CN109346919A - Include silver sulfide/vulcanization silver-colored zinc core-shell quanta dots coffee cyclic laser and preparation method thereof - Google Patents
Include silver sulfide/vulcanization silver-colored zinc core-shell quanta dots coffee cyclic laser and preparation method thereof Download PDFInfo
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- CN109346919A CN109346919A CN201811199503.0A CN201811199503A CN109346919A CN 109346919 A CN109346919 A CN 109346919A CN 201811199503 A CN201811199503 A CN 201811199503A CN 109346919 A CN109346919 A CN 109346919A
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- silver
- silver sulfide
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01S—DEVICES USING THE PROCESS OF LIGHT AMPLIFICATION BY STIMULATED EMISSION OF RADIATION [LASER] TO AMPLIFY OR GENERATE LIGHT; DEVICES USING STIMULATED EMISSION OF ELECTROMAGNETIC RADIATION IN WAVE RANGES OTHER THAN OPTICAL
- H01S5/00—Semiconductor lasers
- H01S5/10—Construction or shape of the optical resonator, e.g. extended or external cavity, coupled cavities, bent-guide, varying width, thickness or composition of the active region
- H01S5/1042—Optical microcavities, e.g. cavity dimensions comparable to the wavelength
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01S—DEVICES USING THE PROCESS OF LIGHT AMPLIFICATION BY STIMULATED EMISSION OF RADIATION [LASER] TO AMPLIFY OR GENERATE LIGHT; DEVICES USING STIMULATED EMISSION OF ELECTROMAGNETIC RADIATION IN WAVE RANGES OTHER THAN OPTICAL
- H01S5/00—Semiconductor lasers
- H01S5/30—Structure or shape of the active region; Materials used for the active region
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Abstract
Silver sulfide/vulcanization silver-colored zinc core-shell quanta dots coffee cyclic laser and preparation method thereof is included the invention discloses a kind of, which includes the quartz base plate being arranged upwards in turn, includes silver sulfide/vulcanization silver-colored zinc core-shell quanta dots silica annulus.The present invention substitutes the lead salt quantum dot of the minimum weight of quantum state 8 degeneracy using the silver sulfide quantum dot of the 2 weight degeneracy of minimum quantum state of low toxicity, to realize the near infrared light gain of Low threshold, by coating the silver sulfide kirsite shell that Zn-ef ficiency content gradually increases from inside to outside in silver sulfide quantum dot surface, it constructs the surface of gentle interface potential barrier and passivation silver sulfide quantum dot, gain of light threshold value can be further decreased.Quantum dot is embedded in stability and the service life that can be improved laser in silica.Coffee ring is prepared with the mixed liquor of silver sulfide/vulcanization silver-colored zinc core-shell quanta dots and Perhydropolysilazane, can finally obtain Low threshold, high stability and environmental-friendly coffee ring near-infrared quantum dot laser.
Description
Technical field
Silver sulfide/vulcanization silver-colored zinc core-shell quanta dots coffee cyclic laser and its preparation side are included the present invention relates to a kind of
Method belongs to the technical field of semiconductor photoelectronic device.
Background technique
Near infrared laser can be widely applied to the fields such as optic communication, remote sensing and the generation of relevant plasma.The amount of benefiting from
Sub- confinement effect, semiconductor-quantum-point has shown a variety of superior performances as optical gain material, such as launch wavelength is with ruler
The laser activity of very little adjustable, potential low laser threshold and temperature-insensitive.Currently, utilizing the close red of molecular beam epitaxy preparation
Outer quantum dot laser has begun business application.Compared to the quantum dot of epitaxial growth, Colloidal Quantum Dots have smaller ruler
Very little and more uniform size distribution, thus there is stronger quantum confined effect and narrower emission peak.The most common near-infrared
Emitting Colloidal Quantum Dots is lead salt (vulcanized lead, lead selenide and lead telluride) quantum dot.They are rock-salt type structure, in Brillouin zone
L point have 4 equivalent energy band minimum values.Considering that 2 spin degeneracy again, the minimum quantum state of lead salt quantum dot is 8 weight degeneracys,
Exciton number in average each quantum dot will be more than 4 to be just able to achieve population inversion.This makes the gain of light threshold value of lead salt quantum dot
It is high, it is difficult to realize the gain of light.Currently, there is an urgent need to search out the novel Colloidal Quantum Dots of one kind to realize the close red of Low threshold
The outer gain of light.
In recent years, the silver sulfide quantum dot of less toxic 2 weight degeneracy of minimum quantum state in the second infrared window due to having
Excellent photoluminescent property and cause strong concern.At present about the research of silver sulfide quantum dot focus on mostly preparation method with
And in-vivo imaging, it is not yet had been reported that in the potential application of laser field.
Only replace lead salt quantum dot that can't obtain optimal near infrared light gain with silver sulfide quantum dot.In colloid amount
Auger recombination is very efficient in son point, this makes the gain of light threshold value of Colloidal Quantum Dots be higher than the quantum dot of epitaxial growth, hinders
The development of Colloidal Quantum Dots laser.
Coffee ring quantum dot laser be it is a kind of it is novel, preparation process is simple and supports the laser of single-mode output.Currently,
Coffee ring quantum dot laser is as made from being added on quartz base plate the toluene dispersant liquid drop of a droplet quantum dot mostly.
The evaporation dynamics of drop will be left a well-defined micron-scale by the domination of coffee ring effect in substrate after evaporation
Annulus.This annulus is made of the quantum dot of dense accumulation, and the refractive index cataclysm of its boundary will bring very strong light anti-
Feedback, the section constitution Fabry-Perot-type cavity of annulus, light field vibrate and amplify between the inner and outer boundary of annulus.However, directly will amount
Son point exposure can reduce stability and the service life of laser in air.
Summary of the invention
The object of the present invention is to provide it is a kind of include silver sulfide/vulcanization silver-colored zinc core-shell quanta dots coffee cyclic laser and its
Preparation method, to obtain Low threshold, high stability and environmental-friendly coffee ring near-infrared quantum dot laser.
To achieve the above object, the technical solution adopted by the present invention are as follows:
It is a kind of to include silver sulfide/vulcanization silver-colored zinc core-shell quanta dots coffee cyclic laser, including the stone being arranged upwards in turn
English substrate includes silver sulfide/vulcanization silver-colored zinc core-shell quanta dots silica annulus.
Silver sulfide/vulcanization silver-colored zinc core-shell quanta dots silica annulus that includes should by silica annulus and insertion
Silver sulfide/vulcanization silver-colored zinc core-shell quanta dots composition in silica annulus.
The silver sulfide/vulcanization silver-colored zinc core-shell quanta dots are uniformly distributed in silica annulus.
The silver sulfide/vulcanization silver-colored zinc core-shell quanta dots are by silver sulfide quantum dot and are coated on the silver sulfide quantum dot table
The silver sulfide kirsite shell in face forms.
The Zn-ef ficiency content of the silver sulfide kirsite shell gradually increases from inside to outside.
The silver sulfide/vulcanization silver-colored zinc core-shell quanta dots are as optical gain medium.
A kind of preparation method including silver sulfide/vulcanization silver-colored zinc core-shell quanta dots coffee cyclic laser, including following step
It is rapid:
(1) silver sulfide quantum dot is prepared using high temperature thermal decomposition method；
(2) SILAR method is utilized, by being gradually reduced the injection rate of silver ion precursor while increasing
The injection rate of zincification ion precursor, in the sulphur that silver sulfide quantum dot surface cladding Zn-ef ficiency content gradually increases from inside to outside
Change silver-colored zinc alloy shell, obtains silver sulfide/vulcanization silver-colored zinc core-shell quanta dots；
(3) it disperses silver sulfide/vulcanization silver-colored zinc core-shell quanta dots that step (2) obtains in toluene, then by silver sulfide/sulphur
The toluene dispersion liquid for changing silver-colored zinc core-shell quanta dots is mixed with Perhydropolysilazane, is then added drop-wise on quartz base plate to be included
Silver sulfide/vulcanization silver-colored zinc core-shell quanta dots silica annulus.
The utility model has the advantages that
Silver sulfide quantum dot is monocline crystal phase, and minimum quantum state only has 2 to spin again degeneracy, can be realized the close red of Low threshold
The outer gain of light.Research shows that interface potential barrier gentle between core and shell material can make Auger rate reduce 3 orders of magnitude or more, subtract
Few boundary defect can also significantly inhibit auger recombination.Therefore, if silver sulfide quantum dot surface coat Zn-ef ficiency content from it is interior to
The silver sulfide kirsite shell gradually increased outside can to construct the surface of gentle interface potential barrier and passivation silver sulfide quantum dot
Auger recombination is inhibited to further decrease gain of light threshold value.
Quantum dot is embedded in silica to be able to solve, quantum dot exposure directly can be reduced into laser in air
The problem of stability and service life.Perhydropolysilazane is a kind of novel coating material, can be at room temperature in atmospheric atmosphere
It is converted into inorganic silicon dioxide.Preparing coffee ring with the mixed liquor of quantum dot and Perhydropolysilazane can obtain in high quality
Silica annulus containing quantum dot, to improve stability and the service life of coffee ring quantum dot laser.
The present invention substitutes the heavy degeneracy of minimum quantum state 8 using the silver sulfide quantum dot of the 2 weight degeneracy of minimum quantum state of low toxicity
Lead salt quantum dot, to realize the near infrared light gain of Low threshold, by silver sulfide quantum dot surface coat Zn-ef ficiency content
The silver sulfide kirsite shell gradually increased from inside to outside, to construct the table of gentle interface potential barrier and passivation silver sulfide quantum dot
Face can further decrease gain of light threshold value.Quantum dot is embedded in stability and the longevity that can be improved laser in silica
Life.Coffee ring is prepared with the mixed liquor of silver sulfide/vulcanization silver-colored zinc core-shell quanta dots and Perhydropolysilazane, can finally be obtained low
Threshold value, high stability and environmental-friendly coffee ring near-infrared quantum dot laser.
Detailed description of the invention
Fig. 1 is silver sulfide/vulcanization silver-colored zinc core-shell quanta dots structural schematic diagram；
Fig. 2 is the structural schematic diagram for including silver sulfide/vulcanization silver-colored zinc core-shell quanta dots coffee cyclic laser.
In figure: 1- silver sulfide quantum dot, 2- silver sulfide kirsite shell, 3- quartz base plate, 4- include silver sulfide/vulcanization silver-colored zinc
The silica annulus of core-shell quanta dots.
Specific embodiment
Further explanation is done to the present invention with reference to the accompanying drawing.
Silver sulfide/vulcanization silver-colored zinc core-shell quanta dots coffee cyclic laser is included as shown in Fig. 2, of the invention, including according to
The secondary quartz base plate 3 set up includes silver sulfide/vulcanization silver-colored zinc core-shell quanta dots silica annulus 4.
Include silver sulfide/vulcanization silver-colored zinc core-shell quanta dots silica annulus 4 by silica annulus and be embedded in this two
Silver sulfide/vulcanization silver-colored zinc core-shell quanta dots composition in silica annulus.Silver sulfide/vulcanization silver-colored zinc core-shell quanta dots are in titanium dioxide
It is uniformly distributed in silicon annulus.As shown in Figure 1, silver sulfide/vulcanization silver-colored zinc core-shell quanta dots by silver sulfide quantum dot 1 and are coated on
The silver sulfide kirsite shell 2 on 1 surface of silver sulfide quantum dot forms.The Zn-ef ficiency content of silver sulfide kirsite shell 2 is from inside to outside
It gradually increases.Silver sulfide/vulcanization silver-colored zinc core-shell quanta dots are optical gain mediums, and less toxic minimum quantum state only has 2 spin letters again
And silver sulfide quantum dot 1, can be realized the near infrared light gain of Low threshold, by 1 surface of silver sulfide quantum dot coat zinc
The silver sulfide kirsite shell 2 that constituent content gradually increases from inside to outside, to construct gentle interface potential barrier and passivation vulcanization silver content
The surface of son point 1, can further decrease gain of light threshold value.Silver sulfide/vulcanization silver-colored zinc core-shell quanta dots are embedded in silica
In can be improved stability and the service life of coffee ring quantum dot laser.Have benefited from including the silica ring edges of quantum dot
The refractive index cataclysm at place, light field is between the inner and outer boundary of interior Containing Sulfur silver/vulcanization silver-colored zinc core-shell quanta dots silica annulus 4
Oscillation and amplification.
The preparation method for including silver sulfide/vulcanization silver-colored zinc core-shell quanta dots coffee cyclic laser of the invention, including with
Lower step:
(1) the silver sulfide quantum dot of near infrared emission is prepared using high temperature thermal decomposition method；
(2) utilize SILAR method, by 2 hours reaction process by concentration be 0.1 mM/
The injection rate of the silver ion precursor of milliliter gradually decreases to 0.5 ml/hour from 5 mls/hour, while being by concentration
The injection rate of the zinc ion precursor of 0.1 mM/milliliter progressively increases to 5 mls/hour from 0.5 ml/hour, 2
The silver sulfide kirsite shell that micromolar silver sulfide quantum dot surface cladding Zn-ef ficiency content gradually increases from inside to outside, obtains sulphur
Change silver/vulcanization silver-colored zinc core-shell quanta dots；
(3) it disperses silver sulfide/vulcanization silver-colored zinc core-shell quanta dots that step (2) obtains in toluene by the mass ratio of 1:5,
Silver sulfide/vulcanization silver-colored zinc core-shell quanta dots toluene dispersion liquid is mixed with Perhydropolysilazane by the mass ratio of 1:1 again, then
It is added drop-wise on quartz base plate to obtain and includes silver sulfide/vulcanization silver-colored zinc core-shell quanta dots silica annulus.
The above is only a preferred embodiment of the present invention, it is noted that for the ordinary skill people of the art
For member, various improvements and modifications may be made without departing from the principle of the present invention, these improvements and modifications are also answered
It is considered as protection scope of the present invention.
Claims (7)
1. a kind of include silver sulfide/vulcanization silver-colored zinc core-shell quanta dots coffee cyclic laser, it is characterised in that: including upwards in turn
The quartz base plate (3) of setting includes silver sulfide/vulcanization silver-colored zinc core-shell quanta dots silica annulus (4).
2. according to claim 1 include silver sulfide/vulcanization silver-colored zinc core-shell quanta dots coffee cyclic laser, feature exists
In: it is described include silver sulfide/vulcanization silver-colored zinc core-shell quanta dots silica annulus (4) by silica annulus and be embedded in this two
Silver sulfide/vulcanization silver-colored zinc core-shell quanta dots composition in silica annulus.
3. according to claim 2 include silver sulfide/vulcanization silver-colored zinc core-shell quanta dots coffee cyclic laser, feature exists
In: the silver sulfide/vulcanization silver-colored zinc core-shell quanta dots are uniformly distributed in silica annulus.
4. according to claim 2 include silver sulfide/vulcanization silver-colored zinc core-shell quanta dots coffee cyclic laser, feature exists
In: the silver sulfide/vulcanization silver-colored zinc core-shell quanta dots are by silver sulfide quantum dot (1) and are coated on the silver sulfide quantum dot (1)
The silver sulfide kirsite shell (2) on surface forms.
5. according to claim 4 include silver sulfide/vulcanization silver-colored zinc core-shell quanta dots coffee cyclic laser, feature exists
In: the Zn-ef ficiency content of the silver sulfide kirsite shell (2) gradually increases from inside to outside.
6. according to claim 1 include silver sulfide/vulcanization silver-colored zinc core-shell quanta dots coffee cyclic laser, feature exists
In: the silver sulfide/vulcanization silver-colored zinc core-shell quanta dots are as optical gain medium.
7. a kind of preparation method for including silver sulfide/vulcanization silver-colored zinc core-shell quanta dots coffee cyclic laser, it is characterised in that: packet
Include following steps:
(1) silver sulfide quantum dot is prepared using high temperature thermal decomposition method；
(2) SILAR method is utilized, by being gradually reduced the injection rate of silver ion precursor while increasing zinc
The injection rate of ion precursor, in the silver sulfide that silver sulfide quantum dot surface cladding Zn-ef ficiency content gradually increases from inside to outside
Kirsite shell obtains silver sulfide/vulcanization silver-colored zinc core-shell quanta dots；
(3) it disperses silver sulfide/vulcanization silver-colored zinc core-shell quanta dots that step (2) obtains in toluene, then by silver sulfide/silver sulfide
The toluene dispersion liquid of zinc core-shell quanta dots is mixed with Perhydropolysilazane, is then added drop-wise on quartz base plate to obtain interior Containing Sulfur
Silver/vulcanization silver-colored zinc core-shell quanta dots silica annulus.
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201811199503.0A CN109346919A (en) | 2018-10-15 | 2018-10-15 | Include silver sulfide/vulcanization silver-colored zinc core-shell quanta dots coffee cyclic laser and preparation method thereof |
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| Application Number | Priority Date | Filing Date | Title |
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| CN201811199503.0A CN109346919A (en) | 2018-10-15 | 2018-10-15 | Include silver sulfide/vulcanization silver-colored zinc core-shell quanta dots coffee cyclic laser and preparation method thereof |
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Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102718180A (en) * | 2012-06-28 | 2012-10-10 | 中国科学院苏州纳米技术与纳米仿生研究所 | Concentric ring core nano silicon micro-disk micro-cavity device and preparation method thereof |
| CN106199789A (en) * | 2015-07-22 | 2016-12-07 | 宁波激智科技股份有限公司 | A kind of prism film of stimulated luminescence |
-
2018
- 2018-10-15 CN CN201811199503.0A patent/CN109346919A/en active Pending
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102718180A (en) * | 2012-06-28 | 2012-10-10 | 中国科学院苏州纳米技术与纳米仿生研究所 | Concentric ring core nano silicon micro-disk micro-cavity device and preparation method thereof |
| CN106199789A (en) * | 2015-07-22 | 2016-12-07 | 宁波激智科技股份有限公司 | A kind of prism film of stimulated luminescence |
Non-Patent Citations (1)
| Title |
|---|
| 廖晨: ""金属表面、光学多层膜和谐振腔对量子点光学性质的调制特性研究"", 《中国博士学位论文全文数据库 基础科学辑》 * |
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Application publication date: 20190215 |
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