CN109193343A - Include micro- disk cavity laser of silver selenide/selenizing silver-colored zinc core-shell quanta dots and preparation method thereof - Google Patents

Include micro- disk cavity laser of silver selenide/selenizing silver-colored zinc core-shell quanta dots and preparation method thereof Download PDF

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Publication number
CN109193343A
CN109193343A CN201811193781.5A CN201811193781A CN109193343A CN 109193343 A CN109193343 A CN 109193343A CN 201811193781 A CN201811193781 A CN 201811193781A CN 109193343 A CN109193343 A CN 109193343A
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silver
selenizing
silver selenide
selenide
quanta dots
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CN201811193781.5A
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廖晨
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Nanjing Post and Telecommunication University
Nanjing University of Posts and Telecommunications
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Nanjing Post and Telecommunication University
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Priority to CN201811193781.5A priority Critical patent/CN109193343A/en
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    • HELECTRICITY
    • H01ELECTRIC ELEMENTS
    • H01SDEVICES 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
    • H01S5/00Semiconductor lasers
    • H01S5/30Structure or shape of the active region; Materials used for the active region
    • H01S5/34Structure or shape of the active region; Materials used for the active region comprising quantum well or superlattice structures, e.g. single quantum well [SQW] lasers, multiple quantum well [MQW] lasers or graded index separate confinement heterostructure [GRINSCH] lasers
    • H01S5/341Structures having reduced dimensionality, e.g. quantum wires
    • H01S5/3412Structures having reduced dimensionality, e.g. quantum wires quantum box or quantum dash

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  • Physics & Mathematics (AREA)
  • Condensed Matter Physics & Semiconductors (AREA)
  • General Physics & Mathematics (AREA)
  • Electromagnetism (AREA)
  • Optics & Photonics (AREA)
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Abstract

Micro- disk cavity laser of silver selenide/selenizing 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 selenide/selenizing 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 selenide 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 selenide kirsite shell that Zn-ef ficiency content gradually increases from inside to outside in silver selenide quantum dot surface, it constructs the surface of gentle interface potential barrier and passivation silver selenide 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 selenide/selenizing 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

Include the micro- disk cavity laser of silver selenide/selenizing silver-colored zinc core-shell quanta dots and its preparation Method
Technical field
The micro- disk cavity laser of silver selenide/selenizing 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 selenide 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 selenide 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 selenide 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 selenide/selenizing 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 selenide/selenizing silver-colored zinc core-shell quanta dots, including the silicon being arranged upwards in turn Substrate, silicon cylinder and include silver selenide/selenizing silver-colored zinc core-shell quanta dots silica discs.
Silver selenide/selenizing silver-colored zinc core-shell quanta dots silica discs that include should by silica discs and insertion Silver selenide/selenizing silver-colored zinc core-shell quanta dots composition in silica discs.
The silver selenide/selenizing silver-colored zinc core-shell quanta dots are uniformly distributed in silica discs.
The silver selenide/selenizing silver-colored zinc core-shell quanta dots are by silver selenide quantum dot and are coated on the silver selenide quantum dot table The silver selenide kirsite shell in face forms.
The Zn-ef ficiency content of the silver selenide kirsite shell gradually increases from inside to outside.
The silver selenide/selenizing 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 selenide/selenizing 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 selenide/selenizing silver-colored zinc core-shell quanta dots, including following step It is rapid:
(1) silver selenide 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 selenium that silver selenide quantum dot surface cladding Zn-ef ficiency content gradually increases from inside to outside Change silver-colored zinc alloy shell, obtains silver selenide/selenizing silver-colored zinc core-shell quanta dots;
(3) it disperses silver selenide/selenizing silver-colored zinc core-shell quanta dots that step (2) obtains in toluene, then by silver selenide/selenium 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 selenide/selenizing 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 selenide/selenizing 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 selenide quantum dot is rectangle 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 selenide quantum dot surface The silver selenide kirsite shell that content gradually increases from inside to outside, to construct gentle interface potential barrier and passivation silver selenide 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 selenide 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 selenide quantum dot surface coat Zn-ef ficiency content The silver selenide kirsite shell gradually increased from inside to outside, to construct the table of gentle interface potential barrier and passivation silver selenide 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 selenide/selenizing 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 selenide/selenizing 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 selenide/selenizing silver-colored zinc core-shell quanta dots.
In figure: 1- silver selenide quantum dot, 2- silver selenide kirsite shell, 3- silicon substrate, 4- silicon cylinder, 5- include silver selenide/ The silica discs of selenizing 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 selenide/selenizing silver-colored zinc core-shell quanta dots, including according to The secondary silicon substrate 3 set up, silicon cylinder 4 and include silver selenide/selenizing silver-colored zinc core-shell quanta dots silica discs 5.
Include silver selenide/selenizing silver-colored zinc core-shell quanta dots silica discs 5 by silica discs and be embedded in this two Silver selenide/selenizing silver-colored zinc core-shell quanta dots composition in silica discs.Silver selenide/selenizing silver-colored zinc core-shell quanta dots are in titanium dioxide It is uniformly distributed in silicon disk.As shown in Figure 1, silver selenide/selenizing silver-colored zinc core-shell quanta dots by silver selenide quantum dot 1 and are coated on The silver selenide kirsite shell 2 on 1 surface of silver selenide quantum dot forms.The Zn-ef ficiency content of silver selenide kirsite shell 2 is from inside to outside It gradually increases.Silver selenide/selenizing 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 selenide quantum dot 1, can be realized the near infrared light gain of Low threshold, by 1 surface of silver selenide quantum dot coat zinc The silver selenide kirsite shell 2 that constituent content gradually increases from inside to outside, to construct gentle interface potential barrier and passivation selenizing silver content The surface of son point 1, can further decrease gain of light threshold value.Silver selenide/selenizing 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 selenide/selenizing 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 selenide/selenizing silver-colored zinc core-shell quanta dots silica discs 5 The area of bottom surface, silicon cylinder 4 will include silver selenide/selenizing 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 selenide/selenizing silver-colored zinc core-shell quanta dots silica discs 5 are included.
The preparation method for including the micro- disk cavity laser of silver selenide/selenizing silver-colored zinc core-shell quanta dots of the invention, including with Lower step:
(1) the silver selenide 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 selenide kirsite shell that micromolar silver selenide quantum dot surface cladding Zn-ef ficiency content gradually increases from inside to outside, obtains selenium Change silver/selenizing silver-colored zinc core-shell quanta dots;
(3) it disperses silver selenide/selenizing silver-colored zinc core-shell quanta dots that step (2) obtains in toluene by the mass ratio of 1:5, Silver selenide/selenizing 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 selenide/selenizing 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 selenide/selenizing 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 selenide/selenizing 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 selenide/selenizing silver-colored zinc core-shell quanta dots silica discs (5).
2. according to claim 1 include the micro- disk cavity laser of silver selenide/selenizing silver-colored zinc core-shell quanta dots, feature exists In: it is described include silver selenide/selenizing silver-colored zinc core-shell quanta dots silica discs (5) by silica discs and be embedded in this two Silver selenide/selenizing silver-colored zinc core-shell quanta dots composition in silica discs.
3. according to claim 2 include the micro- disk cavity laser of silver selenide/selenizing silver-colored zinc core-shell quanta dots, feature exists In: the silver selenide/selenizing 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 selenide/selenizing silver-colored zinc core-shell quanta dots, feature exists In: the silver selenide/selenizing silver-colored zinc core-shell quanta dots are by silver selenide quantum dot (1) and are coated on the silver selenide quantum dot (1) The silver selenide kirsite shell (2) on surface forms.
5. according to claim 4 include the micro- disk cavity laser of silver selenide/selenizing silver-colored zinc core-shell quanta dots, feature exists In: the Zn-ef ficiency content of the silver selenide kirsite shell (2) gradually increases from inside to outside.
6. according to claim 1 include the micro- disk cavity laser of silver selenide/selenizing silver-colored zinc core-shell quanta dots, feature exists In: the silver selenide/selenizing 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 selenide/selenizing 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 selenide/selenizing 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 selenide/selenizing silver-colored zinc core-shell quanta dots, it is characterised in that: packet Include following steps:
(1) silver selenide 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 selenide that silver selenide quantum dot surface cladding Zn-ef ficiency content gradually increases from inside to outside Kirsite shell obtains silver selenide/selenizing silver-colored zinc core-shell quanta dots;
(3) it disperses silver selenide/selenizing silver-colored zinc core-shell quanta dots that step (2) obtains in toluene, then by silver selenide/silver selenide 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 selenide/selenizing silver-colored zinc core-shell quanta dots silicon dioxide film will be included using reactive ion dry etching to be etched into Include silver selenide/selenizing 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.
CN201811193781.5A 2018-10-15 2018-10-15 Include micro- disk cavity laser of silver selenide/selenizing silver-colored zinc core-shell quanta dots and preparation method thereof Pending CN109193343A (en)

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Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN110819349A (en) * 2019-11-06 2020-02-21 上海南麟电子股份有限公司 Silver selenide/silver selenide sulfide core-shell quantum dot, electro-optic modulator and preparation method

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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

Patent Citations (2)

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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

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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》 *

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN110819349A (en) * 2019-11-06 2020-02-21 上海南麟电子股份有限公司 Silver selenide/silver selenide sulfide core-shell quantum dot, electro-optic modulator and preparation method
CN110819349B (en) * 2019-11-06 2020-08-11 上海南麟电子股份有限公司 Silver selenide/silver selenide sulfide core-shell quantum dot, electro-optic modulator and preparation method

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