CN118040460B - Preparation method of perovskite nano laser based on metal array microcavity - Google Patents
Preparation method of perovskite nano laser based on metal array microcavity Download PDFInfo
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Classifications
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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
- H01S5/02—Structural details or components not essential to laser action
- H01S5/026—Monolithically integrated components, e.g. waveguides, monitoring photo-detectors, drivers
- H01S5/0268—Integrated waveguide grating router, e.g. emission of a multi-wavelength laser array is combined by a "dragon router"
-
- 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
- H01S5/02—Structural details or components not essential to laser action
- H01S5/022—Mountings; Housings
- H01S5/0233—Mounting configuration of laser chips
- H01S5/02345—Wire-bonding
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- Physics & Mathematics (AREA)
- Condensed Matter Physics & Semiconductors (AREA)
- General Physics & Mathematics (AREA)
- Electromagnetism (AREA)
- Optics & Photonics (AREA)
- Physical Or Chemical Processes And Apparatus (AREA)
Abstract
The invention discloses a preparation method of a perovskite nano laser based on a metal array microcavity, and belongs to the technical field of laser and nano. Firstly, preparing a metal array microcavity, and taking the prepared metal array microcavity as a resonant cavity. And then preparing a quasi two-dimensional perovskite film, and coating the prepared quasi two-dimensional perovskite film on the prepared metal array microcavity. And then preparing a top metal electrode, and coating the prepared top metal electrode on the prepared quasi-two-dimensional perovskite film for encapsulation and reinforcement. The invention realizes the full-band, high-power, narrow-bandwidth and strong-coherence nano laser by a simple and economical method. The invention has simple process, low cost and good batch property, can realize customization as required, and has important significance for realizing the development of the emerging optical fields such as on-chip integration, optical calculation and the like and promoting the realization of the application thereof.
Description
Technical Field
The invention relates to a preparation method of a nano laser, in particular to a preparation method of a perovskite nano laser based on a metal array microcavity, and belongs to the technical field of laser and nano.
Background
In modern technology, lasers are very popular in the fields of display, measurement, processing, communication, national defense and the like with high brightness, high collimation, high monochromaticity and high coherence. The laser is based on spontaneous radiation, that is, after electrons in atoms absorb energy and transition from a low energy level to a high energy level, the energy is released in the form of photons when the electrons return to the low energy level, a pumping source is added to excite the atoms, a material with light amplifying capability is selected as a gain medium, and then mode selection is carried out by means of a proper cavity, so that the output photons are regulated and controlled to have highly uniform optical characteristics. Based on the above, the three elements of the laser are a resonant cavity, a pump source and a gain medium. At present, the miniaturization and integration trend of the instrument is obvious, but the miniaturization progress of the laser light source is not ideal: at present, the smallest laser on the market is still in macroscopic level, and has huge volume relative to application fields such as on-chip integration, based on the macroscopic level, the laser emission capable of breaking through the diffraction limit to realize the sub-wavelength level becomes a mode of standing, scientific researchers can not approximately and simultaneously throw eyes to the micro-nano laser, wherein the plasmon laser limits the light field by means of electromagnetic waves generated by the collective oscillation of free electrons on the metal surface, can realize sub-wavelength constraint and can generate extremely large field enhancement, and the diffraction limit is broken through. However, the metal dielectric has larger loss, so that the low-threshold and high-power laser emission is difficult to realize, the laser emission capability is limited at present, the laser cannot be separated from a laboratory stage, the mass production cannot be realized at present, and the laser emission device is put into application. The perovskite material has the advantages of high quantum yield, flexible and adjustable band gap and high carrier mobility when being used as a good gain material, but is easy to accumulate energy and break down when being used as a laser gain medium, and the condition of sudden termination of laser emission under continuous optical pumping, namely the phenomenon of laser death, can occur.
Therefore, the laser in the prior art has larger volume, and cannot meet the requirements of high power and miniaturization, which is contrary to the requirements of miniaturization, on-chip integration, quantum communication and other application of the existing scientific instrument; meanwhile, the existing small laser diode has the advantages of small volume and low cost compared with a laser, but the emitted light beam has poor collimation, low coherence, low power and low brightness, and can not well meet the application requirements.
Disclosure of Invention
The invention aims to solve the problems of breaking through diffraction limit, realizing micro-nano laser emission and manufacturing a sub-wavelength level laser, uses a perovskite material with high quantum yield, flexible and adjustable band gap and high carrier mobility as a gain medium, combines a micro-nano array microcavity to perform local action on an optical field, and realizes the emission of high-power, narrow-bandwidth, high-coherence and high-collimation electric injection sub-wavelength level perovskite nano laser in an electric injection mode. And further provides a preparation method of the perovskite nano laser based on the metal array microcavity.
The technical scheme adopted by the invention for solving the problems is as follows:
A preparation method of perovskite nanometer laser based on metal array microcavity, the preparation method of the perovskite nano laser based on the metal array microcavity is realized by the following steps:
s1: preparing a metal array microcavity, and taking the prepared metal array microcavity as a resonant cavity;
S2: preparing a quasi two-dimensional perovskite film, and coating the prepared quasi two-dimensional perovskite film on the metal array microcavity prepared in the step S1;
s3: and (3) preparing a top metal electrode, and coating the prepared top metal electrode on the quasi-two-dimensional perovskite film prepared in the step (S2) for encapsulation and reinforcement.
Further, the step of preparing the metal array microcavity in S1 includes:
S1.1: cutting a metal sheet into a round substrate, flattening the metal substrate by a hydraulic press, sequentially using absolute ethyl alcohol and ultrapure water for ultrasonic cleaning, and repeatedly cleaning until the surface is free of oil films and impurities;
s1.2: taking out the cleaned metal substrate obtained in the step S1.1, drying, and carrying out ice water bath polishing in the prepared acidic polishing solution;
S1.3: washing the surface of the polished metal substrate obtained in the step S1.2 with absolute ethyl alcohol to obtain an acidic solution, blow-drying, and then transferring and imprinting the surface of the polished metal substrate in a hydraulic press by means of a high-hardness metal film with an initial structure, so that the initial structure is transferred onto the metal substrate;
s1.4: placing the metal substrate which is well stamped in the step S1.3 into an oxidizing solution for oxidization to obtain a metal array microcavity and an oxide substrate thereof;
S1.5: and (3) taking out the metal substrate after the oxidation of S1.4, cleaning the metal substrate by using absolute ethyl alcohol, and soaking the metal substrate in weak acid to remove a residual oxidation layer, thereby obtaining the metal array microcavity.
Further, the material of the metal array microcavity is one of gold, silver, aluminum, copper and tin.
Further, the thickness of the metal sheet in S1.1 is 0.1 to 4mm.
Further, the diameter of the circular substrate described in S1.1 is 8 to 50mm.
Further, the acidic polishing solution in S1.2 is one of hydrochloric acid, nitric acid and perchloric acid.
Further, the polishing voltage of the ice water bath in the step S1.2 is 6-30V/piece, the current is 0.2-5A/piece, and the time is 0.5-5 min.
Further, the oxidizing solution in S1.4 is one of carbonic acid, citric acid, hydrofluoric acid, oxalic acid, sulfurous acid and phosphoric acid.
Further, the oxidation voltage in S1.4 is 2-15V/piece, the current is 0.2-53A/piece, and the time is 0-16 h.
Further, the weak acid in S1.5 is one of chromic acid, phosphoric acid and oxalic acid.
Further, the soaking time in S1.5 is 2-24 hours.
Further, the step of preparing the quasi two-dimensional perovskite thin film in S2 includes:
S2.1: preparing a precursor reaction solution: dissolving macromolecular organic matters, monovalent metal halides and divalent metal halides in a polar organic solvent, stirring, and filtering for standby to obtain a precursor reaction solution;
S2.2: dropwise adding the precursor reaction solution obtained in the step S2.1 into the right center of the metal array microcavity in an isolated water-oxygen environment, and then spin-coating;
s2.3: and annealing the S2.2 spin-coated quasi-two-dimensional perovskite film.
Further, the macromolecular organic matter in the S2.1 is one of naphthylmethylamine, phenethylamine, n-butylamine, phenylbutylamine and triethylamine.
Further, the monovalent metal halide in S2.1 is denoted as a 'X, where a' is one of potassium, cesium, rubidium, lead, tin, germanium, methylamine, and formamidine, and X is one or more of halogen elements Cl, br, and I.
Further, the divalent metal halide in S2.1 is represented by B 2 X, and the concentration is 0.01-1.2mol/L, wherein B is one of potassium, cesium, rubidium, lead, tin and germanium, and X is one or more of halogen elements Cl, br and I.
Further, the polar organic solvent in S2.1 is one of dimethyl sulfoxide, N-N dimethylformamide, gamma-hydroxybutyric acid lactone, N-methylpyrrolidone and ethylene glycol methyl ether.
Further, the stirring mode in the step S2.1 is that a magnetic stirrer is used for stirring, the stirring temperature is 25-120 ℃, the rotating speed of the magnetic stirrer is 500-4000 rpm, and the stirring time is 2-18 h;
Further, the filtration mode described in S2.1 is nylon NY membrane disposable oil filter filtration.
Further, the rotating speed of the spin coating in S2.2 is 2000-8000 r/min.
Further, the annealing temperature in S2.3 is 60-150 ℃ and the time is 10-120S.
Further, the top electrode is an indium tin oxide coating.
Further, the preparation step of the top electrode comprises the following steps:
s3.1: dissolving indium tin oxide powder in meta-xylene to form a suspension;
S3.2: spin-coating the suspension obtained in the step S3.1 on the quasi two-dimensional perovskite film;
s3.3: and annealing the top electrode spin-coated in the step S3.2.
Further, the mass concentration of the suspension in S3.1 is 0.2 to 20mg/mL.
Further, the rotating speed of the spin coating in the step S3.2 is 2000-6000 r/min.
Further, the annealing temperature in S3.3 is 80-150 ℃ and the time is 20-80S.
The beneficial effects of the invention are as follows:
1. According to the preparation method of the perovskite nano laser based on the metal array microcavity, the perovskite material quasi-two-dimensional perovskite film with high quantum yield, flexible and adjustable band gap and high carrier mobility is used as a gain material of nano laser, the nano array microcavity is combined, the distribution mode of carrier injection is changed, a brand-new feedback mechanism is established by utilizing plasmon polaritons generated by the array microcavity and local actions thereof, the laser death is broken through, and the problems of easy breakdown and low output power when the perovskite material is used as a laser gain medium under the general condition are solved.
2. According to the preparation method of the perovskite nano laser based on the metal array microcavity, the quasi-two-dimensional perovskite film is compounded on the metal array microcavity and then covered with the transparent electrode for packaging, so that the advantages of high quantum yield, adjustable luminescence full-band, high carrier mobility of the quasi-two-dimensional perovskite film, capability of realizing laser emission by breaking through diffraction limit and optimizing carrier injection distribution of the nano array microcavity are combined, and the full-band, high-power, narrow-bandwidth and strong-coherence nano laser is realized by a simple and economical method.
3. Compared with the traditional laser, the method successfully breaks through the diffraction limit, realizes the sub-wavelength magnitude laser emission, has simple process, low cost and good batch property, can realize customization as required, and is beneficial to the development and application of the emerging optical fields such as on-chip integration, optical calculation and the like.
Drawings
Fig. 1 is a schematic flow chart of the present invention.
FIG. 2 is a schematic diagram of the structure of a metal array microcavity according to the present invention.
Fig. 3 is a schematic structural diagram of a perovskite micro nano laser prepared by the invention.
Fig. 4 is an electroluminescence spectrum of a perovskite nanolaser prepared in accordance with the present invention.
FIG. 5 is a schematic diagram of pump power density, laser intensity and laser half-width of perovskite nano laser prepared by the invention.
In the figure: 1. a metal array microcavity; 2. a quasi-two-dimensional perovskite thin film; 3. a top metal electrode; wavelength, wavelength; intensity, laser intensity; pump density, pump power density; FWHM, laser half-width.
Detailed Description
The invention is further described below with reference to the accompanying drawings:
the first embodiment is as follows: referring to fig. 1-5, the present embodiment is described, as shown in fig. 1-3, as a method for preparing a perovskite nano laser based on a metal array microcavity, where the method is implemented by the following steps:
S1: preparing a metal array microcavity 1, and taking the prepared metal array microcavity 1 as a resonant cavity. The material of the metal array microcavity 1 is a nano array or an array microcavity manufactured by processing one of gold (Au), silver (Ag), aluminum (Al), copper (Cu) and tin (Sn), the metal array microcavity 1 is manufactured by an oxidation method, and the steps for preparing the metal array microcavity 1 comprise:
S1.1: cutting a metal sheet into a round substrate, flattening the metal substrate by a hydraulic press, sequentially using absolute ethyl alcohol and ultrapure water for ultrasonic cleaning, and repeatedly cleaning until the surface is free of oil films and impurities. Preferably, the thickness of the metal sheet is 0.1-4 mm, so that the preparation of the substrate is facilitated, and the diameter of the circular substrate is 8-50 mm, so that the generation of the metal array microcavity 1 is facilitated.
S1.2: and (3) taking out the cleaned metal substrate obtained in the step S1.1, drying, and carrying out ice water bath polishing in the prepared acidic polishing solution (hydrochloric acid, nitric acid and perchloric acid). The polishing voltage of the ice water bath is 6-30V/piece, the current is 0.2-5A/piece, and the time is 0.5-5 min, so as to remove the surface oxide film, tiny scratches and other impurities.
S1.3: and (3) flushing the surface residual acid solution of the polished metal substrate obtained in the step (S1.2) by using absolute ethyl alcohol, drying, transferring and stamping in a hydraulic press by using a high-hardness metal film with an initial structure, and transferring the initial structure onto the metal substrate.
S1.4: and (3) placing the metal substrate which is embossed in the step (S1.3) into an oxidizing solution (carbonic acid, citric acid, hydrofluoric acid, oxalic acid, sulfurous acid and phosphoric acid) for oxidization, wherein the voltage of the oxidization is 2-15V/sheet, the current is 0.2-53A/sheet, and the time is 0-16 h, so as to obtain the metal array microcavity 1 with the thickness of about 5-3000 nm and the array period of 100-1000 nm and the oxide substrate thereof.
S1.5: and (3) taking out the metal substrate after the oxidation of S1.4, cleaning the metal substrate by using absolute ethyl alcohol, soaking the metal substrate in weak acid (chromic acid, phosphoric acid and oxalic acid) for 2-24 hours to remove the residual oxide layer, and obtaining an array microcavity on the substrate, wherein the structural type of the array microcavity depends on various parameters in the oxidation process to a great extent.
S2: and (3) preparing a quasi two-dimensional perovskite film 2, and coating the prepared quasi two-dimensional perovskite film 2 on the metal array microcavity 1 prepared in the step (S1). The material of the quasi two-dimensional perovskite film 2 is perovskite material, which is prepared by a precursor colloidal solution spin-coating method, the quasi two-dimensional perovskite film 2 is prepared by the spin-coating method on the metal array microcavity 1, and the specific preparation steps are as follows:
S2.1: preparing a precursor reaction solution: dissolving macromolecular organic matter (AX), monovalent metal halide (A' X) and divalent metal halide (BX 2) in a polar organic solvent, stirring, and filtering for standby to obtain a precursor reaction solution. The macromolecular organic matter is one of Naphthylmethylamine (NMAX), phenethylamine (PEAX), n-Butylamine (BAX), phenylbutylamine (PBAX) and Triethylamine (TEAX), and X is one or more of halogen elements Cl, br and I. In the monovalent metal halide (A 'X), A' is one of potassium (K), cesium (Cs), rubidium (Rb), lead (Pb), tin (Sn), germanium (Ge), methylamine (MA) and Formamidine (FA), and X is one or a mixture of a plurality of halogen elements Cl, br and I. In the divalent metal halide (BX), B is one of potassium (K), cesium (Cs), rubidium (Rb), lead (Pb), tin (Sn) and germanium (Ge), and X is one or more of halogen elements Cl, br and I, and the concentration is 0.01-1.2mol/L. The polar organic solvent is one of dimethyl sulfoxide (DMSO), N-N Dimethylformamide (DMF), gamma-hydroxybutyric acid lactone (GBL), N-methylpyrrolidone (NMP) and ethylene glycol methyl ether (MOE). The preferable stirring mode is that a magnetic stirrer is used for stirring, the stirring temperature is 25-120 ℃, the rotating speed of the magnetic stirrer is 500-4000 rpm, and the stirring time is 2-18 h, so that the stirring effect is better. The filtering mode is that a nylon NY membrane disposable oil filter is used for filtering, so that the filtering effect is better.
S2.2: dropwise adding the precursor reaction solution obtained in the step S2.1 into the right center of the metal array microcavity 1 in an isolated water-oxygen environment, and then spin-coating; preferably, 50-1000 mu L of precursor solution is dripped into the center of the array microcavity at a rotating speed of 300-800 rpm, then the rotating speed is increased to 2000-8000 rpm, and spin-coating is performed for 20-90 s, so that the quasi-two-dimensional perovskite film 2 which has uniform thickness and has the composition of A2-A' n-1BnX3n+1 is finally obtained, wherein n represents the thickness of a regular hexagonal octahedral layer between organic layers.
S2.3: and annealing the S2.2 spin-coated quasi-two-dimensional perovskite film 2, wherein the annealing temperature is 60-150 ℃ and the time is 10-120S.
S3: and (3) preparing a top metal electrode 3, and coating the prepared top metal electrode 3 on the quasi-two-dimensional perovskite film 2 prepared in the step (S2) for encapsulation and reinforcement. The top electrode is an indium tin oxide coating, which is formed by spin-coating and deposition by a solution method. The preparation steps of the top electrode comprise:
s3.1: dissolving indium tin oxide powder in meta-xylene to form a suspension;
s3.2: spin-coating the suspension obtained in the step S3.1 on the quasi two-dimensional perovskite film 2;
s3.3: and annealing the top electrode spin-coated in the step S3.2.
The top electrode is an indium tin oxide coating, which is prepared by dissolving indium tin oxide powder in m-xylene to form 0.2-20 mg/mL suspension, spin-coating the suspension on the quasi-two-dimensional perovskite film 2 at a rotating speed of 2000-6000 r/min, and annealing for 20-80 s at a temperature of 80-150 ℃ to obtain the compact transparent indium tin oxide coating.
Example 1
Preparing a metal array microcavity 1:
Cutting an aluminum sheet with the thickness of 0.8mm into a round substrate with the diameter of 24mm, flattening the round substrate by a hydraulic press, sequentially using absolute ethyl alcohol and ultrapure water for ultrasonic cleaning, and repeatedly cleaning until the surface is free of oil films and impurities;
taking out the cleaned aluminum substrate, drying, carrying out ice water bath polishing for 2.5min under the condition of 6V voltage and 0.5A current of each piece in the prepared hydrochloric acid polishing solution, and removing surface oxide films, tiny scratches and other impurities;
Washing the polished aluminum substrate with absolute ethyl alcohol to clean hydrochloric acid solution remained on the surface, blow-drying, transferring and imprinting in a hydraulic press by means of a nickel film with an initial structure, and transferring the initial structure onto a metal substrate;
placing the imprinted aluminum substrate in perchloric acid oxidizing solution, and oxidizing for 4 hours at a voltage of 12V and a current of 0.3A to obtain an aluminum array microcavity with a thickness of about 300nm and an array period of 500nm and an oxide substrate thereof;
Taking out the oxidized aluminum substrate, washing with absolute ethyl alcohol, soaking in chromic acid for 9 hours, and removing the residual oxide layer to obtain the complete array microcavity on the aluminum substrate.
Preparing a quasi two-dimensional perovskite thin film 2:
Dissolving 0.06mol/L PbBr 2, NMABr and CsBr in a mixed polar organic solvent of DMF=7:3 to form an organic-inorganic metal halide perovskite precursor solution;
placing the solution on a magnetic stirrer with the rotating speed of 900rpm at room temperature, and stirring for 6 hours;
filtering the solution in a nylon NY membrane disposable oil filter for standby;
in an isolated water-oxygen environment, dropwise adding 400 mu L of precursor solution into the center of the array microcavity at a rotating speed of 600rpm, then increasing the rotating speed to 5500rpm, and spin-coating for 50s to finally obtain a quasi-two-dimensional perovskite film 2 which is uniform in thickness and has a composition of (NMA) 2-Csn-1PbnBr3n+1, wherein n represents the thickness of a regular hexagonal octahedral layer between organic layers;
The spin-coated quasi-two-dimensional perovskite thin film 2 was annealed on a heating plate at 120 ℃ for 60s.
Preparing a top metal electrode 3:
Dissolving indium tin oxide powder in m-xylene to form 15mg/mL suspension;
spin-coating the suspension on the quasi-two-dimensional perovskite film 2 at a rotating speed of 4000r/min, and annealing for 30s at 130 ℃ to obtain a compact and transparent indium tin oxide coating.
Finally, the perovskite nano laser with the light-emitting wavelength of 526nm, the half-peak width of 0.07nm, the laser threshold value of 3.2 mu J/cm 2, the output power of 3.9mW, the beam quality factor of 0.96, the working current of 78mA and the threshold current of 65mA can be obtained.
Example 2
Preparing a metal array microcavity 1:
Cutting a silver sheet with the thickness of 1.2mm into a round substrate with the diameter of 10mm, flattening the substrate by a hydraulic press, sequentially using absolute ethyl alcohol and ultrapure water for ultrasonic cleaning, and repeatedly cleaning until the surface is free of oil films and impurities;
Taking out the cleaned silver substrate, drying, carrying out ice water bath polishing for 1.5min under the condition of 4V voltage and 0.8A current of each piece in the prepared nitric acid polishing solution, and removing surface oxide films, tiny scratches and other impurities;
Washing the polished silver substrate with absolute ethyl alcohol to clean nitric acid solution remained on the surface, blow-drying, transferring and imprinting in a hydraulic press by means of a nickel film with an initial structure, and transferring the initial structure onto a metal substrate;
Placing the imprinted silver substrate in phosphoric acid oxidizing solution, and oxidizing for 2 hours at a voltage of 9V and a current of 0.5A to obtain a silver array microcavity with a thickness of about 200nm and an array period of 600nm and an oxide substrate thereof;
and taking out the oxidized silver substrate, washing the silver substrate by using absolute ethyl alcohol, soaking the silver substrate in chromic acid for 9 hours, and removing a residual oxide layer to obtain a complete array microcavity on the silver substrate.
Preparing a quasi two-dimensional perovskite thin film 2:
dissolving 0.06mol/L of CrCl 2, PEACl and KCl in a mixed polar organic solvent of DMF=2:8 to form an organic-inorganic metal halide perovskite precursor solution;
Placing the solution on a magnetic stirrer with the rotating speed of 800rpm at room temperature, and stirring for 12 hours;
filtering the solution in a nylon NY membrane disposable oil filter for standby;
In an isolated water-oxygen environment, dropwise adding 300 mu L of precursor solution into the center of the array microcavity at a rotating speed of 400rpm, then increasing the rotating speed to 4500rpm, and spin-coating for 80 seconds to finally obtain a quasi-two-dimensional perovskite film 2 which is uniform in thickness and has a composition of (PEA) 2-Kn-1CrnCl3n+1, wherein n represents the thickness of a regular hexagonal octahedral layer between organic layers;
the spin-coated quasi-two-dimensional perovskite thin film 2 was annealed on a hot plate at 75 ℃ for 20s.
Preparing a top metal electrode 3:
Dissolving indium tin oxide powder in meta-xylene to form 10mg/mL suspension;
spin-coating the suspension on the quasi-two-dimensional perovskite film 2 at a rotating speed of 3000r/min, and annealing for 20s at 90 ℃ to obtain a compact and transparent indium tin oxide coating.
Finally, the perovskite nano laser with the luminous wavelength of 409nm, the half-peak width of 0.41nm, the laser threshold value of 9.4 mu J/cm 2, the output power of 2.7mW, the beam quality factor of 0.94, the working current of 90mA and the threshold current of 75mA can be obtained.
As shown in fig. 4 and fig. 5, the perovskite material with high quantum yield, flexible and adjustable band gap and high carrier mobility is used as a gain medium, and the micro-nano array microcavity is combined to perform local action on an optical field, so that the emission of the perovskite nano laser with high power, narrow bandwidth, high coherence and high collimation in the electric injection sub-wavelength level is realized by an electric injection mode. Breaks through diffraction limit and realizes micro-nano laser emission.
The present invention is not limited to the preferred embodiments, but is capable of modification in all respects, including as disclosed herein, and other embodiments and modifications will be apparent to those skilled in the art, upon consideration of the foregoing disclosure, without departing from the scope of the present invention, however, any simple modification, equivalent replacement, improvement, etc. of the above embodiments, such as changing the face recognition to the vehicle recognition or the person recognition, still fall within the scope of the technical solution of the present invention, according to the technical spirit of the present invention.
Claims (8)
1. A preparation method of a perovskite nano laser based on a metal array microcavity is characterized by comprising the following steps: the preparation method of the perovskite nano laser based on the metal array microcavity is realized by the following steps:
s1: preparing a metal array microcavity, wherein the prepared metal array microcavity is used as a resonant cavity, the metal array microcavity is made of one of gold, silver, aluminum, copper and tin, and the step of preparing the metal array microcavity comprises the following steps of:
S1.1: cutting metal sheet into round base, flattening the metal base by hydraulic press, ultrasonic cleaning with absolute ethyl alcohol and ultrapure water successively, repeating cleaning until there is no oil film and impurity on the surface,
S1.2: taking out the cleaned metal substrate obtained in the step S1.1, drying, carrying out ice water bath polishing in the prepared acidic polishing solution,
S1.3: washing the surface of the polished metal substrate obtained in the step S1.2 with absolute ethyl alcohol to obtain an acidic solution, blow-drying, transferring and imprinting the initial structure onto the metal substrate by means of a high-hardness metal film with the initial structure in a hydraulic press,
S1.4: the metal substrate which is well stamped in the step S1.3 is placed in oxidizing solution for oxidization, so as to obtain a metal array microcavity and an oxide substrate thereof, wherein the oxidizing solution is one of carbonic acid, citric acid, hydrofluoric acid, oxalic acid, sulfurous acid and phosphoric acid, the oxidizing voltage is 2-15V/sheet, the current is 0.2-53A/sheet, the time is 0-16 h,
S1.5: taking out the metal substrate oxidized in the step S1.4, washing the metal substrate by using absolute ethyl alcohol, soaking the metal substrate in weak acid to remove a residual oxide layer, and obtaining a metal array microcavity;
S2: preparing a quasi two-dimensional perovskite film, and coating the prepared quasi two-dimensional perovskite film on the metal array microcavity prepared in the step S1;
s3: and (3) preparing a top metal electrode, and coating the prepared top metal electrode suspension on the quasi-two-dimensional perovskite film prepared in the step (S2) for packaging and reinforcing.
2. The method for preparing the perovskite nano laser based on the metal array microcavity, as set forth in claim 1, is characterized in that: the step of preparing the quasi two-dimensional perovskite thin film in the S2 comprises the following steps:
S2.1: preparing a precursor reaction solution: dissolving macromolecular organic matters, monovalent metal halides and divalent metal halides in a polar organic solvent, stirring, and filtering for standby to obtain a precursor reaction solution;
S2.2: dropwise adding the precursor reaction solution obtained in the step S2.1 into the right center of the metal array microcavity in an isolated water-oxygen environment, and then spin-coating;
s2.3: and annealing the S2.2 spin-coated quasi-two-dimensional perovskite film.
3. The method for preparing the perovskite nano laser based on the metal array microcavity according to claim 2, which is characterized in that: the macromolecular organic matter in the S2.1 is one of naphthylmethylamine, phenethylamine, n-butylamine, phenylbutylamine and triethylamine.
4. The method for preparing the perovskite nano laser based on the metal array microcavity according to claim 2, which is characterized in that: the monovalent metal halide in S2.1 is expressed as A 'X, wherein A' is one of potassium, cesium and rubidium, and X is one or more of halogen elements Cl, br and I.
5. The method for preparing the perovskite nano laser based on the metal array microcavity according to claim 2, which is characterized in that: the divalent metal halide in S2.1 is represented as B 2 X, and the concentration is 0.01-1.2mol/L, wherein B is one of lead, tin and germanium, and X is one or a mixture of more of halogen elements Cl, br and I.
6. The method for preparing the perovskite nano laser based on the metal array microcavity according to claim 2, which is characterized in that: the polar organic solvent in the S2.1 is one of dimethyl sulfoxide, N-N dimethylformamide, gamma-hydroxybutyric acid lactone, N-methylpyrrolidone and ethylene glycol methyl ether.
7. The method for preparing the perovskite nano laser based on the metal array microcavity, as set forth in claim 1, is characterized in that: the top electrode is an indium tin oxide coating.
8. The method for preparing the perovskite nano laser based on the metal array microcavity, as set forth in claim 7, is characterized in that: the preparation steps of the top electrode comprise:
s3.1: dissolving indium tin oxide powder in meta-xylene to form a suspension;
s3.2: spin-coating the suspension obtained in the step S3.1 on the quasi two-dimensional perovskite film;
s3.3: and annealing the top electrode spin-coated in the step S3.2.
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