Wavelength-tunable perovskite micro / nano-laser and preparation method thereof

Abstract

The present disclosure provides a wavelength-tunable perovskite micro-nano laser and a preparation method, and relates to a micro-nano optical device. The method comprises the following steps: performing ultraviolet ozone treatment on a substrate surface; adding an anti-solvent of a perovskite material into a semi-sealed container, and placing the treated substrate on a support in the semi-sealed container; adding a solution dropwise to the surface of the treated substrate, and then performing semi-sealing; heating the bottom of the semi-sealed container to a preset temperature, so that the anti-solvent volatilizes into the solution to increase the supersaturation of the solution surface, and perovskite micro-nano lasers are grown at the gas-liquid interface; and drying the solvent of the solution on the substrate surface to form perovskite micro-nano lasers on the substrate.

Description

Technical Field

[0001] This disclosure relates to the field of micro-nano optical device technology, and in particular to a wavelength-tunable perovskite micro-nano laser and its fabrication method. Background Technology

[0002] Micro- and nano-semiconductor optoelectronic devices, due to their small size, excellent performance, and ease of integration, have significant application prospects in communication, sensing, and lighting fields. Perovskite nanolasers are a novel type of micro- and nano-semiconductor optoelectronic device, possessing advantages such as high quality factor and tunable lasing wavelength, and can be mass-produced at low cost using solution methods. However, traditional solution-based production often utilizes an antisolvent atmosphere created by sealing the antisolvent in a container. This closed environment results in a long growth cycle, exceeding 12 hours. Furthermore, byproducts such as large-sized crystals are easily obtained in the solution, leading to low raw material utilization. In addition, due to factors such as component segregation, it is difficult to obtain lasers with tunable emission wavelengths. Summary of the Invention

[0003] In view of this, the present disclosure provides a wavelength-tunable perovskite micro / nano laser and its fabrication method, which at least partially solves the above-mentioned technical problems.

[0004] This disclosure provides a method for fabricating a wavelength-tunable perovskite micro / nano laser, comprising: treating a substrate surface with ultraviolet ozone; adding an anti-solvent of perovskite material to a semi-sealed container, placing the treated substrate on a support inside the semi-sealed container; dripping a solution onto the treated substrate surface to complete the semi-sealing; heating the bottom of the semi-sealed container to a preset temperature to allow the anti-solvent to evaporate into the solution to increase the supersaturation of the solution surface, thereby growing a perovskite micro / nano laser at the gas-liquid interface; and drying the solvent in the solution on the substrate surface to form a perovskite micro / nano laser on the substrate.

[0005] According to embodiments of this disclosure, the substrate material includes one of quartz, indium tin oxide, silicon, and aluminum oxide; the ultraviolet ozone treatment of the substrate surface includes: cleaning the substrate; and performing ultraviolet ozone treatment on the cleaned substrate at room temperature for 15 min to 30 min.

[0006] According to embodiments of this disclosure, the antisolvent includes one of acetonitrile, toluene, and chlorobenzene, and the amount of antisolvent used is 0.5 mL to 3 mL.

[0007] According to embodiments of this disclosure, the solute in the solution includes one or more of cesium lead bromine and cesium lead chloride, with a concentration of 0.04 mol / L to 0.1 mol / L; the solvent in the solution includes dimethyl sulfoxide; 0 to 100% by volume of antisolvent may be added to the solution before use, and the antisolvent includes acetonitrile, toluene, and chlorobenzene; the volume of the solution used is 1 μL to 6 μL.

[0008] According to embodiments of this disclosure, the solution further includes additives, including one or more of methylammonium chloride, methylammonium bromide, butylammonium bromide, formamidinium hydrobromide, and phenylethylammonium bromide, with a concentration of 0 to 0.04 mol / L.

[0009] According to embodiments of this disclosure, the preset temperature range is 35°C to 40°C.

[0010] According to embodiments of this disclosure, drying the solvent of a solution on a substrate surface to form a perovskite micro / nano laser includes: drying the solvent of the solution on the substrate surface for 1 to 6 hours to allow the perovskite micro / nano laser grown at the gas-liquid interface to move toward the edge of the liquid film and remain on the substrate after contacting the gas-liquid-solid three-phase junction.

[0011] According to embodiments of this disclosure, the semi-sealed container is a glass container, with a glass right-angle vent pipe on the side wall of the glass container and an inclined plate above the support; the semi-sealing is achieved by dripping a solution onto the surface of the treated substrate, which includes: achieving semi-sealing of the semi-sealed container based on the glass right-angle vent pipe; the method further includes: allowing the volatile anti-solvent to contact the inclined plate and condense and drip to the bottom of the semi-sealed container.

[0012] According to embodiments of this disclosure, the method further includes: installing a condensation reflux device at the end of a glass right-angle vent tube, and recovering the evaporated antisolvent through the condensation reflux device.

[0013] Another aspect of this disclosure provides a wavelength-tunable perovskite micro / nano laser, which is prepared using the above-described method. The emission spectrum of the wavelength-tunable perovskite micro / nano laser covers a wavelength range of 425 nm to 557 nm.

[0014] The wavelength-tunable perovskite micro / nano laser and its fabrication method provided in this disclosure can achieve at least the following technical effects:

[0015] By using ultraviolet-ozone treatment to activate the substrate surface, the solution spreads fully, increasing the surface area in contact with the antisolvent atmosphere. Furthermore, the introduction of the antisolvent of the perovskite material into the solution enhances the solution saturation. The gas-liquid interface exhibits a higher degree of supersaturation than the substrate and the solution, thus enabling the perovskite micro / nano laser to grow rapidly at the interface and significantly shortening the growth cycle.

[0016] Furthermore, the gas-liquid interface growth method significantly reduces the amount of precursor solution required, the full spread of the solution accelerates the reaction process, and the semi-sealed environment accelerates solvent evaporation, thereby greatly shortening the growth cycle.

[0017] In addition, the preparation method is low-cost and simple, and the prepared perovskite micro-nano materials have good crystallinity and smooth surface morphology. The lasers constructed from these materials have tunable emission wavelengths, with emission peak wavelengths covering 425–557 nm, and have broad application prospects. Attached Figure Description

[0018] The above and other objects, features and advantages of this disclosure will become clearer from the following description of embodiments with reference to the accompanying drawings, in which:

[0019] Figure 1 A flowchart illustrating a method for fabricating a wavelength-tunable perovskite micro / nano laser according to an embodiment of the present disclosure is shown.

[0020] Figure 2 A schematic diagram illustrates a semi-sealed container structure used for growing perovskite micro / nano lasers according to embodiments of the present disclosure.

[0021] Figure 3 A scanning electron microscope image of a perovskite micro / nano laser according to an embodiment of the present disclosure is shown schematically.

[0022] Figure 4 The illustration schematically shows the emission spectrum of a perovskite micro / nano laser obtained by femtosecond laser pumping according to an embodiment of the present disclosure.

[0023] Figure 5 The diagram illustrates the polarization characteristics of the emission emitted by a perovskite micro / nano laser according to an embodiment of the present disclosure in an operational state.

[0024] Figure 6 The emission spectrum of a perovskite micro / nano laser according to several embodiments of the present disclosure is illustrated in an operational state. Detailed Implementation

[0025] To make the objectives, technical solutions, and advantages of this disclosure clearer, the following detailed description is provided in conjunction with specific embodiments and accompanying drawings. Obviously, the described embodiments are only some, not all, of the embodiments of this disclosure. All other embodiments obtained by those skilled in the art based on the embodiments of this disclosure without inventive effort are within the scope of protection of this disclosure.

[0026] The terminology used herein is for the purpose of describing particular embodiments only and is not intended to limit this disclosure. The terms “comprising,” “including,” etc., as used herein indicate the presence of the stated features, steps, operations, and / or components, but do not exclude the presence or addition of one or more other features, steps, operations, or components.

[0027] In this disclosure, unless otherwise expressly specified and limited, the terms "installation," "connection," "linking," "fixing," etc., should be interpreted broadly. For example, they can refer to a fixed connection, a detachable connection, or an integral part; they can refer to a mechanical connection, an electrical connection, or a connection that allows communication between them; they can refer to a direct connection or an indirect connection through an intermediate medium; they can refer to the internal communication of two components or the interaction between two components. Those skilled in the art can understand the specific meaning of the above terms in this disclosure according to the specific circumstances.

[0028] In the description of this disclosure, it should be understood that the terms "longitudinal", "length", "circumferential", "front", "rear", "left", "right", "top", "bottom", "inner", "outer", etc., indicate the orientation or positional relationship based on the orientation or positional relationship shown in the accompanying drawings, and are only for the convenience of describing this disclosure and simplifying the description, and do not indicate or imply that the subsystem or element referred to must have a specific orientation, or be constructed and operated in a specific orientation, and therefore should not be construed as a limitation of this disclosure.

[0029] Throughout the accompanying drawings, identical elements are represented by the same or similar reference numerals. Conventional structures or configurations have been omitted where they may cause confusion in understanding this disclosure. Furthermore, the shapes, dimensions, and positional relationships of the components in the drawings do not reflect their actual size, scale, or actual positional relationships. Additionally, any reference symbols enclosed in parentheses should not be construed as limiting this disclosure.

[0030] Similarly, to simplify this disclosure and aid in understanding one or more of the various aspects of the disclosure, in the above description of exemplary embodiments of the present disclosure, various features of the present disclosure are sometimes grouped together in a single embodiment, figure, or description thereof. The use of terms such as "one embodiment," "some embodiments," "example," "specific example," or "some examples," etc., refers to a specific feature, structure, material, or characteristic described in connection with that embodiment or example, which is included in at least one embodiment or example of the present disclosure. In this specification, illustrative expressions of the above terms do not necessarily refer to the same embodiment or example. Furthermore, the specific features, structures, materials, or characteristics described may be combined in any suitable manner in one or more embodiments or examples.

[0031] Furthermore, the terms "first" and "second" are used for descriptive purposes only and should not be construed as indicating or implying relative importance or implicitly specifying the number of technical features indicated. Therefore, a feature defined as "first" or "second" may explicitly or implicitly include one or more of that feature. In the description of this disclosure, "multiple" means at least two, such as two, three, etc., unless otherwise explicitly specified.

[0032] Figure 1A flowchart illustrating a method for fabricating a wavelength-tunable perovskite micro / nano laser according to an embodiment of the present disclosure is shown.

[0033] like Figure 1 As shown, the preparation method may include, for example, operations S101 to S103.

[0034] In operation S101, the substrate surface is subjected to ultraviolet ozone treatment.

[0035] In embodiments of this disclosure, ultraviolet ozone treatment of the substrate surface may include cleaning the substrate. The cleaned substrate is then subjected to ultraviolet ozone treatment for 15 to 30 minutes at room temperature. The substrate material includes one of quartz, indium tin oxide, silicon (100) oxide, and aluminum oxide.

[0036] For example, a quartz (SiO2) substrate with dimensions of 15mm × 15mm and a thickness of 1mm is provided. The substrate is first cleaned with diluted detergent, then ultrasonically cleaned for 20 minutes each with deionized water, acetone, and isopropanol, and finally placed in ethanol for later use. After removing the substrate from the ethanol, the ethanol on the substrate surface is dried with dry nitrogen gas, and then subjected to ultraviolet ozone treatment at room temperature for 15 minutes.

[0037] In operation S102, the antisolvent of the perovskite material is added to a semi-sealed container, and the treated substrate is placed on a support inside the semi-sealed container.

[0038] In the embodiments of this disclosure, the antisolvent may include one of acetonitrile, toluene, and chlorobenzene, and the amount of antisolvent used may be 0.5 mL to 3 mL.

[0039] For example, 98% anhydrous acetonitrile can be added.

[0040] In operation S103, after the solution is dropped onto the treated substrate surface, a semi-sealing is completed. The bottom of the semi-sealed container is heated to a preset temperature, so that the antisolvent evaporates into the solution to increase the supersaturation of the solution surface, thereby growing a perovskite micro / nano laser at the gas-liquid interface.

[0041] In embodiments of this disclosure, the solute in the solution may include one or more of cesium lead bromine and cesium lead chloride, with a concentration of 0.04 mol / L to 0.1 mol / L. The solvent in the solution may include dimethyl sulfoxide. The volume of the solution may be 1 μL to 6 μL. Before use, an antisolvent, including acetonitrile, toluene, or chlorobenzene, may be added at a volume ratio of 0 to 100%.

[0042] For example, the solution can be a pre-prepared 0.05 mol / L cesium lead bromide (CsPbBr3) dimethyl sulfoxide solution, to which an equal volume ratio of 99.8% acetonitrile is added before dropwise addition. Alternatively, the solution can be a pre-prepared 0.05 mol / L cesium lead chloride (CsPbCl3) solution or a 0.05 mol / L mixed solution of cesium lead chloride and cesium lead bromide, to which 50% to 100% by volume ratio of 99.8% acetonitrile is added before dropwise addition. The solution volume can be 1.5 μL. Upon contact with the substrate surface, the solution exhibits wetting properties, and the droplet spreads to form a liquid film capable of covering the entire substrate surface.

[0043] Furthermore, the solution may also include additives, which may include one or more of methylammonium chloride, methylammonium bromide, butylammonium bromide, formamidinium hydrobromide, and phenylethylammonium bromide, at a concentration of 0–0.04 mol / L.

[0044] In the embodiments of this disclosure, the preset temperature range can be 35°C to 40°C.

[0045] For example, heat the bottom of a semi-sealed container to 37.5°C.

[0046] In operation S204, the solvent of the solution on the substrate surface is dried to form a perovskite micro / nano laser on the substrate.

[0047] In embodiments of this disclosure, drying the solvent of the substrate surface solution to form the perovskite micro / nano laser on the substrate includes: drying the solvent of the substrate surface solution for 1 to 6 hours to allow the perovskite micro / nano laser grown at the gas-liquid interface to move toward the edge of the liquid film and remain on the substrate after contacting the gas-liquid-solid three-phase intersection.

[0048] For example, it takes 2 hours to dry the solvent from the bottom of the heated semi-sealed container to the substrate surface.

[0049] When high-temperature acetonitrile vapor comes into contact with the liquid surface of the lower-temperature substrate, it liquefies and enters the solution, causing a rapid increase in the supersaturation of the solution surface. This, in turn, allows the perovskite micro / nano laser to grow rapidly at the gas-liquid interface. During the solvent drying process on the substrate surface, the perovskite micro / nano lasers grown at the gas-liquid interface move towards the edge of the liquid film. After contacting the three-phase junction of gas, liquid, and solid, they remain on the substrate, resulting in a relatively uniform distribution of perovskite micro / nano lasers across the entire substrate.

[0050] Figure 2 A schematic diagram illustrates a semi-sealed container structure used for growing perovskite micro / nano lasers according to embodiments of the present disclosure.

[0051] like Figure 2As shown, the semi-sealed container is a glass container with a right-angled glass vent tube on its side wall and an inclined plate above the support. The right-angled glass vent tube achieves a semi-sealed, rather than a fully sealed, effect on the semi-sealed container. The inclined plate allows the volatile anti-solvent to condense and drip to the bottom of the semi-sealed container after contacting the plate.

[0052] For example, a semi-sealed container uses a glass container with an inner diameter of 15cm. Its side wall has a glass right-angle vent tube with a side length of 3cm and an inner diameter of 1cm, and an internal support about 8cm high. Acetonitrile evaporates from the bottom of the container at a higher temperature to form acetonitrile vapor. The acetonitrile vapor condenses and drips to the bottom of the container after contacting the top of the container at a lower temperature or the inclined plate on the support, thus realizing the recycling of acetonitrile.

[0053] In this embodiment, the method further includes: installing a condensation reflux device at the end of the glass right-angle vent tube, and recovering the volatilized antisolvent through the condensation reflux device to further reduce reagent consumption.

[0054] Based on the above-described method for fabricating wavelength-tunable perovskite micro / nano lasers, this disclosure also provides a wavelength-tunable perovskite micro / nano laser. The emission spectrum of the wavelength-tunable perovskite micro / nano laser, fabricated using the above method, covers a wavelength range of 425 nm to 557 nm.

[0055] For example, perovskite micro / nano lasers can be obtained by pumping with 350nm, 400nm, or 800nm ​​femtosecond lasers.

[0056] To demonstrate the advantages of the wavelength-tunable perovskite micro / nano laser and its fabrication method provided in this disclosure, some test data are listed below for illustration.

[0057] Figure 3 A scanning electron microscope image of a perovskite micro / nano laser according to an embodiment of the present disclosure is shown schematically.

[0058] like Figure 3 As shown, the perovskite micro / nano laser has a well-preserved surface morphology, sharp edges and corners, and a flat end face.

[0059] Figure 4 The illustration schematically shows the emission spectrum of a perovskite micro / nano laser obtained by femtosecond laser pumping according to an embodiment of the present disclosure.

[0060] like Figure 4 As shown, after the pump power reaches the threshold condition, the full width at half maximum (FWHM) of the emission peak decreases and the intensity increases significantly. At this time, the perovskite micro / nano laser is in working condition.

[0061] Figure 5 The diagram illustrates the polarization characteristics of the emission emitted by a perovskite micro / nano laser according to an embodiment of the present disclosure in an operational state.

[0062] like Figure 5 As shown, 0° corresponds to the long side of the micro / nano laser, indicating that the emission of the micro / nano laser has good polarization characteristics.

[0063] Figure 6 The emission spectrum of a perovskite micro / nano laser according to several embodiments of the present disclosure is illustrated in an operational state.

[0064] like Figure 6 As shown, the emission peak wavelength of the micro / nano laser covers 425nm to 557nm.

[0065] In summary, the wavelength-tunable perovskite micro / nano laser and its fabrication method provided in this disclosure have a short growth cycle, low cost, simple process, and the perovskite micro / nano material prepared has good crystallinity and smooth surface morphology.

[0066] The above description is merely a specific embodiment of this disclosure, but the scope of protection of this application is not limited thereto. Any changes or substitutions made within the spirit and principles of this disclosure should be covered within the scope of protection of this application. Therefore, the scope of protection of this application should be determined by the scope of the claims.

Claims

1. A method for fabricating a wavelength-tunable perovskite micro / nano laser, comprising: The substrate surface is subjected to ultraviolet ozone treatment to activate the substrate surface; An antisolvent for perovskite material is added to a semi-sealed container, and the treated substrate is placed on a support inside the semi-sealed container; the semi-sealed container is a glass container, and the side wall of the glass container is provided with a glass right-angle vent tube. After adding a solution to the treated substrate surface, the semi-sealed container is partially sealed by the glass right-angle vent tube. The bottom of the semi-sealed container is heated to a preset temperature, so that the antisolvent evaporates into the solution to increase the supersaturation of the solution surface, thereby growing the perovskite micro / nano laser at the gas-liquid interface. The solvent of the solution on the substrate surface is dried to form the perovskite micro / nano laser on the substrate. The solvent of the solution on the substrate surface is dried for 1 h to 6 h to allow the perovskite micro / nano laser grown at the gas-liquid interface to move toward the edge of the liquid film and remain on the substrate after contacting the gas-liquid-solid three-phase intersection point.

2. The method for fabricating a wavelength-tunable perovskite micro / nano laser according to claim 1, wherein, The substrate material includes one of quartz, indium tin oxide, silicon, and aluminum oxide; the ultraviolet ozone treatment of the substrate surface includes: The substrate is cleaned; At room temperature, the cleaned substrate is subjected to ultraviolet ozone treatment for 15 to 30 minutes.

3. The method for fabricating a wavelength-tunable perovskite micro / nano laser according to claim 1, wherein, The antisolvent includes one of acetonitrile, toluene, and chlorobenzene, and the amount of the antisolvent used is 0.5 mL to 3 mL.

4. The method for fabricating a wavelength-tunable perovskite micro / nano laser according to claim 1 or 3, wherein, The solute in the solution includes one or more of cesium lead bromine and cesium lead chloride, with a concentration of 0.04 mol / L to 0.1 mol / L; the solvent in the solution includes dimethyl sulfoxide; 0 to 100% by volume of antisolvent may be added to the solution before use, the antisolvent including acetonitrile, toluene, and chlorobenzene; the volume of the solution used is 1 μL to 6 μL.

5. The method for fabricating a wavelength-tunable perovskite micro / nano laser according to claim 4, wherein, The solution also includes additives, which include one or more of methylammonium chloride, methylammonium bromide, butylammonium bromide, formamidinium hydrobromide, and phenylethylammonium bromide, with a concentration of 0–0.04 mol / L.

6. The method for fabricating a wavelength-tunable perovskite micro / nano laser according to claim 1, wherein, The preset temperature range is 35 ℃~40 ℃.

7. The method for fabricating a wavelength-tunable perovskite micro / nano laser according to claim 1, wherein, An inclined flat plate is provided above the support; The method further includes: allowing the volatile antisolvent to contact the inclined plate and then condense and drip to the bottom of the semi-sealed container.

8. The method for fabricating a wavelength-tunable perovskite micro / nano laser according to claim 7, further comprising: A condensation reflux device is installed at the end of the glass right-angle vent pipe to recover the evaporated anti-solvent.

9. A wavelength-tunable perovskite micro / nano laser, fabricated using the method described in any one of claims 1-8, wherein the emission spectrum of the wavelength-tunable perovskite micro / nano laser covers a wavelength range of 425 nm to 557 nm.

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