CN109346924A - Include silver telluride/telluride silver-colored zinc core-shell quanta dots vertical cavity surface emitting laser and preparation method thereof - Google Patents
Include silver telluride/telluride silver-colored zinc core-shell quanta dots vertical cavity surface emitting laser and preparation method thereof Download PDFInfo
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- CN109346924A CN109346924A CN201811193807.6A CN201811193807A CN109346924A CN 109346924 A CN109346924 A CN 109346924A CN 201811193807 A CN201811193807 A CN 201811193807A CN 109346924 A CN109346924 A CN 109346924A
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- telluride
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- colored zinc
- shell quanta
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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
- H01S5/34—Structure 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
- H01S5/341—Structures having reduced dimensionality, e.g. quantum wires
- H01S5/3412—Structures having reduced dimensionality, e.g. quantum wires quantum box or quantum dash
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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
- H01S5/18—Surface-emitting [SE] lasers, e.g. having both horizontal and vertical cavities
- H01S5/183—Surface-emitting [SE] lasers, e.g. having both horizontal and vertical cavities having only vertical cavities, e.g. vertical cavity surface-emitting lasers [VCSEL]
- H01S5/18361—Structure of the reflectors, e.g. hybrid mirrors
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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
- H01S5/18—Surface-emitting [SE] lasers, e.g. having both horizontal and vertical cavities
- H01S5/185—Surface-emitting [SE] lasers, e.g. having both horizontal and vertical cavities having only horizontal cavities, e.g. horizontal cavity surface-emitting lasers [HCSEL]
- H01S5/187—Surface-emitting [SE] lasers, e.g. having both horizontal and vertical cavities having only horizontal cavities, e.g. horizontal cavity surface-emitting lasers [HCSEL] using Bragg reflection
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- Condensed Matter Physics & Semiconductors (AREA)
- General Physics & Mathematics (AREA)
- Electromagnetism (AREA)
- Optics & Photonics (AREA)
- Optical Elements Other Than Lenses (AREA)
Abstract
Silver telluride/telluride silver-colored zinc core-shell quanta dots vertical cavity surface emitting laser and preparation method thereof is included the invention discloses a kind of, which includes the quartz base plate being arranged upwards in turn, lower high reflective mirror, includes silver telluride/telluride silver-colored zinc core-shell quanta dots silicon dioxide layer and upper high reflective mirror.The present invention substitutes the lead salt quantum dot of the minimum weight of quantum state 8 degeneracy using the silver telluride 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 telluride kirsite shell that Zn-ef ficiency content gradually increases from inside to outside in silver telluride quantum dot surface, it constructs the surface of gentle interface potential barrier and passivation silver telluride quantum dot, gain of light threshold value can be further decreased.Silver telluride/telluride silver-colored zinc core-shell quanta dots silica membrane " folder " will be included between two panels high reflective mirror, can finally obtain Low threshold, high-quality-factor and environmental-friendly vertical-cavity surface-emitting near-infrared quantum dot laser.
Description
Technical field
Silver telluride/telluride silver-colored zinc core-shell quanta dots vertical cavity surface emitting laser and its system are included the present invention relates to a kind of
Preparation 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 (such as vulcanized lead, lead selenide and lead telluride) quantum dot.They are rock-salt type structure, in Brillouin
The L point in area has 4 equivalent energy band minimum values.Consider that 2 spin degeneracy again, the minimum quantum state of lead salt quantum dot is 8 heavy degeneracys
, the 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 of lead salt quantum dot
It is worth high, the gain of light difficult to realize.Currently, there is an urgent need to search out the novel Colloidal Quantum Dots of one kind to realize the close of Low threshold
The infrared gain of light.
In recent years, the silver telluride 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 telluride quantum dot focus on mostly preparation method with
And cytotoxicity, 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 telluride 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.
Vertical cavity surface emitting laser have integrated level it is high, easily in fiber coupling and preparation process can real-time detection etc. it is excellent
Point.However the coupling of Colloidal Quantum Dots and planar cavity could not be realized always well.Currently, most common way is lower high anti-
Spin coating includes the organic polymer thin film of quantum dot on mirror, then deposits upper high reflective mirror on the polymer film and constitutes Fabry-
Perot cavity.Since organic polymer differs larger with the coefficient of expansion of inorganic upper high reflective mirror material, it is difficult to obtain high-quality-factor
Resonant cavity.
Summary of the invention
Silver telluride/telluride silver-colored zinc core-shell quanta dots vertical cavity surface-emitting laser is included the object of the present invention is to provide a kind of
Device and preparation method thereof is swashed with obtaining Low threshold, high-quality-factor and environmental-friendly vertical-cavity surface-emitting near-infrared quantum dots
Light device.
To achieve the above object, the technical solution adopted by the present invention are as follows:
It is a kind of to include silver telluride/telluride silver-colored zinc core-shell quanta dots vertical cavity surface emitting laser, including set upwards in turn
The quartz base plate set, includes silver telluride/telluride silver-colored zinc core-shell quanta dots silicon dioxide layer and upper high reflective mirror at lower high reflective mirror.
It is described to include silver telluride/telluride silver-colored zinc core-shell quanta dots silicon dioxide layer by silicon dioxide film and be embedded in the dioxy
Silver telluride/telluride silver-colored zinc core-shell quanta dots composition in SiClx film.
The silver telluride/telluride silver-colored zinc core-shell quanta dots are uniformly distributed in silicon dioxide film.
The silver telluride/telluride silver-colored zinc core-shell quanta dots are by silver telluride quantum dot and are coated on the silver telluride quantum dot table
The silver telluride kirsite shell in face forms.
The Zn-ef ficiency content of the silver telluride kirsite shell gradually increases from inside to outside.
The silver telluride/telluride silver-colored zinc core-shell quanta dots are as optical gain medium.
The lower high reflective mirror is distributed bragg reflector mirror, alternately folded by 7 titanium dioxide layers and 6 silicon dioxide layers
Add composition, the optical thickness of titanium dioxide layer and silicon dioxide layer is the 1/4 of the reflection kernel wavelength of lower high reflective mirror.
The reflectivity of the lower high reflective mirror is greater than 99.5%
The upper high reflective mirror is distributed bragg reflector mirror, alternately folded by 6 titanium dioxide layers and 5 silicon dioxide layers
Add composition, the optical thickness of titanium dioxide layer and silicon dioxide layer is the 1/4 of the reflection kernel wavelength of upper high reflective mirror.
The reflectivity of the upper high reflective mirror is less than 99%.
A kind of preparation method including silver telluride/telluride silver-colored zinc core-shell quanta dots vertical cavity surface emitting laser, it is special
Sign is: the following steps are included:
(1) silver telluride 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 tellurium that silver telluride quantum dot surface cladding Zn-ef ficiency content gradually increases from inside to outside
Change silver-colored zinc alloy shell, obtains silver telluride/telluride silver-colored zinc core-shell quanta dots；
(3) electron beam evaporation method 7 titanium dioxide layers of alternating deposit and 6 silicon dioxide layers on a quartz substrate are utilized
To obtain lower high reflective mirror；
(4) it disperses silver telluride/telluride silver-colored zinc core-shell quanta dots that step (2) obtains in toluene, then by silver telluride/tellurium
The toluene dispersion liquid for changing silver-colored zinc core-shell quanta dots is mixed with Perhydropolysilazane, is then spin coated on lower high reflective mirror and is included
Silver telluride/telluride silver-colored zinc core-shell quanta dots silicon dioxide layer；
(5) 6 titanium dioxide layers of alternating deposit on the radio-frequency magnetron sputter method inside silicon dioxide layer containing quantum dot are utilized
Upper high reflective mirror is obtained with 5 silicon dioxide layers.
The utility model has the advantages that silver telluride 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 telluride quantum dot surface
The silver telluride kirsite shell that content gradually increases from inside to outside, to construct gentle interface potential barrier and passivation silver telluride quantum dot
Surface is able to suppress auger recombination and further decreases gain of light threshold value.
Inorganic silicon dioxide and the coefficient of expansion of inorganic upper high reflective mirror material are identical or close, and the two can be good at simultaneous
Hold.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 the vertical-cavity surface-emitting quantum dot laser of high-quality-factor.
The present invention substitutes the heavy degeneracy of minimum quantum state 8 using the silver telluride 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 telluride quantum dot surface coat Zn-ef ficiency content from
It is interior to the silver telluride kirsite shell gradually increased outside, to construct the surface of gentle interface potential barrier and passivation silver telluride quantum dot,
Gain of light threshold value can be further decreased.Inorganic silicon dioxide and the coefficient of expansion of inorganic upper high reflective mirror material are identical or close,
The two can be good at being compatible with.Silver telluride/telluride silver-colored zinc core-shell quanta dots silica membrane " folder " will be included in two panels height
Between anti-mirror, it can finally obtain Low threshold, high-quality-factor and environmental-friendly vertical-cavity surface-emitting near-infrared quantum dots and swash
Light device.
Detailed description of the invention
Fig. 1 is silver telluride/telluride silver-colored zinc core-shell quanta dots structural schematic diagram；
Fig. 2 is the structural schematic diagram for including silver telluride/telluride silver-colored zinc core-shell quanta dots vertical cavity surface emitting laser.
In figure: 1- silver telluride quantum dot, 2- silver telluride kirsite shell, 3- quartz base plate, 4- titanium dioxide layer, 5- titanium dioxide
Silicon layer, 6- include silver telluride/telluride silver-colored zinc core-shell quanta dots silicon dioxide layer.
Specific embodiment
Further explanation is done to the present invention with reference to the accompanying drawing.
As shown in Fig. 2, of the invention includes silver telluride/telluride silver-colored zinc core-shell quanta dots vertical cavity surface emitting laser,
Including be arranged upwards in turn quartz base plate 3, lower high reflective mirror, include silver telluride/telluride silver-colored zinc core-shell quanta dots silica
Layer 6 and upper high reflective mirror.
Silver telluride/telluride silver-colored zinc core-shell quanta dots silicon dioxide layer 6 is included by silicon dioxide film and is embedded in the titanium dioxide
Silver telluride/telluride silver-colored zinc core-shell quanta dots composition in silicon fiml.Silver telluride/telluride silver-colored zinc core-shell quanta dots are in silicon dioxide film
It is uniformly distributed.As shown in Figure 1, silver telluride/telluride silver-colored zinc core-shell quanta dots are by silver telluride quantum dot 1 and are coated on the silver telluride
The silver telluride kirsite shell 2 on 1 surface of quantum dot forms.The Zn-ef ficiency content of silver telluride kirsite shell 2 gradually increases from inside to outside.
Silver telluride/telluride silver-colored zinc core-shell quanta dots are optical gain mediums, less toxic minimum quantum state only have 2 again spin degeneracy silver telluride
Quantum dot 1 can be realized the near infrared light gain of Low threshold, by 1 surface of silver telluride quantum dot coat Zn-ef ficiency content from
It is interior to the silver telluride kirsite shell 2 gradually increased outside, to construct the table of gentle interface potential barrier and passivation silver telluride quantum dot 1
Face can further decrease gain of light threshold value.Inorganic silicon dioxide is identical as the coefficient of expansion of inorganic upper high reflective mirror material or connects
Closely, by being in silver telluride/telluride silver-colored zinc core-shell quanta dots insertion silica in order to which obtain high-quality-factor includes quantum dot
Vertical cavity surface emitting laser.Light field is in the top and bottom for including silver telluride/telluride silver-colored zinc core-shell quanta dots silicon dioxide layer 6
Between vibrate and amplification.
Lower high reflective mirror is distributed bragg reflector mirror, is alternately superimposed by 7 titanium dioxide layer 4 and 6 silicon dioxide layers 5
It constitutes, the optical thickness of titanium dioxide layer 4 and silicon dioxide layer 5 is the 1/4 of the reflection kernel wavelength of lower high reflective mirror.It is lower high anti-
The reflectivity of mirror is greater than 99.5%, and reflection high as far as possible is provided for resonant cavity.
Upper high reflective mirror is distributed bragg reflector mirror, is alternately superimposed by 6 titanium dioxide layer 4 and 5 silicon dioxide layers 5
It constitutes, the optical thickness of titanium dioxide layer 4 and silicon dioxide layer 5 is the 1/4 of the reflection kernel wavelength of upper high reflective mirror.It is upper high anti-
The reflectivity of mirror provides part reflection, the vertical high reflective mirror outgoing of another part light less than 99%, for resonant cavity.
The preparation method for including silver telluride/telluride silver-colored zinc core-shell quanta dots vertical cavity surface emitting laser of the invention,
The following steps are included:
(1) the silver telluride 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 telluride kirsite shell that micromolar silver telluride quantum dot surface cladding Zn-ef ficiency content gradually increases from inside to outside, obtains tellurium
Change silver/telluride silver-colored zinc core-shell quanta dots；
(3) electron beam evaporation method 7 titanium dioxide layers of alternating deposit and 6 silicon dioxide layers on a quartz substrate are utilized
To obtain lower high reflective mirror；
(4) it disperses silver telluride/telluride silver-colored zinc core-shell quanta dots that step (2) obtains in toluene by the mass ratio of 1:5,
Silver telluride/telluride 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 lower high reflective mirror to obtain and includes silver telluride/telluride silver-colored zinc core-shell quanta dots silicon dioxide layer；
(5) 6 titanium dioxide layers of alternating deposit on the radio-frequency magnetron sputter method inside silicon dioxide layer containing quantum dot are utilized
Upper high reflective mirror is obtained with 5 silicon dioxide layers.
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 (9)
1. a kind of include silver telluride/telluride silver-colored zinc core-shell quanta dots vertical cavity surface emitting laser, it is characterised in that: including according to
The secondary quartz base plate (3) set up, includes silver telluride/telluride silver-colored zinc core-shell quanta dots silicon dioxide layer (6) at lower high reflective mirror
With upper high reflective mirror.
2. according to claim 1 include silver telluride/telluride silver-colored zinc core-shell quanta dots vertical cavity surface emitting laser,
Be characterized in that: silver telluride/telluride silver-colored zinc core-shell quanta dots silicon dioxide layer (6) that includes should by silicon dioxide film and insertion
Silver telluride/telluride silver-colored zinc core-shell quanta dots composition in silicon dioxide film.
3. according to claim 2 include silver telluride/telluride silver-colored zinc core-shell quanta dots vertical cavity surface emitting laser,
Be characterized in that: the silver telluride/telluride silver-colored zinc core-shell quanta dots are uniformly distributed in silicon dioxide film.
4. according to claim 2 include silver telluride/telluride silver-colored zinc core-shell quanta dots vertical cavity surface emitting laser,
Be characterized in that: the silver telluride/telluride silver-colored zinc core-shell quanta dots are by silver telluride quantum dot (1) and are coated on the silver telluride quantum
The silver telluride kirsite shell (2) on point (1) surface forms.
5. according to claim 4 include silver telluride/telluride silver-colored zinc core-shell quanta dots vertical cavity surface emitting laser,
Be characterized in that: the Zn-ef ficiency content of the silver telluride kirsite shell (2) gradually increases from inside to outside.
6. according to claim 1 include silver telluride/telluride silver-colored zinc core-shell quanta dots vertical cavity surface emitting laser,
Be characterized in that: the silver telluride/telluride silver-colored zinc core-shell quanta dots are as optical gain medium.
7. according to claim 1 include silver telluride/telluride silver-colored zinc core-shell quanta dots vertical cavity surface emitting laser,
Be characterized in that: the lower high reflective mirror is distributed bragg reflector mirror, by 7 titanium dioxide layers (4) and 6 silicon dioxide layers
(5) alternately superposition is constituted, and the optical thickness of titanium dioxide layer (4) and silicon dioxide layer (5) is the reflection kernel of lower high reflective mirror
The 1/4 of wavelength；The reflectivity of the lower high reflective mirror is greater than 99.5%.
8. according to claim 1 include silver telluride/telluride silver-colored zinc core-shell quanta dots vertical cavity surface emitting laser,
Be characterized in that: the upper high reflective mirror is distributed bragg reflector mirror, by 6 titanium dioxide layers (4) and 5 silicon dioxide layers
(5) alternately superposition is constituted, and the optical thickness of titanium dioxide layer (4) and silicon dioxide layer (5) is the reflection kernel of upper high reflective mirror
The 1/4 of wavelength；The reflectivity of the upper high reflective mirror is less than 99%.
9. a kind of preparation method for including silver telluride/telluride silver-colored zinc core-shell quanta dots vertical cavity surface emitting laser, feature
It is: the following steps are included:
(1) silver telluride 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 telluride that silver telluride quantum dot surface cladding Zn-ef ficiency content gradually increases from inside to outside
Kirsite shell obtains silver telluride/telluride silver-colored zinc core-shell quanta dots；
(3) using electron beam evaporation method, 7 titanium dioxide layers of alternating deposit and 6 silicon dioxide layers are obtained on a quartz substrate
High reflective mirror must be descended；
(4) it disperses silver telluride/telluride silver-colored zinc core-shell quanta dots that step (2) obtains in toluene, then by silver telluride/silver telluride
The toluene dispersion liquid of zinc core-shell quanta dots is mixed with Perhydropolysilazane, is then spin coated on lower high reflective mirror and is included telluride to obtain
Silver/telluride silver-colored zinc core-shell quanta dots silicon dioxide layer；
(5) 6 titanium dioxide layers of alternating deposit on the radio-frequency magnetron sputter method inside silicon dioxide layer containing quantum dot and 5 are utilized
Silicon dioxide layer obtains upper high reflective mirror.
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| CN201811193807.6A CN109346924A (en) | 2018-10-15 | 2018-10-15 | Include silver telluride/telluride silver-colored zinc core-shell quanta dots vertical cavity surface emitting laser and preparation method thereof |
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Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS54121754A (en) * | 1978-03-14 | 1979-09-21 | Mitsubishi Electric Corp | Infrared ray transmission window |
| CN102124405A (en) * | 2008-05-30 | 2011-07-13 | 欧帕鲁克斯有限公司 | Tunable Bragg stack |
| 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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2018
- 2018-10-15 CN CN201811193807.6A patent/CN109346924A/en active Pending
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS54121754A (en) * | 1978-03-14 | 1979-09-21 | Mitsubishi Electric Corp | Infrared ray transmission window |
| CN102124405A (en) * | 2008-05-30 | 2011-07-13 | 欧帕鲁克斯有限公司 | Tunable Bragg stack |
| 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 (3)
| Title |
|---|
| CHI CHEN: "Cation Exchange-Based Facile Aqueous Synthesis of Small, Stable, and Nontoxic Near-Infrared Ag2Te/ZnS Core/Shell Quantum Dots Emitting in the Second Biological Window", 《ACS APPLIED MATERIALS & INTERFACES》 * |
| 佟存柱: "1.3μm GaAs基量子点垂直腔面发射激光器结构设计与分析", 《物理学报》 * |
| 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 |