CN109167252A - Include micro- disk cavity laser of silver sulfide/vulcanization silver-colored zinc core-shell quanta dots and preparation method thereof - Google Patents
Include micro- disk cavity laser of silver sulfide/vulcanization silver-colored zinc core-shell quanta dots and preparation method thereof Download PDFInfo
- Publication number
- CN109167252A CN109167252A CN201811193810.8A CN201811193810A CN109167252A CN 109167252 A CN109167252 A CN 109167252A CN 201811193810 A CN201811193810 A CN 201811193810A CN 109167252 A CN109167252 A CN 109167252A
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- China
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- silver
- silver sulfide
- vulcanization
- quanta dots
- colored zinc
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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
-
- 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
Abstract
Micro- disk cavity laser of silver sulfide/vulcanization silver-colored zinc core-shell quanta dots and preparation method thereof is included the invention discloses a kind of, which includes the silicon substrate being arranged upwards in turn, silicon cylinder and include silver sulfide/vulcanization silver-colored zinc core-shell quanta dots silica discs.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 silica to can be avoided and coats the decline of quantum dot bring quality factor on micro- disk chamber.Micro- disk chamber is prepared with silver sulfide/vulcanization silver-colored zinc core-shell quanta dots silica membrane is included, can finally obtain Low threshold, high-quality-factor and environmental-friendly micro- disk chamber near-infrared quantum dot laser.
Description
Technical field
The micro- disk cavity laser of silver sulfide/vulcanization silver-colored zinc core-shell quanta dots 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.
Micro- disk cavity laser has many advantages, such as that quality factor is high, prepares convenient and integrability.However Colloidal Quantum Dots with
The coupling of micro- disk chamber could not be realized always well.Currently, most common way is that quantum dot is coated in the dioxy prepared
On the micro- disk chamber of SiClx, the quality factor of micro- disk chamber can be significantly reduced in this way.
Summary of the invention
The object of the present invention is to provide it is a kind of include the micro- disk cavity laser of silver sulfide/vulcanization silver-colored zinc core-shell quanta dots and its
Preparation method, to obtain Low threshold, high-quality-factor and environmental-friendly micro- disk chamber 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 the micro- disk cavity laser of silver sulfide/vulcanization silver-colored zinc core-shell quanta dots, including the silicon being arranged upwards in turn
Substrate, silicon cylinder and include silver sulfide/vulcanization silver-colored zinc core-shell quanta dots silica discs.
Silver sulfide/vulcanization silver-colored zinc core-shell quanta dots silica discs that include should by silica discs and insertion
Silver sulfide/vulcanization silver-colored zinc core-shell quanta dots composition in silica discs.
The silver sulfide/vulcanization silver-colored zinc core-shell quanta dots are uniformly distributed in silica discs.
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.
The area of the silicon cylinder upper bottom surface, which is less than, includes silver sulfide/vulcanization silver-colored zinc core-shell quanta dots silica discs
The area of bottom surface.
A kind of preparation method including the micro- disk cavity laser of silver sulfide/vulcanization silver-colored zinc core-shell quanta dots, 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 spin coated on silicon substrate to obtain interior content
The silicon dioxide film of son point；
(4) silver sulfide/vulcanization silver-colored zinc core-shell quanta dots silicon dioxide film will be included using reactive ion dry etching to carve
It loses into and includes silver sulfide/vulcanization silver-colored zinc core-shell quanta dots silica discs；
(5) the silicon cylinder of support silica discs is obtained with the silicon below xenon difluoride etching silicon dioxide disk.
The utility model has the advantages that silver sulfide quantum dot is monocline crystal phase, minimum quantum state only has 2 to spin again degeneracy, can be realized low
The near infrared light gain of threshold value.Research shows that interface potential barrier gentle between core and shell material can make Auger rate reduce 3 numbers
More than magnitude, auger recombination can also be significantly inhibited by reducing boundary defect.Therefore, if coating Zn-ef ficiency in silver sulfide quantum dot surface
The silver sulfide kirsite shell that content gradually increases from inside to outside, to construct gentle interface potential barrier and passivation silver sulfide quantum dot
Surface is able to suppress auger recombination and further decreases gain of light threshold value.
Quantum dot, which is embedded in silica, can be avoided coats under quantum dot bring quality factor on micro- disk chamber
Drop.Perhydropolysilazane is a kind of novel coating material, can be converted into inorganic titanium dioxide at room temperature in atmospheric atmosphere
Silicon.The mixed liquor of spin coating quantum dot and Perhydropolysilazane can obtain the silica membrane for including quantum dot of high quality,
Condition is provided to prepare micro- disk chamber quantum dot laser of high-quality-factor.
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 can be avoided in silica and coats quantum on micro- disk chamber
Point bring quality factor decline.Micro- disk chamber is prepared with silver sulfide/vulcanization silver-colored zinc core-shell quanta dots silica membrane is included,
Low threshold, high-quality-factor and environmental-friendly micro- disk chamber near-infrared quantum dot laser can finally be obtained.
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 the micro- disk cavity laser of silver sulfide/vulcanization silver-colored zinc core-shell quanta dots.
In figure: 1- silver sulfide quantum dot, 2- silver sulfide kirsite shell, 3- silicon substrate, 4- silicon cylinder, 5- include silver sulfide/
Vulcanize the silica discs of silver-colored zinc core-shell quanta dots.
Specific embodiment
Further explanation is done to the present invention with reference to the accompanying drawing.
As described in Figure 2, of the invention to include the micro- disk cavity laser of silver sulfide/vulcanization silver-colored zinc core-shell quanta dots, including according to
The secondary silicon substrate 3 set up, silicon cylinder 4 and include silver sulfide/vulcanization silver-colored zinc core-shell quanta dots silica discs 5.
Include silver sulfide/vulcanization silver-colored zinc core-shell quanta dots silica discs 5 by silica discs and be embedded in this two
Silver sulfide/vulcanization silver-colored zinc core-shell quanta dots composition in silica discs.Silver sulfide/vulcanization silver-colored zinc core-shell quanta dots are in titanium dioxide
It is uniformly distributed in silicon disk.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 avoided on micro- disk chamber coat quantum dot bring quality factor decline.Have benefited from including the silica circle of quantum dot
The refringence of disk and air, light field is along the inner sidewall for including silver sulfide/vulcanization silver-colored zinc core-shell quanta dots silica discs 5
Oscillation and amplification.
The area of 4 upper bottom surface of silicon cylinder, which is less than, to be included under silver sulfide/vulcanization silver-colored zinc core-shell quanta dots silica discs 5
The area of bottom surface, silicon cylinder 4 will include silver sulfide/vulcanization silver-colored zinc core-shell quanta dots silica discs 5 and silicon base 3 every
From prevention light field leaks into silicon base 3 from silver sulfide/vulcanization silver-colored zinc core-shell quanta dots silica discs 5 are included.
The preparation method for including the micro- disk cavity laser of silver sulfide/vulcanization silver-colored zinc core-shell quanta dots 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 spun on silicon substrate and obtains the silicon dioxide film for including quantum dot；
(4) silver sulfide/vulcanization silver-colored zinc core-shell quanta dots silicon dioxide film will be included using reactive ion dry etching to carve
It loses into and includes silver sulfide/vulcanization silver-colored zinc core-shell quanta dots silica discs；
(5) the silicon cylinder of support silica discs is obtained with the silicon below xenon difluoride etching silicon dioxide disk.
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 (8)
1. a kind of include the micro- disk cavity laser of silver sulfide/vulcanization silver-colored zinc core-shell quanta dots, it is characterised in that: including upwards in turn
The silicon substrate (3) of setting, silicon cylinder (4) and include silver sulfide/vulcanization silver-colored zinc core-shell quanta dots silica discs (5).
2. according to claim 1 include the micro- disk cavity laser of silver sulfide/vulcanization silver-colored zinc core-shell quanta dots, feature exists
In: it is described include silver sulfide/vulcanization silver-colored zinc core-shell quanta dots silica discs (5) by silica discs and be embedded in this two
Silver sulfide/vulcanization silver-colored zinc core-shell quanta dots composition in silica discs.
3. according to claim 2 include the micro- disk cavity laser of silver sulfide/vulcanization silver-colored zinc core-shell quanta dots, feature exists
In: the silver sulfide/vulcanization silver-colored zinc core-shell quanta dots are uniformly distributed in silica discs.
4. according to claim 2 include the micro- disk cavity laser of silver sulfide/vulcanization silver-colored zinc core-shell quanta dots, 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 the micro- disk cavity laser of silver sulfide/vulcanization silver-colored zinc core-shell quanta dots, 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 the micro- disk cavity laser of silver sulfide/vulcanization silver-colored zinc core-shell quanta dots, feature exists
In: the silver sulfide/vulcanization silver-colored zinc core-shell quanta dots are as optical gain medium.
7. according to claim 1 include the micro- disk cavity laser of silver sulfide/vulcanization silver-colored zinc core-shell quanta dots, feature exists
In: the area of silicon cylinder (4) upper bottom surface, which is less than, includes silver sulfide/vulcanization silver-colored zinc core-shell quanta dots silica discs
(5) area of bottom surface.
8. a kind of preparation method for including the micro- disk cavity laser of silver sulfide/vulcanization silver-colored zinc core-shell quanta dots, 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 spin coated on silicon substrate and is included quantum dot to obtain
Silicon dioxide film；
(4) silver sulfide/vulcanization silver-colored zinc core-shell quanta dots silicon dioxide film will be included using reactive ion dry etching to be etched into
Include silver sulfide/vulcanization silver-colored zinc core-shell quanta dots silica discs；
(5) the silicon cylinder of support silica discs is obtained with the silicon below xenon difluoride etching silicon dioxide disk.
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201811193810.8A CN109167252A (en) | 2018-10-15 | 2018-10-15 | Include micro- disk cavity laser of silver sulfide/vulcanization silver-colored zinc core-shell quanta dots and preparation method thereof |
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| Application Number | Priority Date | Filing Date | Title |
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| CN201811193810.8A CN109167252A (en) | 2018-10-15 | 2018-10-15 | Include micro- disk cavity laser of silver sulfide/vulcanization silver-colored zinc core-shell quanta dots and preparation method thereof |
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| CN109167252A true CN109167252A (en) | 2019-01-08 |
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| CN104466657A (en) * | 2014-11-07 | 2015-03-25 | 南京大学 | Chip-integrated 2-micrometer wavelength micro laser |
| CN104861864A (en) * | 2014-02-20 | 2015-08-26 | 韩国科学技术研究院 | Coating composisiotn having polysilazane and wavelength converting agent and wavelength converting sheet prepared using the same |
| CN105264042A (en) * | 2013-06-05 | 2016-01-20 | 柯尼卡美能达株式会社 | Optical material, optical film, and light-emitting device |
| CN106601886A (en) * | 2016-12-30 | 2017-04-26 | Tcl集团股份有限公司 | Nanocrystal with quantum well energy level structure and preparation method thereof, and semiconductor device |
| CN107787352A (en) * | 2015-03-27 | 2018-03-09 | 奈科斯多特股份公司 | The core shell nanometer sheet continuously launched |
-
2018
- 2018-10-15 CN CN201811193810.8A patent/CN109167252A/en active Pending
Patent Citations (6)
| 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 |
| CN105264042A (en) * | 2013-06-05 | 2016-01-20 | 柯尼卡美能达株式会社 | Optical material, optical film, and light-emitting device |
| CN104861864A (en) * | 2014-02-20 | 2015-08-26 | 韩国科学技术研究院 | Coating composisiotn having polysilazane and wavelength converting agent and wavelength converting sheet prepared using the same |
| CN104466657A (en) * | 2014-11-07 | 2015-03-25 | 南京大学 | Chip-integrated 2-micrometer wavelength micro laser |
| CN107787352A (en) * | 2015-03-27 | 2018-03-09 | 奈科斯多特股份公司 | The core shell nanometer sheet continuously launched |
| CN106601886A (en) * | 2016-12-30 | 2017-04-26 | Tcl集团股份有限公司 | Nanocrystal with quantum well energy level structure and preparation method thereof, and semiconductor device |
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