loose layer (1-1) on a quartz base tube by using an improved chemical vapor deposition method to reach a semitransparent glass state at a high temperature;
alternately depositing PbS quantum dots, rare earth oxides and metal oxides on the inner tube wall;
thirdly, repeating the second step, controlling the distribution condition of the doped particles through the deposition cycle period, and forming a doped layer (1-2);
fourthly, performing rod shrinkage treatment on the quartz base tube to form an optical fiber preform;
and fifthly, drawing the optical fiber.
The rare earth oxide alternately and circularly deposited in the second step and the third step is Er2O3The metal oxide is Al2O3With GeO2The gas phase precursor of the Pb source is bis (2,2,6,6-tetramethyl-3, 5-heptanedionate) lead; the precursor material of the S source is H2S and N2Mixture of (A) and (B), H2The concentration of S is 1-15%; the gas-phase precursor of the Er source is as follows: tris (2,2,6,6-tetramethyl-3, 5-heptanedione) erbium, wherein the precursor material of the O source is ozone or deionized water; the precursor of the Al source is trimethylaluminum.
The heating temperature of the Pb source is controlled to be 100-300 ℃, the pulse time of the Pb source is 200-500 ms, and the purging time is 0.5-5 s; s source pulse time is 100-300 ms, and purging time is 0.5-10S; the pulse time of the Er source is 300-800 ms, and the purging time is 1-3 s; the pulse time of the O source is 200-1000 ms, and the purging time is 1.5-5 s; the pulse time of the Al source is 50-300 ms, and the purging time is 200-500 ms; the pulse time of the radio frequency plasma is 1-3 s, and the power of the plasma is controlled to be 200-700W; the temperature of the whole reaction cavity is uniform, the reaction temperature is 150-400 ℃, and the gas flow rate is controlled to be 50-800 sccm.
The cycle period of the third step is 50-3000 periods, and the deposition concentration of the quantum dots and the rare earth oxide material is 0.01-4 mol%.
The invention has the beneficial effects that:
the invention provides a semiconductor quantum dot and rare earth codoped quartz amplification optical fiber and a preparation method thereof by combining semiconductor quantum dots and rare earth erbium oxide materials with optical fiber preparation by utilizing the advantages of a thermal atomic layer deposition (T-ALD) technology or the advantages of a plasma enhanced atomic layer deposition (PE-ALD) technology. The size and the band gap of the semiconductor material are regulated and controlled, so that an energy transfer process exists between the semiconductor material and rare earth ions; because the semiconductor quantum dots are small in size, the scattering of light can be almost ignored, and therefore the doped optical fiber does not have large scattering loss; compared with the conventional co-doped fiber, the quantum dot has a smaller excitation threshold, the scattering cross section of the quantum dot is far smaller than the absorption cross section of the quantum dot, and the pumping power of the quantum dot fiber amplifier is far higher than the excitation threshold power of the quantum dot fiber amplifier, so that the excited radiation is dominant, the spontaneous radiation is limited, the gain is increased, and the noise coefficient is reduced. In addition, the Stokes shift caused by the quantum size effect reduces the reabsorption of the light in the emission peak wave band, and the rare earth ions have no Stokes shift due to the fixed energy level structure, so that the rare earth doped optical fiber doped with semiconductor quantum dots with a certain concentration can solve the key scientific problems of limited amplification gain bandwidth, large noise coefficient and the like of the rare earth doped optical fiber, obviously enhance the luminous intensity of the rare earth doped optical fiber, and has application potential in the fields of ultra-wide spectrum, high gain, low loss and low noise quartz optical fiber amplifiers.
Compared with the prior art, the invention has the following obvious substantive and significant advantages:
1) by adopting the T-ALD technology, the PE-ALD technology or the combined technology of the T-ALD technology and the PE-ALD technology, the deposition temperature is lower, the efficiency is higher, the uniformity of the doped ion material is good, the dispersibility is high, the doping concentration is high and controllable, and the film density is high;
2) the semiconductor quantum dot and rare earth co-doped quartz amplification optical fiber has high gain, wide spectrum, high gain efficiency, low loss and low noise coefficient;
3) the structure is simple, the price is low, the industrialized production is easy, and the method can be used for constructing lasers, optical amplifiers, sensors and the like.
Drawings
FIG. 1 is a block diagram of the architecture of one embodiment of the present invention.
FIG. 2 is a block diagram of the core structure according to one embodiment of the present invention.
Fig. 3 is a process flow diagram of the thermal atomic layer deposition technique or the plasma enhanced atomic layer deposition technique combined with the alternate deposition of the semiconductor quantum dots and the rare earth co-doped material according to the embodiment of the invention.
Detailed Description
The invention is described in detail below with reference to the figures and specific embodiments.
The structure of the semiconductor quantum dot and rare earth co-doped quartz amplifying fiber is shown in figure 1, a fiber core 1 is doped with PbS quantum dots and rare earth, and a cladding 2 is made of pure quartz material with lower refractive index than that of the fiber core. Referring to FIG. 2, the core 1 includes an outer bulk silica layer 1-1 and a middle doped layer 1-2, and the doped layer 1-2 is doped with PbS quantum dots, rare earth oxides and metal oxides. The rare earth oxide is Er2O3The metal oxide is aluminum oxide Al2O3With germanium oxide GeO of increasing refractive index profile2。
PbS quantum dots, rare earth oxides and metal oxides are alternately deposited. The nano semiconductor PbS quantum dot and rare earth Er co-doped material layer alternately deposits a proper amount of semiconductor quantum dot and rare earth erbium oxide, aluminum oxide and germanium oxide co-doped material by utilizing a thermal atomic layer deposition technology (T-ALD), a plasma enhanced atomic layer deposition technology (PE-ALD) or a combined technology of T-ALD and PE-ALD.
The deposition thickness is 10-1000 nm, and the doping concentration range of the nano semiconductor PbS is controlled to be 0.01-3 mol%; the concentration range of rare earth Er ions is controlled to be 0.01-4 mol%; the concentration range of Al ions is controlled to be 0.1-10 mol%, and the concentration range of Ge ions is controlled to be 1-10 mol%.
The optical fiber parameters are as follows: the diameter of the fiber core is 4.0-100.0 μm, the diameter of the cladding is 125.0-400.0 μm, the difference of the refractive index of the fiber core and the refractive index of the cladding is 0.4-3.5%, the absorption wavelength range of the optical fiber is 600-1600 nm, and the fluorescence spectrum range is 900-2000 nm; the gain range is 1000-1700 nm.
The preparation method of the semiconductor quantum dot and rare earth co-doped quartz amplifying fiber comprises the following steps:
1) firstly, depositing a cladding layer and a silica loose layer by using a Modified Chemical Vapor Deposition (MCVD) method to reach a semitransparent glass state at a high temperature;
2) then, uniformly and circularly depositing nano semiconductor PbS quantum dots and rare earth Er in a high-purity quartz base tube by utilizing a thermal atomic layer deposition method (T-ALD), a plasma-enhanced atomic layer deposition technology (PE-ALD) or a combined technology of T-ALD and PE-ALD2O3Alumina, germania materials; the steps of each deposition cycle of the inner wall of the quartz tube are as follows: exposure to a solution containing Pb2+Under precursor gas phase pulse-cleaning the reaction chamber-exposing to a gas containing S2-Under precursor gas phase pulse, cleaning reaction cavity, exposing to Er-containing gas phase pulse3+Is exposed to a precursor gas phase pulse-cleaning the reaction chamber-containing 02-Precursor gas phase pulse lower-cleaning reaction chamber-alternately depositing Al2O3And GeO2；
3) Repeating the process of 2), and controlling the doping concentration of the doped semiconductor material, the rare earth ions and the distribution condition of the doped particles through the deposition cycle period;
4) performing rod shrinkage treatment on the deposition cladding and the fiber core quartz base tube by MCVD technology to form a semiconductor quantum dot and rare earth co-doped optical fiber preform;
5) and finally, drawing the semiconductor quantum dot and rare earth co-doped optical fiber preform into the semiconductor quantum dot and rare earth co-doped quartz amplifying optical fiber by using a drawing tower.
The cycle period in the step 3) is 50-3000 cycles.
The step 2) and the step 3) are carried out with the cyclic deposition and alternate deposition of the nano semiconductor PbS quantum dots and the rare earth Er2O3The gas phase precursor of the Pb source used by the material is as follows: bis (2,2,6,6-Tetramethyl-3, 5-heptanedionate) lead, Bis (2,2,6,6-Tetramethyl-3, 5-heptanedionate) lead (II), Pb (TMHD)2(ii) a The precursor material of the S source is H2S and N2Mixture of (A) and (B), H2The concentration of S is 1-15%; the gas-phase precursor of the Er source is as follows: tris (2,2,6,6-tetramethyl-3,5-heptanedionato) Erbium, Erbium-tris (2,2,6,6-tetramethyl-3, 5-heptanated)ionate)，Er(TMHD)3(ii) a The precursor material of the O source used is ozone (suitable for T-ALD and PE-ALD) or deionized water (suitable for T-ALD); the precursor of the Al source is Al (CH)3)3(TMA), trimethylaluminum.
The step 2) and the step 3) are carried out with the cyclic deposition and alternate deposition of the nano semiconductor PbS quantum dots and the rare earth Er2O3The heating temperature of a Pb source of the material is controlled to be 100-300 ℃, the pulse time of the Pb source is 200-500 ms, and the purging time is 0.5-5 s; s source pulse time is 100-300 ms, and purging time is 0.5-10S; the pulse time of the Er source is 300-800 ms, and the purging time is 1-3 s; the pulse time of the O source is 200-1000 ms, and the purging time is 1.5-5 s; the pulse time of the Al source is 50-300 ms, and the purging time is 200-500 ms; the pulse time of the radio frequency plasma is 1-3 s, and the power of the plasma is controlled to be 200-700W; the temperature of the whole reaction cavity is uniform, the reaction temperature is 150-400 ℃, and the gas flow rate is controlled to be 50-800 sccm.
Example 1:
referring to fig. 1 and 2, the semiconductor quantum dot and rare earth co-doped silica amplifying optical fiber comprises a fiber core 1 and a cladding 2, wherein the fiber core 1 comprises an outer silica loose layer 1-1 and a middle nano semiconductor PbS quantum dot and rare earth Er co-doped material layer 1-2; the core 1 is located in the middle of the cladding 2. The silicon dioxide loose layer 1-1 is made of high-purity silicon dioxide or silicon dioxide material doped with a small amount of high-refractive index GeO 2. The nano semiconductor PbS quantum dot and rare earth Er co-doped material layer 1-2 alternately deposits a proper amount of semiconductor quantum dot and rare earth Er oxide, aluminum oxide and germanium oxide co-doped material by utilizing a T-ALD technology. Through repeated cycle period, the doping concentration and the doping particle distribution of the semiconductor PbS quantum dots and the rare earth erbium oxide are adjusted to ensure that the deposition thickness is 200nm, and then aluminum oxide and germanium oxide are deposited, wherein the concentration is controlled to be 3.0 mol%. The cladding 2 is made of a pure silica material having a lower refractive index than the core 1. And finally, MCVD high-temperature rod shrinkage is adopted to obtain an optical fiber preform, and the optical fiber preform is placed in a wire drawing tower to be drawn to prepare the semiconductor quantum dot and rare earth co-doped quartz amplifying optical fiber. The optical fiber performance parameters are as follows: the diameter of the fiber core 1 is 6 microns, the diameter of the cladding 2 is 125 microns, the refractive index difference between the fiber core 1 and the cladding 2 is about 0.5%, the absorption peak range of the optical fiber is 600-1500 nm, the fluorescence spectrum range is 900-1600 nm, and the gain range is 1000-1500 nm.
Example 2:
the present embodiment is substantially the same as the first embodiment, except that the process parameters are different, and the structural parameters of the optical fiber are adjusted.
Referring to fig. 1 and 2, the semiconductor quantum dot and rare earth co-doped silica amplifying optical fiber comprises a fiber core 1 and a cladding 2, wherein the fiber core 1 comprises an outer silica loose layer 1-1 and a middle nano semiconductor PbS quantum dot and rare earth Er co-doped material layer 1-2; the core 1 is located in the middle of the cladding 2. The silicon dioxide loose layer 1-1 is made of high-purity silicon dioxide or silicon dioxide material doped with a small amount of high-refractive index GeO 2. The nano semiconductor PbS quantum dot and rare earth Er co-doped material layer 1-2 is formed by alternately depositing a proper amount of semiconductor quantum dot and rare earth Er oxide, aluminum oxide and germanium oxide co-doped material by utilizing T-ALD. Through repeated cycle period, the doping concentration and the doping particle distribution of the semiconductor PbS quantum dots and the rare earth erbium oxide are adjusted to ensure that the deposition thickness is 500nm, and then alumina and germanium oxide are deposited, wherein the concentration is controlled to be 5.0 mol%. The cladding 2 is made of a pure silica material having a lower refractive index than the core 1. And finally, MCVD high-temperature rod shrinkage is adopted to obtain an optical fiber preform, and the optical fiber preform is placed in a wire drawing tower to be drawn to prepare the semiconductor quantum dot and rare earth co-doped quartz amplifying optical fiber. The optical fiber performance parameters are as follows: the diameter of the fiber core 1 is 8 mu m, the diameter of the cladding 2 is 130 mu m, the refractive index difference between the fiber core 1 and the cladding 2 is about 0.8%, the absorption peak range of the optical fiber is 750-1550 nm, the fluorescence spectrum range is 900-1700 nm, and the gain range is 1000-1700 nm.
Example 3:
referring to fig. 1 and 2, the semiconductor quantum dot and rare earth co-doped silica amplifying optical fiber comprises a fiber core 1 and a cladding 2, wherein the fiber core 1 comprises an outer silica loose layer 1-1 and a middle nano semiconductor PbS quantum dot and rare earth Er co-doped material layer 1-2; the core 1 is located in the middle of the cladding 2. The silicon dioxide loose layer 1-1 is high-purity silicon dioxide or is doped with a small amount of high-refractive-index GeO2The silica material of (1). The nano semiconductor PbS quantum dot and rare earthThe Er co-doped material layer 1-2 utilizes the technology of combining T-ALD and PE-ALD to deposit a proper amount of semiconductor quantum dots and rare earth erbium oxide, aluminum oxide and germanium oxide co-doped materials. The method mainly comprises the following steps: firstly, alternately depositing PbS quantum dots and rare earth erbium oxide by utilizing T-ALD (T-ALD), wherein the deposition thickness is 400 nm; then, alumina and germanium oxide were alternately deposited by PE-ALD with the concentration controlled at 4.0 mol%. The cladding 2 is made of a pure silica material having a lower refractive index than the core 1. And finally, MCVD high-temperature rod shrinkage is adopted to obtain an optical fiber preform, and the optical fiber preform is placed in a wire drawing tower to be drawn to prepare the semiconductor quantum dot and rare earth co-doped quartz amplifying optical fiber. The optical fiber performance parameters are as follows: the diameter of the fiber core 1 is 10 mu m, the diameter of the cladding 2 is 1135 mu m, the refractive index difference between the fiber core 1 and the cladding 2 is about 1.0%, the absorption peak range of the optical fiber is 800-1600 nm, the fluorescence spectrum range is 1000-1700 nm, and the gain range is 1100-1700 nm.
Claims (10)
1. A semiconductor quantum dot and rare earth co-doped quartz amplification optical fiber comprises a fiber core (1) and a cladding (2), and is characterized in that: the fiber core (1) is doped with PbS quantum dots and rare earth.
2. The semiconductor quantum dot and rare earth co-doped silica amplification fiber of claim 1, wherein: the fiber core (1) comprises a silica loose layer (1-1) on the outer layer and a doping layer (1-2) in the middle, and PbS quantum dots, rare earth oxides and metal oxides are doped in the doping layer (1-2).
3. The semiconductor quantum dot and rare earth co-doped silica amplification fiber of claim 2, wherein: the rare earth oxide is Er2O3The metal oxide is aluminum oxide Al2O3With germanium oxide GeO2。
4. The semiconductor quantum dot and rare earth co-doped silica amplification fiber of claim 3, wherein: PbS quantum dots, rare earth oxides and metal oxides are alternately deposited.
5. The semiconductor quantum dot and rare earth co-doped silica amplification fiber according to claim 4, wherein: the deposition thickness is 10-1000 nm, and the doping concentration range of the nano semiconductor PbS is controlled to be 0.01-3 mol%; the concentration range of rare earth Er ions is controlled to be 0.01-4 mol%; the concentration range of Al ions is controlled to be 0.1-10 mol%, and the concentration range of Ge ions is controlled to be 1-10 mol%.
6. The semiconductor quantum dot and rare earth co-doped silica amplification fiber according to any one of claims 1 to 5, wherein: the diameter of the fiber core (1) is 4.0-100.0 μm, the diameter of the cladding (2) is 125.0-400.0 μm, the refractive index difference between the fiber core (1) and the cladding (2) is 0.4-3.5%, the absorption wavelength range of the optical fiber is 600-1600 nm, and the fluorescence spectrum range is 900-2000 nm; the gain range is 1000-1700 nm.
7. A preparation method of a semiconductor quantum dot and rare earth co-doped quartz amplification optical fiber is characterized by comprising the following steps:
firstly, depositing a cladding (2) and a silicon dioxide loose layer (1-1) on a quartz base tube by using an improved chemical vapor deposition method to reach a semitransparent glass state at a high temperature;
alternately depositing PbS quantum dots, rare earth oxides and metal oxides on the inner tube wall;
thirdly, repeating the second step, controlling the distribution condition of the doped particles through the deposition cycle period, and forming a doped layer (1-2);
fourthly, performing rod shrinkage treatment on the quartz base tube to form an optical fiber preform;
and fifthly, drawing the optical fiber.
8. The method for preparing the semiconductor quantum dot and rare earth co-doped quartz amplification fiber according to claim 7, wherein the method comprises the following steps: in the second step and the third step, the rare earth oxide deposited in the alternating circulation mode is Er2O3The metal oxide is Al2O3With GeO2The gas phase precursor of the Pb source is bis (2,2,6,6-tetramethyl-3, 5-heptanedionate) lead; the precursor material of the S source is H2S and N2Mixture of (A) and (B), H2S concentration of1-15%; the gas-phase precursor of the Er source is as follows: tris (2,2,6,6-tetramethyl-3, 5-heptanedione) erbium, wherein the precursor material of the O source is ozone or deionized water; the precursor of the Al source is trimethylaluminum.
9. The method for preparing the semiconductor quantum dot and rare earth co-doped quartz amplification fiber according to claim 8, wherein the method comprises the following steps: the heating temperature of the Pb source is controlled to be 100-300 ℃, the pulse time of the Pb source is 200-500 ms, and the purging time is 0.5-5 s; s source pulse time is 100-300 ms, and purging time is 0.5-10S; the pulse time of the Er source is 300-800 ms, and the purging time is 1-3 s; the pulse time of the O source is 200-1000 ms, and the purging time is 1.5-5 s; the pulse time of the Al source is 50-300 ms, and the purging time is 200-500 ms; the pulse time of the radio frequency plasma is 1-3 s, and the power of the plasma is controlled to be 200-700W; the temperature of the whole reaction cavity is uniform, the reaction temperature is 150-400 ℃, and the gas flow rate is controlled to be 50-800 sccm.
10. The method for preparing the semiconductor quantum dot and rare earth co-doped quartz amplification fiber according to claim 8, wherein the method comprises the following steps: the cycle period of the third step is 50-3000 periods, and the deposition concentration of the quantum dots and the rare earth oxide material is 0.01-4 mol%.
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| CN1963575A (en) * | 2005-11-08 | 2007-05-16 | 阿尔卡特公司 | Amplifying optical fiber |
| CN101792567A (en) * | 2010-02-11 | 2010-08-04 | 浙江工业大学 | Quantum dot optical fiber core material with PMMA as substrate and preparation and application thereof |
| CN105467511A (en) * | 2015-12-16 | 2016-04-06 | 上海大学 | Bi/Er or Bi/Er/Al co-doped quartz fiber and preparation method thereof |
| CN105467510A (en) * | 2015-12-16 | 2016-04-06 | 上海大学 | Nano-semiconductor PbS-doped quartz amplifying fiber and preparation method for same |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1963575A (en) * | 2005-11-08 | 2007-05-16 | 阿尔卡特公司 | Amplifying optical fiber |
| CN101792567A (en) * | 2010-02-11 | 2010-08-04 | 浙江工业大学 | Quantum dot optical fiber core material with PMMA as substrate and preparation and application thereof |
| CN105467511A (en) * | 2015-12-16 | 2016-04-06 | 上海大学 | Bi/Er or Bi/Er/Al co-doped quartz fiber and preparation method thereof |
| CN105467510A (en) * | 2015-12-16 | 2016-04-06 | 上海大学 | Nano-semiconductor PbS-doped quartz amplifying fiber and preparation method for same |
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