CN108365511B - LED pumped perovskite quantum dot continuous laser and preparation method thereof - Google Patents
LED pumped perovskite quantum dot continuous laser and preparation method thereof Download PDFInfo
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- H01S3/00—Lasers, i.e. devices using stimulated emission of electromagnetic radiation in the infrared, visible or ultraviolet wave range
- H01S3/09—Processes or apparatus for excitation, e.g. pumping
- H01S3/091—Processes or apparatus for excitation, e.g. pumping using optical pumping
- H01S3/0915—Processes or apparatus for excitation, e.g. pumping using optical pumping by incoherent light
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- H01S3/00—Lasers, i.e. devices using stimulated emission of electromagnetic radiation in the infrared, visible or ultraviolet wave range
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- H01S3/00—Lasers, i.e. devices using stimulated emission of electromagnetic radiation in the infrared, visible or ultraviolet wave range
- H01S3/14—Lasers, i.e. devices using stimulated emission of electromagnetic radiation in the infrared, visible or ultraviolet wave range characterised by the material used as the active medium
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Abstract
The invention relates to an LED pumped perovskite quantum dot continuous laser and a preparation method thereof. A preparation method of an LED pumped perovskite quantum dot continuous laser comprises the following steps: forming a photonic crystal structure or a grating structure on a light-emitting surface of the light-emitting diode LED; and preparing a composite luminescent film composed of perovskite quantum dot materials and polymers on the photonic crystal structure or the grating structure, wherein the LED is a pumping source of the laser, the photonic crystal structure or the grating structure is a resonant cavity of the laser, and the composite luminescent film is a gain medium of the laser.
Description
Technical Field
The invention relates to the technical field of laser, in particular to an LED pumped perovskite quantum dot continuous laser and a preparation method thereof.
Background
The colloidal quantum dots are an important luminescent material, and have the advantages of solution preparation, adjustable luminescent wavelength, narrow emission peak, high quantum yield and the like. The perovskite quantum dot material is a novel luminescent material and has important application value in the fields of display, light-emitting diodes, laser and the like. Compared with II-VI and III-V quantum dots, the perovskite quantum dot has the advantages of simple preparation process, low manufacturing cost, high quantum yield, narrow half-peak width and the like. By regulating and controlling the components and the structure, the perovskite quantum dots can easily realize the full coverage of a visible light region.
At present, the application of perovskite materials to lasers has been partially studied at home and abroad. In 2014, a panel of professor inspired blooms by southern ocean science of singapore observed near-infrared planar whispering gallery mode laser emission from highly crystalline organic-inorganic perovskite platelets, which in turn observed color tunable whispering gallery mode laser emission from cesium lead halide perovskite platelets. UK swordProfessor Richard h. friend, bridge university, studied the laser emission of gold mirror/perovskite semiconductor thin film/bragg mirror structures with an excitation threshold of only 0.2 μ J/pulse. Professor Zhu Xiaoyang of the university of Columbia, USA, obtains low-threshold, high-quality factor FP mode laser from single crystal organic-inorganic perovskite nanowire. The N.C.Giebink group at Pennsylvania State university reports CH3NH3PbI3Random laser excitation of microcrystalline networks, the report first used perovskite materials for random laser to obtain laser threshold of 200 μ Jcm-2. In addition, perovskite lasers have been partially studied by a research group of professor poperi, university of california, university of berkeley, a research group of professor Zhao Yongsheng, institute of chemistry, Chinese academy of sciences, and the like.
However, the above reported perovskite quantum dot lasers require femtosecond and nanosecond laser pumping, and the obtained lasers are femtosecond or nanometer pulse lasers. Femtosecond or nano laser is huge in size and expensive, and is extremely not beneficial to practical application. Developing quantum dot continuous lasers that can be pumped using electricity or LEDs is a hot spot in current quantum dot material laser applications.
Disclosure of Invention
The perovskite quantum dot has the advantages of simple preparation process, low cost, high luminous efficiency, narrow half-peak width and continuously adjustable luminous wavelength within the range of 400nm-800nm, and is an excellent luminescent material. When the traditional quantum dot/polymer composite optical film is prepared, complex processes such as quantum dot synthesis, passivation, post-treatment film forming and the like are needed, the perovskite quantum dot optical film can be prepared in situ, and the quantum dot/polymer composite optical film with high fluorescence efficiency can be obtained by controlling the crystallization process of perovskite materials and polymers. The perovskite quantum dot optical film is simple in preparation process and easy to prepare in batches and integrate and apply.
In view of the above, the present invention provides an LED pumped perovskite quantum dot continuous laser and a method for manufacturing the same, in which a photonic crystal structure or a grating structure is directly formed on a light emitting surface of an LED as a pump source as a resonant cavity of the laser, and a composite luminescent film made of a perovskite quantum dot material and a polymer is manufactured on the photonic crystal structure or the grating structure as a gain medium of the laser, thereby achieving high integration of the entire laser, and having advantages of simple manufacturing process, low price, and the like. Because the LED can be directly connected with electricity to work, the invention also indirectly realizes the electrically pumped continuous laser.
According to one aspect of the invention, a preparation method of an LED pumped perovskite quantum dot continuous laser is provided, and comprises the following steps: forming a photonic crystal structure or a grating structure on the light-emitting surface of the light-emitting diode LED, or packaging the light-emitting diode LED by using a packaging cover plate with the light-emitting surface having the photonic crystal structure or the grating structure; and preparing a composite luminescent film composed of perovskite quantum dot materials and polymers on the photonic crystal structure or the grating structure, wherein the LED is a pumping source of the laser, the photonic crystal structure or the grating structure is a resonant cavity of the laser, and the composite luminescent film is a gain medium of the laser.
Preferably, the LED is any one selected from the group consisting of: a semiconductor light emitting diode; quantum dot light emitting diodes QLEDs; an Organic Light Emitting Diode (OLED); the Micro-LED is a high-density Micro-small-size LED array integrated on a chip; and the light-emitting material of the perovskite light-emitting diode is a perovskite material.
Preferably, the light exit surface of the LED comprises a hard transparent material selected from the group comprising glass and ITO glass.
Preferably, the light emitting surface of the LED comprises a flexible transparent material selected from the group consisting of plastic, metal foil, ultra-thin glass, paper substrate and bio-composite film substrate.
Preferably, the photonic crystal structure or the grating structure is formed by an imprinting or etching method.
Preferably, the composite luminescent film is prepared by an in-situ method comprising: transferring the solution of the perovskite quantum dot precursor and the polymer to the light emitting surface of the LED through spin coating, spray coating, ink-jet printing or electrostatic spinning; and drying and evaporating the solvent to form the composite luminescent film on the light-emitting surface of the LED.
Preferably, the perovskite quantum dot material is an organic salt and/or an inorganic salt of perovskite quantum dots, and the structural general formula is ABX3And/or A2BX6And/or AB2X5And/or A4BX6And/or A3B2X9Wherein A is a metal cation or a positively charged organic amine ion, B is a metal cation, and X is a halogen ion; the polymer is a transparent polymer that is soluble in a polar organic solvent.
Preferably, A is Rb+、Cs+、Na+、K+、Li+、NH＝C(NH2)2H+、NH＝CRNH3 +Or RNH3 +Wherein R is a saturated linear or branched alkyl group, an unsaturated linear or branched alkyl group or an aromatic group having 1 to 8 carbon atoms in the chain, and B is Pb2 +、Sn2+、Mn2+、Ge2+、In3+、Sb3+、Bi3+Or Cu2+X is F-、Cl-、Br-、I-、CN-And SCN-At least one of; the polymer is at least one selected from polyvinylidene fluoride, cellulose acetate, cyano cellulose, polyacrylonitrile, vinylidene fluoride-trifluoroethylene copolymer, polyurethane rubber, polystyrene, polyethylene terephthalate, polycarbonate, cellulose triacetate, polymethyl acrylate, styrene-acrylonitrile copolymer, polyethylene naphthalate, polyether sulfone and polyvinyl chloride.
Preferably, the LED emits light at a wavelength less than the lasing wavelength of the continuous laser.
According to another aspect of the present invention, there is provided an LED pumped perovskite quantum dot continuum laser comprising: the pumping source is a Light Emitting Diode (LED); the resonant cavity is of a photonic crystal structure or a grating structure formed on the light emergent surface of the LED; and the gain medium is a composite luminescent film which is prepared on the photonic crystal structure or the grating structure and is composed of perovskite quantum dot materials and polymers.
Preferably, the LED is any one selected from the group consisting of: a semiconductor light emitting diode; quantum dot light emitting diodes QLEDs; an Organic Light Emitting Diode (OLED); the Micro-LED is a high-density Micro-small-size LED array integrated on a chip; and the light-emitting material of the perovskite light-emitting diode is a perovskite material.
Preferably, the laser emission wavelength of the continuous laser is continuously adjustable within the range of 400nm-800 nm.
Compared with the prior art, one or more embodiments in the above scheme can have the following advantages or beneficial effects: a photonic crystal structure or a grating structure is directly formed on a light-emitting surface of an LED serving as a pumping source to serve as a resonant cavity of a laser, and a composite luminescent film composed of a perovskite quantum dot material and a polymer is prepared on the photonic crystal structure or the grating structure to serve as a gain medium of the laser, so that high integration of the whole laser is achieved, and the laser has the advantages of being simple in preparation process, low in price and the like. Because the LED can be directly connected with electricity to work, the invention also indirectly realizes the electrically pumped continuous laser.
Additional features and advantages of the invention will be set forth in the description which follows, and in part will be obvious from the description, or may be learned by practice of the invention. The objectives and other advantages of the invention will be realized and attained by the structure particularly pointed out in the written description and claims hereof as well as the appended drawings.
Drawings
The accompanying drawings, which are included to provide a further understanding of the invention and are incorporated in and constitute a part of this specification, illustrate embodiments of the invention and together with the description serve to explain the principles of the invention and not to limit the invention. In the drawings, like parts are designated with like reference numerals, and the drawings are not drawn to scale in reality.
Fig. 1 is a schematic view of an LED having a photonic crystal structure or a grating structure according to an embodiment of the present invention.
FIG. 2 is a schematic diagram of an LED pumped perovskite quantum dot continuum laser according to an embodiment of the invention.
Detailed Description
The following detailed description of the embodiments of the present invention will be provided with reference to the drawings and examples, so that how to apply the technical means to solve the technical problems and achieve the technical effects can be fully understood and implemented. It should be noted that, as long as there is no conflict, the embodiments and the features of the embodiments of the present invention may be combined with each other, and the technical solutions formed are within the scope of the present invention.
In the following description, for purposes of explanation, numerous specific details are set forth in order to provide a thorough understanding of the embodiments of the invention. It will be apparent, however, to one skilled in the art that the present invention may be practiced without some of these specific details or with other methods described herein.
Fig. 1 is a schematic view of an LED having a photonic crystal structure or a grating structure according to an embodiment of the present invention. As shown in fig. 1, in the present embodiment, an LED101 is energized with a current I to emit light, and a photonic crystal structure or a grating structure 102 is formed on a light emitting surface of the LED 101.
In one embodiment, the LED101 may be a semiconductor light emitting diode, a Micro-LED, an Organic Light Emitting Diode (OLED), a quantum dot light emitting diode (QLED), a Perovskite light emitting diode (Perovskite LED), or the like. micro-LEDs are high-density micro-sized LED arrays integrated on a chip. The organic light emitting diode uses an organic polymer material as a light emitting center. Quantum dot light emitting diodes use quantum dot materials as the luminescent centers. The luminescent material of the perovskite light emitting diode is a perovskite material.
In an embodiment, the light emitting surface of the LED101 is made of a hard transparent material, such as glass or ITO glass. In another embodiment, the light emitting surface of the LED101 is made of a flexible transparent material, such as plastic, metal foil, ultra-thin glass, paper substrate, or bio-composite film substrate.
In one embodiment, the photonic crystal structure or grating structure 102 is formed by stamping or etching.
In one embodiment, the photonic crystal structure or grating structure 102 is fabricated directly on the light-emitting surface of the LED 101. In another embodiment, the photonic crystal structure or the grating structure 102 may be fabricated on the light-emitting surface of the LED package cover, and then the LED101 is packaged by the package cover having the photonic crystal structure or the grating structure 102 on the light-emitting surface.
FIG. 2 is a schematic diagram of an LED pumped perovskite quantum dot continuum laser according to an embodiment of the invention. As shown in fig. 2, in the present embodiment, the perovskite quantum dot continuous laser includes a pump source 201, a resonant cavity 202, and a gain medium 203.
The pump source 201 is an LED that is energized with a current I to emit light for exciting the gain medium 203 to emit photons. The resonant cavity 202 is a photonic crystal structure or a grating structure formed on the light emitting surface of the LED, and is configured to amplify photons emitted from the gain medium 203 to output continuous laser light. The gain medium 203 is a composite luminescent film prepared on the photonic crystal structure or the grating structure and composed of perovskite quantum dot materials and polymers, and is used for receiving light radiation of the LED to excite photons.
In this embodiment, the pump source 201 and the resonant cavity 202 may be an LED having a photonic crystal structure or a grating structure according to the embodiment shown in fig. 1, and will not be described again.
In one embodiment, the perovskite quantum dot material is organic salt and/or inorganic salt of perovskite quantum dot, and the structural general formula is ABX3And/or A2BX6And/or AB2X5And/or A4BX6And/or A3B2X9Wherein A is a metal cation or a positively charged organic amine ion, B is a metal cation, and X is a halogen ion.
Preferably, A is Rb+、Cs+、Na+、K+、Li+、NH＝C(NH2)2H+、NH＝CRNH3 +Or RNH3 +Wherein R is a saturated linear or branched alkyl group, an unsaturated linear or branched alkyl group or an aromatic group having 1 to 8 carbon atoms in the chain, and B is Pb2 +、Sn2+、Mn2+、Ge2+、In3+、Sb3+、Bi3+Or Cu2+X is F-、Cl-、Br-、I-、CN-And SCN-At least one of (a).
In one embodiment, the polymer is a transparent polymer that is soluble in a polar organic solvent.
Preferably, the polymer is selected from at least one of polyvinylidene fluoride, cellulose acetate, cyano cellulose, polyacrylonitrile, vinylidene fluoride-trifluoroethylene copolymer, urethane rubber, polystyrene, polyethylene terephthalate, polycarbonate, cellulose triacetate, polymethyl acrylate, styrene-acrylonitrile copolymer, polyethylene naphthalate, polyether sulfone, and polyvinyl chloride.
More preferably, the polymer is selected from at least one of polyvinylidene fluoride, cellulose acetate, cyanocellulose, polyacrylonitrile, vinylidene fluoride-trifluoroethylene copolymer, and cellulose triacetate.
In one embodiment, the gain medium 203 is prepared by an in situ method comprising: transferring the solution of the perovskite quantum dot precursor and the polymer to the light emitting surface of the LED through spin coating, spray coating, ink-jet printing or electrostatic spinning; and drying and evaporating the solvent to form the composite luminescent film on the light-emitting surface of the LED.
In one embodiment, the wavelength of action of the photonic crystal structure or grating structure as the resonant cavity 202 matches the wavelength of emission of the composite luminescent film as the gain medium 203.
In one embodiment, the emission wavelength of the continuous laser light output by the gain medium 203 is continuously tunable in the range of 400nm to 800nm by varying the composition or size of the perovskite quantum dot material.
In one embodiment, the wavelength of light emitted by the pump source 201 is less than the emission wavelength of the continuous laser light output by the continuous laser.
The invention also provides a preparation method of the perovskite quantum dot continuous laser of the LED pump, which comprises the following steps: forming a photonic crystal structure or a grating structure on a light-emitting surface of the light-emitting diode LED; and preparing a composite luminescent film composed of perovskite quantum dot materials and polymers on the photonic crystal structure or the grating structure, wherein the LED is a pumping source of the laser, the photonic crystal structure or the grating structure is a resonant cavity of the laser, and the composite luminescent film is a gain medium of the laser.
In summary, the present invention provides an LED pumped perovskite quantum dot continuous laser and a method for manufacturing the same, wherein a photonic crystal structure or a grating structure is directly formed on a light emitting surface of an LED as a pump source as a resonant cavity of the laser, and a composite luminescent film formed by a perovskite quantum dot material and a polymer is prepared on the photonic crystal structure or the grating structure as a gain medium of the laser, thereby realizing high integration of the entire laser, and having advantages of simple manufacturing process, low price, and the like. Because the LED can be directly connected with electricity to work, the invention also indirectly realizes the electrically pumped continuous laser.
It is to be understood that the disclosed embodiments of the invention are not limited to the particular process steps or materials disclosed herein, but rather, are extended to equivalents thereof as would be understood by those of ordinary skill in the relevant art. It is also to be understood that the terminology used herein is for the purpose of describing particular embodiments only, and is not intended to be limiting.
Reference in the specification to "an embodiment" means that a particular feature, or characteristic described in connection with the embodiment is included in at least one embodiment of the invention. Thus, the appearances of the phrase "an embodiment" appearing in various places throughout the specification are not necessarily all referring to the same embodiment.
Furthermore, the described features or characteristics may be combined in any other suitable manner in one or more embodiments. In the above description, certain specific details are provided, such as thicknesses, amounts, etc., to provide a thorough understanding of embodiments of the invention. One skilled in the relevant art will recognize, however, that the invention may be practiced without one or more of the specific details, or with other methods, components, materials, and so forth.
While the above examples are illustrative of the principles of the present invention in one or more applications, it will be apparent to those of ordinary skill in the art that various changes in form, usage and details of implementation can be made without departing from the principles and concepts of the invention. Accordingly, the invention is defined by the appended claims.
Claims (13)
1. A preparation method of an LED pumped perovskite quantum dot continuous laser comprises the following steps:
forming a photonic crystal structure or a grating structure on the light-emitting surface of the light-emitting diode LED, or packaging the light-emitting diode LED by using a packaging cover plate with the light-emitting surface having the photonic crystal structure or the grating structure; and
preparing a composite luminescent film consisting of perovskite quantum dot materials and polymers on the photonic crystal structure or the grating structure,
the LED is a pumping source of the laser, the photonic crystal structure or the grating structure is a resonant cavity of the laser, and the composite luminescent film is a gain medium of the laser.
2. The method of making a perovskite quantum dot continuum laser of claim 1, wherein the LED is a semiconductor light emitting diode.
3. The method for producing a perovskite quantum dot continuous laser according to claim 1, wherein the LED is any one selected from the group consisting of:
quantum dot light emitting diodes QLEDs;
an Organic Light Emitting Diode (OLED);
the Micro-LED is a high-density Micro-small-size LED array integrated on a chip; and
the light-emitting material of the perovskite light-emitting diode is a perovskite material.
4. The method of making a perovskite quantum dot continuum laser as claimed in claim 1, wherein the light emitting surface of the LED comprises a hard transparent material selected from the group consisting of glass and ITO glass.
5. The method of making a perovskite quantum dot continuum laser of claim 1, wherein the light emitting surface of the LED comprises a flexible transparent material selected from the group consisting of plastic, metal foil, ultra-thin glass, paper substrate, and bio-composite film substrate.
6. The method for preparing a perovskite quantum dot continuous laser according to claim 1, wherein the photonic crystal structure or the grating structure is formed by an imprinting or etching method.
7. The method of fabricating a perovskite quantum dot continuous laser according to claim 1, wherein the composite luminescent film is fabricated by an in-situ method comprising:
transferring the solution of the perovskite quantum dot precursor and the polymer to the light emitting surface of the LED through spin coating, spray coating, ink-jet printing or electrostatic spinning; and
and drying to evaporate the solvent so as to form the composite luminescent film on the light-emitting surface of the LED.
8. The method for producing a perovskite quantum dot continuous laser according to claim 1,
the perovskite quantum dot material is organic salt and/or inorganic salt of perovskite quantum dot, and the structural general formula isABX3And/or A2BX6And/or AB2X5And/or A4BX6And/or A3B2X9Wherein A is a metal cation or a positively charged organic amine ion, B is a metal cation, and X is a halogen ion;
the polymer is a transparent polymer that is soluble in a polar organic solvent.
9. The method for producing a perovskite quantum dot continuous laser according to claim 8,
a is Rb+、Cs+、Na+、K+、Li+、NH＝C(NH2)2H+、NH＝CRNH3 +Or RNH3 +Wherein R is a saturated linear or branched alkyl group, an unsaturated linear or branched alkyl group or an aromatic group having 1 to 8 carbon atoms in the chain, and B is Pb2+、Sn2+、Mn2+、Ge2+、In3+、Sb3+、Bi3+Or Cu2+X is F-、Cl-、Br-、I-、CN-And SCN-At least one of;
the polymer is at least one selected from polyvinylidene fluoride, cellulose acetate, cyano cellulose, polyacrylonitrile, vinylidene fluoride-trifluoroethylene copolymer, polyurethane rubber, polystyrene, polyethylene terephthalate, polycarbonate, cellulose triacetate, polymethyl acrylate, styrene-acrylonitrile copolymer, polyethylene naphthalate, polyether sulfone and polyvinyl chloride.
10. An LED pumped perovskite quantum dot continuum laser comprising:
the pumping source is a Light Emitting Diode (LED);
the resonant cavity is of a photonic crystal structure or a grating structure formed on the light emergent surface of the LED; and
the gain medium is a composite luminescent film which is prepared on the photonic crystal structure or the grating structure and is composed of perovskite quantum dot materials and polymers.
11. The perovskite quantum dot continuum laser of claim 10, wherein the LED is a semiconductor light emitting diode.
12. The perovskite quantum dot continuum laser of claim 10, wherein the LED is any one selected from the group consisting of:
quantum dot light emitting diodes QLEDs;
an Organic Light Emitting Diode (OLED);
the Micro-LED is a high-density Micro-small-size LED array integrated on a chip; and
the light-emitting material of the perovskite light-emitting diode is a perovskite material.
13. The perovskite quantum dot continuum laser of claim 10, wherein a lasing wavelength of the continuum laser is continuously tunable in a range of 400nm to 800 nm.
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| WO2019080925A1 (en) * | 2017-10-27 | 2019-05-02 | 北京理工大学 | Continuous laser employing colloidal quantum dot and manufacturing method thereof |
| CN109193327B (en) * | 2018-10-22 | 2020-07-31 | 长春理工大学 | Preparation method of perovskite micro laser |
| CN109687290B (en) * | 2019-02-22 | 2021-01-15 | 中国科学院半导体研究所 | Electric pumping perovskite composite cavity laser |
| CN110994345A (en) * | 2019-12-17 | 2020-04-10 | 华中科技大学 | Tunable laser based on self-trapping exciton |
| CN111048976A (en) * | 2020-01-09 | 2020-04-21 | 曲阜师范大学 | Inorganic perovskite quantum dot distributed feedback laser |
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| CN104861958A (en) * | 2015-05-14 | 2015-08-26 | 北京理工大学 | Perovskite/polymer composite luminescent material and preparation method thereof |
| CN106785829A (en) * | 2017-01-10 | 2017-05-31 | 中国科学院长春光学精密机械与物理研究所 | A kind of distributed feedback laser and preparation method thereof, distributed feedback laser array |
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