Vacuum evaporation perovskite laser device and application thereof

Abstract

The application discloses a vacuum evaporation perovskite laser device, which comprises a substrate, a conductive substrate, a first layer of transport layer, a gain layer, a second layer of transport layer and a metal electrode, wherein the gain layer is a vacuum evaporation perovskite material, the composition of the perovskite material is ABX3, A is a monovalent cation, B is a metal cation, and X is an anion; and the laser device or the perovskite gain medium realizes laser emission under femtosecond laser pumping. The application realizes preparation of a photoelectric cooperative laser device based on vacuum evaporation perovskite under low-temperature conditions, and the preparation method meets the demand of large-area and batch preparation, is compatible with the industry, and has an industrial application prospect.

Description

Technical Field

[0001] This invention belongs to the field of laser device technology, specifically relating to a vacuum-deposited perovskite laser device and its applications. Background Technology

[0002] High-performance micro / nano laser devices are among the core components of future on-chip photonic information processing systems and integrated optoelectronics. Stimulated emission of photonic materials is a necessary condition for laser generation. Currently, the limited optical gain of traditional photonic materials makes it difficult to overcome the high losses in the miniaturization process of lasers, becoming a major obstacle to the realization of optoelectronic integrated chips. Metal halide perovskites have advantages such as low cost, tunable bandgap, high color purity, high optical gain, and their dimensions can be arbitrarily controlled to obtain enhanced exciton binding energy and gain effects, making them one of the most competitive next-generation gain materials. Lasers generally include a pump source, a gain medium, and a resonant cavity. In current perovskite laser device fabrication, most methods involve complex processes such as solution methods to design and fabricate perovskite gain media, which are time-consuming and difficult to meet the needs of large-scale commercial production. Researchers have been able to achieve lasing of perovskite random lasers on flexible laser substrates using solution methods. However, the formation of such random lasers mainly relies on a lossy scattering mechanism, resulting in generally high threshold energy and high energy consumption. Therefore, there is an urgent need to develop a perovskite laser device that is simple to manufacture, has a low threshold, and low optical loss, in order to promote its practical application in multiple fields.

[0003] While perovskite lasers have made great strides, most of their development remains limited to laboratory-scale solution-based preparation studies, making it difficult to meet the demands of large-scale, highly reproducible industrial production. Summary of the Invention

[0004] The first objective of this invention is to provide a vacuum-deposited perovskite laser device, addressing the problems in the prior art.

[0005] Therefore, the above-mentioned objectives of the present invention are achieved through the following technical solutions:

[0006] A vacuum-deposited perovskite laser device includes a substrate, a conductive substrate, a first transmission layer, a gain layer, a second transmission layer, and a metal electrode. The gain layer is a vacuum-deposited perovskite material with the composition ABX3, where A is a monovalent cation, B is a metal cation, and X is an anion. The laser device or perovskite gain medium achieves laser emission under femtosecond laser pumping.

[0007] While adopting the above technical solutions, the present invention may also adopt or combine the following technical solutions:

[0008] As a preferred technical solution of the present invention: the perovskite material is prepared by vacuum evaporation, and the perovskite evaporation source precursor structure includes AX and BX2.

[0009] As a preferred technical solution of the present invention: the vacuum evaporation perovskite precursor source A is a monovalent cation, including but not limited to cesium ions, methylamine ions and formamidinium ions; B is a metal cation, including but not limited to lead ions and tin ions; X is an anion, including chloride ions, bromide ions and iodide ions.

[0010] As a preferred technical solution of the present invention: organic small molecules are added to the perovskite gain medium for 3-source or 4-source co-distillation, and the organic small molecules include benzylamine, phenethylamine, aromatic amine derivatives, triphenylphosphine oxide and fluorinated triphenylphosphine oxide and their derivatives.

[0011] As a preferred embodiment of the present invention, the conductive substrate comprises tin oxide, indium oxide, zinc oxide, or indium tin oxide.

[0012] As a preferred technical solution of the present invention, the metal electrode is an indium oxide electrode, a magnesium electrode, a silver electrode, or a composite electrode of cesium carbonate and silver.

[0013] As a preferred technical solution of the present invention: the pump source type includes optical pump source, electric pump source or a combination of the two pump sources, and the pumping method includes pulsed pumping and continuous pumping; wherein the optical pumping device structure is composed of a substrate and a perovskite gain medium, and the electric pumping device structure is composed of a substrate, a conductive substrate, a first transmission layer, a gain layer, a second transmission layer and a metal electrode.

[0014] As a preferred technical solution of the present invention: the perovskite gain layer adopts two-source, three-source or four-source co-evaporation, and the size of the perovskite crystal is controlled by adjusting the evaporation rate and the composition of the additives, thereby realizing the control of the laser emission threshold and gain effect of the gain medium.

[0015] The second objective of this invention is to provide an application of a vacuum-deposited perovskite laser device, addressing the problems in the prior art.

[0016] Therefore, the above-mentioned objectives of the present invention are achieved through the following technical solutions:

[0017] The aforementioned vacuum-deposited perovskite laser devices are used in lighting, displays, optoelectronic on-chip integration, and on-chip applications.

[0018] Compared with existing technologies, the vacuum evaporation perovskite laser device and its application of the present invention have the following beneficial effects: By using vacuum evaporation to prepare a perovskite gain layer and combining it with a device structure design optimized by bandgap engineering, the present invention solves the technical problems of poor film quality, such as insufficient uniformity, solvent residue, and porous and non-dense perovskite laser devices prepared by existing solution methods, as well as the inability to meet the requirements of large-area mass production. The present invention achieves the preparation of a perovskite gain medium with uniform and dense film, few defects, and long lifetime, and ultimately realizes the technical effects of integration with silicon-based, glass-based, and flexible substrates, wavelength tunable, low threshold, and high-efficiency optical pump laser emission, laying a solid process and material foundation for the industrial application of perovskite laser devices.

[0019] This invention enables the fabrication of a photoelectric synergistic laser device based on vacuum evaporation perovskite under low-temperature conditions. The fabrication method meets the requirements for large-area, batch fabrication, is compatible with industry, and has promising industrial application prospects. Attached Figure Description

[0020] Figure 1 The diagram shows the perovskite gain material vapor deposition process and the structural diagram of the perovskite laser devices prepared in Examples 1-5.

[0021] Figure 2 The experimental setup for measuring the performance of optically pumped laser devices under electric drive is shown in Figure 2-5 of the perovskite laser devices prepared in Examples 2-5.

[0022] Figure 3 The photoluminescence spectrum of the perovskite gain material prepared in Example 1 is shown below.

[0023] Figure 4 The image shows the scanning electron microscope (SEM) spectrum of the perovskite gain material prepared in Example 1.

[0024] Figure 5 The image shows the pump density-dependent photoluminescence spectrum of the laser device prepared in Example 1 under single-photon excitation. Detailed Implementation

[0025] The present invention will be described in further detail with reference to the accompanying drawings and specific embodiments.

[0026] A photoelectric synergistic laser device based on vacuum-deposited perovskite comprises one or more of the following: vacuum-deposited perovskite material and substrate, conductive electrode, and functional transport layer; wherein the gain layer is a perovskite material.

[0027] According to one embodiment of the present invention, the perovskite material is one or more of metal halide type and metal oxide type perovskite materials.

[0028] According to one embodiment of the present invention, the substrate includes rigid materials such as sapphire, silicon wafers or quartz glass, and also includes flexible substrate materials such as polyvinyl naphthalene, polyimide, polyethylene terephthalate and polydimethylsiloxane.

[0029] According to one embodiment of the present invention, the conductive electrode is a metal oxide such as indium tin oxide, zinc oxide or tin oxide, and a modification layer for changing the work function of the conductive substrate.

[0030] According to one embodiment of the present invention, the functional transport layer is prepared by solution deposition or vacuum evaporation. For example, the functional transport layer prepared by solution deposition may be poly(3,4-ethylenedioxythiophene / polystyrene sulfonate) (PEDOT:PSS), PEDOT:PSS modified with an ionic electroactive polymer, polyvinylcarbazole (PVK), zinc magnesium oxide, etc. The functional transport layer prepared by vacuum evaporation may be 4,4',4''-tris(carbazole-9-yl)triphenylamine (TCTA), molybdenum oxide or lithium fluoride, 1,3,5-tris(1-phenyl-1H-benzimidazol-2-yl)benzene (TPBi), or a co-evaporated compound thereof.

[0031] As a preferred embodiment, a vacuum-deposited perovskite laser device is characterized in that: the pump source type includes an optical pump source, an electric pump source, or a combination of the two pump sources, and the pumping method includes pulsed and continuous pumping; wherein the optical pump device structure consists of a substrate and a perovskite gain medium, and the electric pump device structure consists of a substrate, a conductive substrate, a first transmission layer, a gain layer, a second transmission layer, and a metal electrode.

[0032] An application of perovskite laser devices based on vacuum evaporation includes lighting, display, optoelectronic on-chip integration, and chip applications.

[0033] The present invention has the following beneficial effects:

[0034] The vacuum evaporation process is used to prepare perovskite gain materials, which can achieve high uniformity of perovskite thin films, meet the needs of large-area mass production, be compatible with existing semiconductor production line processes, and can be directly integrated with silicon-based, glass-based and flexible substrates, thus expanding the application scenarios.

[0035] Vacuum evaporation of gain materials avoids the solvent residue problem in solution preparation, forming a dense, non-porous perovskite film, reducing defect states, and extending device lifespan.

[0036] The device design combines optical pumping and electrical injection excitation mechanisms, and optimizes carrier transport, reduces the laser threshold, improves luminous efficiency, and achieves wavelength tunability through band engineering.

[0037] According to another aspect of the present invention, the present invention also provides a method for fabricating the above-mentioned photoelectric synergistic laser device based on vacuum evaporation perovskite, comprising the following steps:

[0038] 1. The first transport layer is deposited on the substrate using spin coating or vacuum thermal evaporation.

[0039] 2. A perovskite gain layer is deposited or grown on the first transport layer using a vacuum thermal evaporation process through multi-source co-evaporation.

[0040] 3. Deposit two transport layers on the perovskite gain layer.

[0041] 4. Based on step (3), deposit metal electrodes or composite electrodes to obtain the photoelectric synergistic laser device based on vacuum evaporation perovskite.

[0042] 5. Generation of perovskite lasers: The pumping method of the laser device may include optical pumping and electric pumping or a combination of both. For optical pumping, the device structure may consist of a substrate and a perovskite gain material or the device obtained in steps (1)-(4). For electric pumping or a combination of pumping including electric pumping, the device structure consists of the device obtained in steps (1)-(4).

[0043] Example 1

[0044] The specific fabrication steps of the laser device based on vacuum evaporation perovskite in this embodiment are as follows:

[0045] 1. Clean the quartz glass with acetone using ultrasonic cleaning for 20 minutes, then clean it with isopropanol using ultrasonic cleaning for 20 minutes, clean it with deionized water for 20 minutes, and finally dry the quartz glass with a nitrogen gun.

[0046] 2. Transfer the cleaned quartz glass to the vacuum evaporation chamber and evacuate the vacuum level to 5.0 × 10⁻⁶. -4 Torr below.

[0047] 3. Using dual-source co-evaporation of FAI and PbI2 precursors, the evaporation rates were 0.1 and 0.05 Å / s, respectively, and the perovskite film thickness was 40-100 nm.

[0048] 4. Encapsulate the perovskite gain material from step (3) using encapsulation glass.

[0049] 5. Test laser emission under femtosecond laser pumping.

[0050] Example 2

[0051] The fabrication method of the optoelectronic synergistic laser device based on vacuum evaporation perovskite in this embodiment includes the following specific fabrication steps:

[0052] 1. Ultrasonically clean the indium tin oxide glass with acetone for 20 min, then ultrasonically clean the quartz glass with isopropanol for 20 min, clean it with deionized water for 20 min, dry the substrate with a nitrogen gun, and treat it with plasma for 15 min.

[0053] 2. PEDOT:PSS is used as the first transport layer and is spin-coated onto the substrate cleaned in step (1).

[0054] 3. Move the hole transport layer to the vacuum evaporation chamber and evacuate the vacuum level to 5.0 × 10⁻⁶. -4 Torr below.

[0055] 4. FAI and PbI2 precursors were deposited by dual-source co-evaporation at evaporation rates of 0.1 and 0.05 Å / s, respectively, with perovskite film thicknesses of 40-100 nm.

[0056] 5. Vacuum evaporation of a 40 nm TPBi second transport layer;

[0057] 6. Vacuum evaporation of 1 nm LiF and 100 nm Al as electrodes completes device fabrication;

[0058] 7. Under femtosecond laser pumping, test laser emission; under current driving, test amplified radiation under the combined effects of current density, voltage, and photoelectric effect.

[0059] Example 3

[0060] The fabrication method of the optoelectronic synergistic laser device based on vacuum evaporation perovskite in this embodiment includes the following specific fabrication steps:

[0061] 1. Ultrasonically clean the indium tin oxide glass with acetone for 20 min, then ultrasonically clean the quartz glass with isopropanol for 20 min, clean it with deionized water for 20 min, dry the substrate with a nitrogen gun, and treat it with plasma for 15 min.

[0062] 2. PEDOT:PSS is used as the first transport layer and is spin-coated onto the substrate cleaned in step (1).

[0063] 3. Move the hole transport layer to the vacuum evaporation chamber and evacuate the vacuum level to below 5.0 × 10⁻⁴ Torr.

[0064] 4. FAI, CsI and PbI2 precursors were deposited by three-source co-evaporation at evaporation rates of 0.1, 0.02 and 0.05 Å / s, respectively, and the perovskite film thickness was 40-100 nm.

[0065] 5. Vacuum evaporation of a 40 nm TPBi second transport layer

[0066] 6. Vacuum evaporation of 1 nm LiF and 100 nm Al as electrodes completes device fabrication.

[0067] 7. Under femtosecond laser pumping, test laser emission; under current driving, test amplified radiation under the combined effects of current density, voltage, and photoelectric effect.

[0068] Example 4

[0069] The fabrication method of the optoelectronic synergistic laser device based on vacuum evaporation perovskite in this embodiment includes the following specific fabrication steps:

[0070] 1. Ultrasonically clean the indium tin oxide glass with acetone for 20 min, then ultrasonically clean the quartz glass with isopropanol for 20 min, clean it with deionized water for 20 min, dry the substrate with a nitrogen gun, and treat it with plasma for 15 min.

[0071] 2. PEDOT:PSS is used as the first transport layer and is spin-coated onto the substrate cleaned in step (1).

[0072] 3. Move the hole transport layer to the vacuum evaporation chamber and evacuate the vacuum level to 5.0 × 10⁻⁶. -4 Torr below.

[0073] 4. Using four-source co-evaporation, FAI, CsI and PbI2 precursors and TFPPO passivating agent were deposited at evaporation rates of 0.1, 0.02, 0.05 and 0.05 Å / s, respectively, and the perovskite film thickness was 40-100 nm.

[0074] 5. Vacuum evaporation of a 40 nm TPBi second transport layer;

[0075] 6. Vacuum evaporation of 1 nm LiF and 100 nm Al as electrodes completes device fabrication;

[0076] 7. Under femtosecond laser pumping, test laser emission; under current driving, test amplified radiation under the combined effects of current density, voltage, and photoelectric effect.

[0077] Example 5

[0078] The fabrication method of the optoelectronic synergistic laser device based on vacuum evaporation perovskite in this embodiment includes the following specific fabrication steps:

[0079] 1. Ultrasonically clean the indium tin oxide glass with acetone for 20 min, then ultrasonically clean the quartz glass with isopropanol for 20 min, clean it with deionized water for 20 min, dry the substrate with a nitrogen gun, and treat it with plasma for 15 min.

[0080] 2. Transfer the cleaned substrate to the vacuum evaporation chamber and evacuate the vacuum level to 5.0 × 10⁻⁶.-4 Torr below.

[0081] 3. Vacuum evaporation deposition of MoO3:TCTA 30 nm and 5 nm TCTA was used as the first transport layer.

[0082] 4. FAI, CsI and PbI2 precursors and TFPPO passivating agent were deposited by dual-source co-evaporation at evaporation rates of 0.1 and 0.05 Å / s, respectively, and the perovskite film thickness was 40-100 nm.

[0083] 5. Vacuum evaporation of a 40 nm TPBi second transport layer

[0084] 6. Vacuum evaporation of 1 nm LiF and 100 nm Al as electrodes completes device fabrication.

[0085] 7. Under femtosecond laser pumping, test laser emission; under current driving, test amplified radiation under the combined effects of current density, voltage, and photoelectric effect.

[0086] from Figure 1 As can be seen, vacuum-deposited perovskite laser devices can directly deposit gain materials within a vacuum cavity. From bottom to top, the layers are: substrate, conductive electrode, first transmission layer, gain material, second transmission layer, and top electrode.

[0087] Figure 2 The diagram shows the experimental setup for measuring the performance of optically pumped laser devices using the perovskite laser devices prepared in Examples 2-5 under electric drive. The main components include a pump laser source, a neutral density filter, a laser device, a long-pass filter, and a spectrometer.

[0088] Figure 3 The images shown are the photoluminescence spectra of the vacuum-deposited FAPbI3 thin films in Examples 1-2. Figure 3 It can be seen that the fluorescence peak is located at 785 nm.

[0089] Figure 4 The images shown are scanning electron microscope images of the vacuum-deposited FAPbI3 thin films in Examples 1-2. As shown in Figure 4, the grain size of the vacuum-deposited FAPbI3 is 103 nm.

[0090] Figure 5 The image shows the variable excitation power spectrum of the FAPbI3 thin film vacuum-deposited under single-photon excitation in Example 1.

[0091] The present invention has the following beneficial effects:

[0092] (1) The vacuum evaporation process can achieve large-area uniform deposition of perovskite thin films under low temperature conditions. The process is simple, highly repeatable, and compatible with existing semiconductor industry technologies. It effectively solves the bottleneck problem of the difficulty in large-scale fabrication of micro-nano laser devices and lays the foundation for commercialization.

[0093] (2) The prepared perovskite laser device has a low threshold characteristic, which helps to reduce the energy consumption of the device and improve the laser emission efficiency, and is suitable for low power optoelectronic integrated systems.

[0094] (3) This laser device has important application value in display technology, optoelectronic chip integration and photonic chip fields, and provides a reliable path for the practical application of high-performance, low-cost micro-nano laser devices.

[0095] The above specific embodiments are used to explain and illustrate the present invention, and are only preferred embodiments of the present invention, not intended to limit the present invention. Any modifications, equivalent substitutions, improvements, etc., made to the present invention within the spirit and scope of the claims shall fall within the protection scope of the present invention.

Claims

1. A vacuum-deposited perovskite laser device, characterized in that, The device includes a substrate, a conductive substrate, a first transport layer, a gain layer, a second transport layer, and a metal electrode. The gain layer is a vacuum-deposited perovskite material with a composition of ABX3, where A is a monovalent cation, B is a metal cation, and X is an anion. The laser device or perovskite gain medium achieves laser emission under femtosecond laser pumping.

2. The vacuum-deposited perovskite laser device as described in claim 1, characterized in that, The perovskite material is prepared by vacuum evaporation, and the perovskite evaporation source precursor structure includes AX and BX2.

3. The vacuum-deposited perovskite laser device as described in claim 1, characterized in that, The vacuum evaporation perovskite precursor source A is a monovalent cation, including but not limited to cesium ions, methylamine ions, and formamidinium ions; B is a metal cation, including but not limited to lead ions and tin ions; and X is an anion, including chloride ions, bromide ions, and iodide ions.

4. The vacuum-deposited perovskite laser device as described in claim 1, characterized in that, Organic small molecules are added to the perovskite gain medium for 3-source or 4-source co-evaporation. The organic small molecules include benzylamine, phenethylamine, aromatic amine derivatives, triphenylphosphine oxide, fluorinated triphenylphosphine oxide and its derivatives.

5. The vacuum-deposited perovskite laser device as described in claim 1, characterized in that: The conductive substrate includes tin oxide, indium oxide, zinc oxide, or indium tin oxide.

6. The vacuum-deposited perovskite laser device as described in claim 1, characterized in that: The metal electrode is an indium oxide electrode, a magnesium electrode, a silver electrode, or a composite electrode of cesium carbonate and silver.

7. The vacuum-deposited perovskite laser device as described in claim 1, characterized in that: Pump source types include optical pump sources, electric pump sources, or a combination of both. Pumping methods include pulsed and continuous pumping. The structure of optical pumping devices consists of a substrate and a perovskite gain medium, while the structure of electric pumping devices consists of a substrate, a conductive substrate, a first transport layer, a gain layer, a second transport layer, and a metal electrode.

8. The vacuum-deposited perovskite laser device as described in claim 2, characterized in that: The perovskite gain layer employs two-source, three-source, or four-source co-evaporation. By adjusting the evaporation rate and the composition of the additives, the size of the perovskite crystal can be controlled, thereby enabling the regulation of the laser emission threshold and gain effect of the gain medium.

9. The application of the vacuum-deposited perovskite laser device according to any one of claims 1-8, characterized in that: It is used in lighting, displays, optoelectronic on-chip integration, and chips.

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