CN103500917A - Sandwich type graphene saturable absorber and preparation method thereof - Google Patents
Sandwich type graphene saturable absorber and preparation method thereof Download PDFInfo
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- CN103500917A CN103500917A CN201310503425.XA CN201310503425A CN103500917A CN 103500917 A CN103500917 A CN 103500917A CN 201310503425 A CN201310503425 A CN 201310503425A CN 103500917 A CN103500917 A CN 103500917A
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Abstract
The invention provides a sandwich type graphene saturable absorber and a preparation method thereof. The sandwich type graphene saturable absorber comprises a bottom layer substrate material, a graphene layer coated on the bottom layer substrate material, and an upper layer substrate material, wherein the three layers are contacted tightly to form a sandwich type structure; a uniform sealing glue-coated layer is formed on the periphery of the sandwich type structure. The method comprises the following steps: depositing a single-layer graphene film on a copper foil; transferring the graphene onto a transparent substrate material by using a wet method transferring technology; placing the same substrate material on the substrate material to which the graphene is attached; compacting to exhaust air between the substrate materials; uniformly coating sealing glue on the periphery of the substrate material to obtain the sandwich type graphene saturable absorber. According to the sandwich type graphene saturable absorber, the graphene can be prevented from undergoing an oxidation reaction with oxygen under laser irradiation, the laser damage resistance threshold of the graphene is increased, and the output power of pulse laser is increased finally.
Description
Technical field
The present invention relates to a kind of Graphene saturated absorbing body and preparation method thereof, belong to ultrashort pulse Solid State Laser saturable absorber preparing technical field.
Background technology
Many characteristics of ultra-short pulse laser make it can be applied in a lot of fields.And to obtain application ultra-short pulse laser so widely, generally by mode-locking technique, realize.Because the passive mode locking technology can produce psec (10
-12s) and even femtosecond (10
-15s) ultrashort pulse of magnitude and its system configuration simply enjoy favor.Passive mode locking is to utilize the non-linear absorption of material or the characteristic of non-linear phase transformation to produce ultrashort laser pulse, and common commercial nonlinear material has semiconductor saturated absorption mirror etc.But the shortcoming of semiconductor saturated absorption mirror passive mode locking technology is: making semiconductor saturated absorption mirror needs relative complex and expensive ultra-clean chamber manufacturing system, about several nanoseconds (10 of the typical recovery time of this class device
-9s).In addition, the light injury threshold of semiconductor saturated absorption mirror is very low, needs particular design.Therefore, finding a kind of Ultrafast recovery time, high light injury threshold, low-cost novel saturated absorbing body is a focus of ultrafast pulse laser field.
Graphene is a kind of new carbon, by the level and smooth film of the tightly packed one-tenth bi-dimensional cellular of monolayer carbon atom shape.Graphene, due to its special structure, is all having excellent characteristic, such as interband optical transition and general light conductivity etc. aspect mechanics, electricity and optics.The conduction band of Graphene and valence band are contacted with the dirac point, and this zero bandgap structure can be to all non-selectivity absorptions of light of all wave bands.This has just determined that Graphene is as the saturated absorption modulation element, is a kind of multifunctional material that application prospect is arranged at many modern photonic propulsions field utmost points such as ultrafast pulse generation, optical fiber soliton communication, optical switches.
In the light path of all-solid state laser, during the low power output of laser, Graphene is more stable, has the saturated absorption characteristic, and the stable mode-locking Laser output is arranged; But (the spot diameter 50-300 micron of laser during the laser high-output power, power reaches 100W, power density is very high), airborne oxygen molecule preferentially reacts with the carbon atom of the defective locations that is positioned at Graphene, cause burning Graphene, make it lose the saturated absorption characteristic, do not have mode-locked laser output.Burning the problem of Graphene in order to solve high power laser light, have the researcher to adopt nitrogen to cover the method on Graphene surface, is exactly constantly to blow at the trial the surface of Graphene with nitrogen, stops Graphene to contact with oxygen, reaches the purpose that improves power output.But need not stop nitrogen in its experimentation, and experimental facilities more complicated.
Summary of the invention
For the problems referred to above, the purpose of this invention is to provide high, the large-area sandwich style Graphene of a kind of simple, efficient, anti-damage threshold saturated absorbing body and preparation method thereof, Graphene in prepared saturable absorber can keep complete chemical constitution, the size of Graphene is in a centimetre magnitude, key point is Graphene and the isolation of airborne oxygen molecule, improves the anti-light injury threshold of Graphene.
For achieving the above object, the present invention takes following technical scheme:
Sandwich style Graphene saturated absorbing body, comprise the graphene layer and the upper strata backing material that are covered with on back lining bottom material, back lining bottom material, and three layers of close contact are sandwiched type structure, and the sandwiched type structure periphery has the even coat of fluid sealant.
Described backing material is the transparent materials such as the thickness quartz that is 0.1-0.5mm, sapphire, glass.
Described fluid sealant is rubber-type, resin type etc.
The preparation method of above-mentioned sandwich style Graphene saturated absorbing body comprises that step is as follows:
(1) graphene film of deposited monolayers on Copper Foil;
(2) wet method shifts: the Cu paper tinsel that will deposit Graphene cuts into square, and even spin coating PMMA, dry thereon, then puts into FeCl
3soaking at room temperature in solution, until Graphene and PMMA film come off from the Cu substrate, and by the Cu corrosion fully, move to Graphene and PMMA film in deionized water solution and move on transparent substrates after rinsing 5-50min, treats natural drying post-drying; The PMMA of oven dry and Graphene and transparent substrates are placed in to acetone soln, until that PMMA removes is clean, then utilize ethanol to clean and natural drying;
(3) get identical backing material and be placed on the backing material with Graphene, compress, get rid of the air between backing material, fluid sealant is coated in around backing material uniformly to the Graphene saturated absorbing body of the formula that sandwiches.
Step (1) concrete steps of the graphene film of deposited monolayers on Copper Foil are: the Cu paper tinsel is placed in to the quartz ampoule flat-temperature zone, by after the quartz ampoule sealing, the air pressure in quartz ampoule is evacuated to ultimate vacuum state 1-4 * 10
-4handkerchief, heat simultaneously temperature risen to growth temperature 800-1100 ℃; Pass into hydrogen annealing 1-30 minute after reaching growth temperature, pass into afterwards methane or acetylene carbon-source gas; After growth 10-100 minutes, close carbon-source gas fast cooling under atmosphere of hydrogen.
The intake of described hydrogen, carbon-source gas is respectively 10-100sccm, 10-300sccm.
The described square length of side of step (2) is preferably 10-20mm.Described oven dry is on the heating plate that is placed in 100-300 ℃ and toasts 5-50min.Described FeCl
3the concentration range of solution is 0.2-1.5mol/L.
Advantage of the present invention is as follows:
(1) adopt Graphene as saturated absorbing body, can be for different wave length;
(2) oxygen in Graphene and outside air is separated from each other, avoid Graphene under Ear Mucosa Treated by He Ne Laser Irradiation with oxygen generation oxidation reaction, improve the anti-light injury threshold of Graphene, finally improve the power output of pulse laser; It is compared with non-sandwich structure Graphene saturated absorbing body and improves power output 40%.
(3) adopt Graphene to have advantages of that as saturated absorbing body saturation intensity is low, recovery time is short, scattering loss is little, damage threshold is high;
(4) preparation process of the present invention is simple, with low cost, is easy to practical application.
The accompanying drawing explanation
Fig. 1 is the structure chart that the embodiment of the present invention 1 prepares the Graphene saturable absorber;
Fig. 2 is the Raman spectrum that the embodiment of the present invention 1 prepares the Graphene saturable absorber;
Fig. 3 is that the embodiment of the present invention 1 prepares the pulse train that Graphene saturable absorber locked mode produces;
Wherein 1. graphene layers, 2. fluid sealant, 3. backing material.
Embodiment
Below in conjunction with accompanying drawing, the preferred embodiments of the present invention are described, should be appreciated that preferred embodiment described herein only limits to interpretation the present invention, is not intended to limit the present invention.Described material all can obtain from open commercial sources if no special instructions.
A kind of preparation method of sandwich style Graphene saturated absorbing body comprises the following steps:
(1) adopt the CVD method to prepare single-layer graphene on the Cu paper tinsel, concrete operations are: the Cu paper tinsel is placed in to the quartz ampoule flat-temperature zone, by after quartz ampoule sealing fully; Utilize vacuum pump that the air pressure in quartz ampoule is evacuated to ultimate vacuum state 3 * 10
-6holder rises to temperature 1050 ℃ of growth temperatures simultaneously; Reach after growth temperature the hydrogen annealing 30 minutes that passes into 50sccm, pass into afterwards the methane gas of 50sccm; After growth 50min, close carbon-source gas fast cooling under atmosphere of hydrogen.
(2) utilize the wet method transfer techniques that Graphene is transferred on glass substrate, concrete operations are: the Cu paper tinsel that will deposit Graphene cuts into 15mm * 15mm square, having even spin coating PMMA on the square Cu paper tinsel of Graphene, be placed on afterwards on the heating plate of 130 ℃ and toast 30min, then put into FeCL
3soaking at room temperature in solution, until Graphene+PMMA film comes off from the Cu substrate, and by the Cu corrosion fully.Graphene+PMMA film is moved in deionized water solution and moves on transparent substrates after rinsing 30min, treat natural dryingly, be placed on the heating plate of 130 ℃ and toast 30min.PMMA+ Graphene+the transparent substrates of oven dry is placed in to acetone soln, until PMMA removes totally, then utilizes ethanol to clean also natural drying.
(3) as shown in Figure 1, get identical glass substrate material 3, be placed on the glass substrate material 3 with Graphene 1, compress, get rid of the air between backing material, fluid sealant 2 is coated in around backing material uniformly to the Graphene saturated absorbing body of the formula that sandwiches.
The Raman spectrum of the saturable absorbing mirror of Graphene shown in Fig. 2, show that the large tracts of land Graphene is not received destruction in preparation process, keep the individual layer integrality, and the number of plies of Graphene is one deck.Be placed in 1064nm Nd:YAG laser shown in Fig. 3, can obtain passive mode locking pulse train.
A kind of preparation method of sandwich style Graphene saturated absorbing body comprises the following steps:
(1) adopt the CVD method to prepare single-layer graphene on the Cu paper tinsel, concrete operations are: the Cu paper tinsel is placed in to the quartz ampoule flat-temperature zone, by after quartz ampoule sealing fully; Utilize vacuum pump that the air pressure in quartz ampoule is evacuated to ultimate vacuum state 2 * 10
-6holder rises to temperature 1000 ℃ of growth temperatures simultaneously; Reach after growth temperature the hydrogen annealing 30 minutes that passes into 50sccm, pass into afterwards the methane gas of 50sccm; After growth 50min, close carbon-source gas fast cooling under atmosphere of hydrogen.
(2) utilize the wet method transfer techniques that Graphene is transferred on glass substrate, concrete operations are: the Cu paper tinsel that will deposit Graphene cuts into 20mm * 20mm square, having even spin coating PMMA on the square Cu paper tinsel of Graphene, be placed on afterwards on the heating plate of 100 ℃ and toast 50min, then put into FeCL
3soaking at room temperature in solution, until Graphene+PMMA film comes off from the Cu substrate, and by the Cu corrosion fully.Graphene+PMMA film is moved in deionized water solution and moves on transparent substrates after rinsing 30min, treat natural dryingly, be placed on the heating plate of 150 ℃ and toast 30min.PMMA+ Graphene+the transparent substrates of oven dry is placed in to acetone soln, until PMMA removes totally, then utilizes ethanol to clean also natural drying.
(3) as shown in Figure 1, get identical quartz substrate material 3, be placed on the quartz substrate material 3 with Graphene 1, compress, get rid of the air between backing material, fluid sealant 2 is coated in around backing material uniformly to the Graphene saturated absorbing body of the formula that sandwiches.
Insert in laser, can obtain the similar passive mode locking pulse train with Fig. 3.
Claims (8)
1. sandwich style Graphene saturated absorbing body, comprise the graphene layer and the upper strata backing material that are covered with on back lining bottom material, back lining bottom material, and three layers of close contact are sandwiched type structure, and the sandwiched type structure periphery has the even coat of fluid sealant.
2. sandwich style Graphene saturated absorbing body according to claim 1, is characterized in that, described backing material is quartz, sapphire or glass transparent material.
3. the preparation method of sandwich style Graphene saturated absorbing body claimed in claim 1, is characterized in that, comprises that step is as follows:
(1) graphene film of deposited monolayers on Copper Foil;
(2) wet method shifts: the Cu paper tinsel that will deposit Graphene cuts into square, and even spin coating PMMA, dry thereon, then puts into FeCl
3soaking at room temperature in solution, until Graphene and PMMA film come off from the Cu substrate, and by the Cu corrosion fully, move to Graphene and PMMA film in deionized water solution and move on transparent substrates after rinsing 5-50min, treats natural drying post-drying; The PMMA of oven dry and Graphene and transparent substrates are placed in to acetone soln, until that PMMA removes is clean, then utilize ethanol to clean and natural drying;
(3) get identical backing material and be placed on the backing material with Graphene, compress, get rid of the air between backing material, fluid sealant is coated in around backing material uniformly to the Graphene saturated absorbing body of the formula that sandwiches.
4. the preparation method of sandwich style Graphene saturated absorbing body according to claim 3, it is characterized in that, step (1) concrete steps of the graphene film of deposited monolayers on Copper Foil are: the Cu paper tinsel is placed in to the quartz ampoule flat-temperature zone, by after the quartz ampoule sealing, the air pressure in quartz ampoule is evacuated to ultimate vacuum state 1-4 * 10
-4handkerchief, heat simultaneously temperature risen to growth temperature 800-1100 ℃; Pass into hydrogen annealing 1-30 minute after reaching growth temperature, pass into afterwards methane or acetylene carbon-source gas; After growth 10-100 minutes, close carbon-source gas fast cooling under atmosphere of hydrogen.
5. the preparation method of sandwich style Graphene saturated absorbing body according to claim 4, is characterized in that, the intake of described hydrogen, carbon-source gas is respectively 10-100sccm, 10-300sccm.
6. the preparation method of sandwich style Graphene saturated absorbing body according to claim 3, is characterized in that, the described square length of side of step (2) is 10-20mm.
7. the preparation method of sandwich style Graphene saturated absorbing body according to claim 3, is characterized in that, described oven dry is on the heating plate that is placed in 100-300 ℃ and toasts 5-50min.
8. the preparation method of sandwich style Graphene saturated absorbing body according to claim 3, is characterized in that, described FeCl
3the concentration range of solution is 0.2-1.5mol/L.
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Cited By (6)
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| CN104836103A (en) * | 2015-04-14 | 2015-08-12 | 苏州大学 | Method for preparing saturable absorber device based on black phosphorus |
| CN105161967A (en) * | 2014-05-28 | 2015-12-16 | 香港理工大学 | Carbon nanomaterial film saturable absorber and preparation method thereof |
| CN105207051A (en) * | 2014-05-28 | 2015-12-30 | 香港理工大学 | Carbon nano-material film saturation absorber and preparation method thereof |
| CN107014799A (en) * | 2017-03-24 | 2017-08-04 | 山东师范大学 | A kind of graphene/silver nano flower-like/PMMA " sandwich " structural flexibility SERS substrates and preparation method thereof |
| CN109149347A (en) * | 2018-09-11 | 2019-01-04 | 中国科学院上海光学精密机械研究所 | Wide range optical time domain apparatus for shaping |
| CN114203326A (en) * | 2021-12-13 | 2022-03-18 | 中国核动力研究设计院 | Graphene-packaged ultrathin nickel-63 radiation source film and preparation method and application thereof |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN104836103B (en) * | 2015-04-14 | 2017-10-27 | 苏州大学 | A kind of method of the saturable absorber device prepared based on black phosphorus |
| CN107014799A (en) * | 2017-03-24 | 2017-08-04 | 山东师范大学 | A kind of graphene/silver nano flower-like/PMMA " sandwich " structural flexibility SERS substrates and preparation method thereof |
| CN107014799B (en) * | 2017-03-24 | 2020-09-01 | 山东师范大学 | Graphene/silver nanoflower/PMMA sandwich structure flexible SERS substrate and preparation method thereof |
| CN109149347A (en) * | 2018-09-11 | 2019-01-04 | 中国科学院上海光学精密机械研究所 | Wide range optical time domain apparatus for shaping |
| CN109149347B (en) * | 2018-09-11 | 2020-10-16 | 中国科学院上海光学精密机械研究所 | Wide-spectrum optical time domain shaping device |
| CN114203326A (en) * | 2021-12-13 | 2022-03-18 | 中国核动力研究设计院 | Graphene-packaged ultrathin nickel-63 radiation source film and preparation method and application thereof |
| CN114203326B (en) * | 2021-12-13 | 2024-04-30 | 中国核动力研究设计院 | Graphene-encapsulated ultrathin nickel-63 radiation source film and preparation method and application thereof |
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