Method for growing formamidine lead iodide perovskite with multiple quantum well fluorescence oscillation peaks
The position, temperature and time of formamidine iodine and lead iodide nanosheets are controlled by tube furnace equipment, and the formamidine iodine perovskite with multiple quantum well fluorescence oscillation peaks are grown, which solves the problems of high cost, complex equipment and difficult control in the existing technology, and achieves low-cost and low-temperature controllable multi-N value luminescence peak growth, which promotes quantum optical research.
Patent Information
- Application Number
- CN202510343422.7
- Authority / Receiving Office
- CN · China
- Patent Type
- Applications(China)
- Current Assignee / Owner
- Filing Date
- 2025-03-21
- Publication Date
- 2025-08-08
AI Technical Summary
The prior art is costly, complex equipment, and incompatible with the CMOS process when preparing multi-quantum well luminescent materials, making it difficult to accurately control growth conditions, resulting in low luminescence efficiency and difficult integration.
Using a tube furnace equipment, by controlling the position, temperature and time of formamidine iodine and lead iodide nanosheets, as well as the flow rate of inert gas, the directional transmission and controllable film formation of gaseous precursors are achieved, and formamidine iodine perovskite with multiple quantum well fluorescence oscillation peaks are grown.
The growth of multi-quantum well fluorescence oscillation peaks with low cost, simple operation and low temperature controllable is achieved, breaking the limitations of the existing technology, and promoting the stable existence of multi-N-value luminous peaks and quantum optical research.
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Figure CN120442239A_ABST
Abstract
Description
Technical Field
[0001] The invention belongs to the technical field of material growth and quantum optics, and relates to a method for growing formamidinium lead iodide perovskite with a multi-quantum well fluorescence oscillation peak, which is low in cost, simple to operate, and controllable at low temperature. Background Art
[0002] With the development of optoelectronic devices, improving luminous efficiency is of great significance. Among them, multi-quantum well luminescence improves luminous efficiency by confining electrons and holes in the wells, increasing their recombination probability. For example, when used in light-emitting diodes (LEDs), it can improve their light extraction efficiency and achieve brighter luminous effects. In semiconductor lasers, multi-quantum wells can reduce the threshold current, increase the output power and beam quality, and enable them to produce high-power, high-quality laser beams with lower power consumption. They are widely used in communications, medical treatment, industrial processing and other fields. Therefore, research on multi-quantum well luminescence is very important for improving the performance of material devices.
[0003] Materials for multi-quantum well luminescence (MQW) are typically prepared using methods such as molecular beam epitaxy (MBE), chemical beam epitaxy (CBE), and molecular beam ion beam epitaxy (MBIBE). However, these methods have the disadvantage of high preparation costs, requiring complex equipment such as ultra-high vacuum systems and multiple beam source furnaces, resulting in high purchase and maintenance costs. These methods are also incompatible with CMOS processes, requiring growth on substrates of specific sizes, which increases the difficulty of integration. Furthermore, these methods have the disadvantage of high process requirements, requiring precise control of ion beam parameters such as energy and beam current density, resulting in demanding growth conditions and requiring high operator skills.
[0004] Perovskite materials, as a new type of semiconductor material, are widely used in optoelectronic fields such as solar cells, light-emitting diodes, and lasers due to their unique structure and properties. They exhibit characteristics such as quantum confinement effects, high exciton binding energy, and narrow emission linewidth. Current research focuses on the optoelectronic applications of single-component perovskite materials with a single N value, or multi-component perovskites with multiple N values, thereby improving the luminescence efficiency of optoelectronic devices through energy level transitions. However, the complexity of multiple chemical components and the difficulty in precisely controlling the ratio of the number N lead to shortcomings such as impure color, mixed emission peaks with multiple N values, low luminescence efficiency of a single N value peak, and difficulty in stabilizing the large N value emission peak, making them difficult to apply in the field of quantum optics. Therefore, the optical research of single-component perovskite materials with multiple N values is extremely important. The growth and preparation of single-component perovskite materials with multiple N value emission peaks will become a key breakthrough in promoting the development of perovskite quantum devices. Summary of the Invention
[0005] In response to the above-mentioned existing technologies, the present invention provides a method for growing formamidinium lead iodide perovskite with multiple quantum well fluorescence oscillation peaks, which is used to prepare a single-component perovskite material with multiple N-value luminescence peaks. It has the characteristics of low cost, simple operation, and low-temperature controllability.
[0006] The technical solutions provided by the present invention are as follows:
[0007] A method for growing formamidinium-lead-iodine perovskite with multiple quantum well fluorescence oscillation peaks is characterized by comprising the following steps: placing formamidinium-iodine in an evaporation zone of a tubular furnace, and placing a lead iodide nanosheet substrate in a deposition zone adjacent to the evaporation zone; introducing an inert gas into the tubular furnace cavity and maintaining a negative pressure environment; controlling the temperature and sintering time of the evaporation zone and the deposition zone in stages to achieve directional transport of the gaseous precursor and controllable film formation, and obtaining the formamidinium-lead-iodine perovskite with multiple quantum well fluorescence oscillation peaks after cooling.
[0008] Furthermore, the deposition time in the deposition zone is greater than the evaporation time in the evaporation zone, and the difference between the two is 1~5h.
[0009] Furthermore, the evaporation temperature of the evaporation zone is 120~195℃, and the evaporation time is 1~6 h; the deposition temperature of the deposition zone is 60~95℃, and the deposition time is 2~7 h.
[0010] Furthermore, the substrate of the lead iodide nanosheets is a flat substrate of Si / SiO2, mica or a glass slide.
[0011] Furthermore, the mass ratio of formamidinium iodine to lead iodide nanosheets is greater than 1:1.
[0012] Furthermore, the inert gas is argon.
[0013] Furthermore, the inert gas flow rate is 10-200 sccm.
[0014] Furthermore, the negative pressure environment pressure is 10 -4 ~10 -2 Pa.
[0015] Furthermore, the time for cooling to room temperature after sintering is 1 to 3 hours.
[0016] Furthermore, a formamidinium lead iodide (FA) with a multi-quantum well fluorescence oscillation peak x PbI 2+x) perovskite growth method, based on the tube furnace equipment, a certain amount of formamidinium iodine (FAI) drug carrier is placed in the evaporation zone, and the lead iodide (PbI2) nanosheet sample on the substrate is placed in the deposition zone; a certain flow rate of argon gas is introduced, and a certain sintering temperature and time are set under a negative pressure environment, including the evaporation temperature and time of formamidinium iodine (FAI) drug in the evaporation zone, and the deposition temperature and time of lead iodide (PbI2) nanosheet sample in the deposition zone; after the sintering is completed, the tube furnace is cooled to room temperature for a certain time, and the formamidinium iodine (FAI) drug carrier and the product formamidinium iodine (FAI) on the substrate are taken out. x PbI 2+x ) perovskite sample, x = 0.1 ~ 2. Record optical photos and scanning electron micrographs, test fluorescence spectra, and use multi-quantum well quadratic function fitting to obtain formamidinium lead iodide (FA) with multi-quantum well fluorescence oscillation peaks. x PbI 2+x ) perovskite. When x>1, the amount of FAI involved in the reaction is excessive, so the sample shows a low-temperature fluorescence quantum well oscillation peak. When x≤1, the amount of FAI involved in the reaction is insufficient, so the sample does not show a low-temperature fluorescence quantum well oscillation peak.
[0017] The dosage of the quantitative formamidinium iodine (FAI) drug is 1 to 10 mg, and the dosage of the lead iodide (PbI2) nanosheets is 0.01 to 0.1 mg.
[0018] The carrier used for the quantitative formamidinium iodine (FAI) drug is a glass slide, a quartz boat, a corundum boat or other carrier that can withstand a temperature of 200°C;
[0019] The formamidinium iodine (FAI) drug is placed in the evaporation zone at a position between -8 and 8 cm with the center of the evaporation zone as the origin, with the left as the negative position and the right as the positive position;
[0020] The substrate of the lead iodide (PbI2) nanosheet sample is a flat substrate such as Si / SiO2, mica, or a glass slide that can withstand temperatures of 200°C.
[0021] The lead iodide (PbI2) nanosheet sample is placed in the deposition area at a position between -8 and 8 cm with the center of the deposition area as the origin, the left as the negative position, and the right as the positive position;
[0022] The evaporation temperature (T1) of the formamidinium iodine (FAI) drug in the evaporation zone is 120-195°C, and the evaporation time (t1) is 1-6 hours;
[0023] The deposition temperature (T2) on the lead iodide (PbI2) nanosheet sample in the deposition area is 60-95°C, and the deposition time (t2=t1+1) is 2-7 hours;
[0024] The present invention also provides a formamidinium lead iodide perovskite with a multiple quantum well fluorescence oscillation peak, which is prepared by the above method.
[0025] Beneficial effects
[0026] The present invention addresses the need for the growth and preparation of perovskite materials with multiple N-value luminescence peaks in a single component, and proposes a method for growing formamidine lead iodide perovskite with multiple quantum well fluorescence oscillation peaks. Based on a tube furnace device, the sample morphology is controlled by controlling the placement of the drug and the sample, the sintering temperature and time of the tube furnace, including the evaporation temperature of the drug and the deposition temperature of the sample and the corresponding time, and the gas flow rate of the argon gas, thereby completing the growth of formamidine lead iodide perovskite with multiple quantum well fluorescence oscillation peaks. The present invention breaks the limitations of the prior art in the growth of perovskite materials with four N-value luminescence peaks and quantum optics research, and realizes the growth of perovskite materials with nine N-value luminescence peaks coexisting, which is beneficial to the study of quantum optics. This is mainly because the present invention is very accurate in the selection of materials and the control of growth conditions. The method of the present invention can flexibly control the growth conditions of perovskite, has the characteristics of low cost, simple operation, and low temperature controllability, and the multiple quantum well fluorescence oscillation peak phenomenon possessed by the prepared sample is helpful for studying the application research of thin perovskite in the field of quantum optics. BRIEF DESCRIPTION OF THE DRAWINGS
[0027] Figure 1 Schematic diagram of the growth of FA-based perovskite with multi-quantum well fluorescence oscillation peaks in an embodiment of the present invention;
[0028] Figure 2 Schematic diagram of sintering conditions for growing FA-based perovskite with or without multi-quantum well fluorescence oscillation peaks in an embodiment of the present invention;
[0029] Figure 3 These are pictures of FA-based perovskites grown with and without multi-quantum well fluorescence oscillation peaks under different sintering conditions and deposition times in the embodiments of the present invention, where (a) is an optical photograph; (b) is a scanning electron microscope image;
[0030] Figure 4 The fluorescence spectra of FA-based perovskite with or without multi-quantum well fluorescence oscillation peaks grown under different sintering conditions and deposition times in the embodiment of the present invention are shown;
[0031] Figure 5 This is a quadratic fitting diagram of the multi-quantum well fluorescence oscillation peaks grown in the present invention. DETAILED DESCRIPTION
[0032] The present invention will be further explained below with reference to the accompanying drawings.
[0033] Example 1
[0034] Based on the tube furnace equipment, 2 mg of FAI drug was placed in the middle of the evaporation zone with a carrier, and 0.04 mg of PbI2 nanosheet sample on Si / SiO2 substrate was placed in the middle of the deposition zone; Ar gas flow rate of 200 sccm was introduced, and the evaporation temperature T1 = 185 ° C and time t1 = 2 h of FAI drug in the evaporation zone, and the deposition temperature T2 = 95 ° C and time t2 = 3 h of PbI2 nanosheet sample in the deposition zone were set; after the sintering was completed, the tube furnace was cooled to room temperature for 3 h, and the FAI drug carrier and the FA on Si / SiO2 substrate were taken out. x PbI 2+x Perovskite samples, test fluorescence spectra such as Figure 4 As shown, the FA with the multi-quantum well fluorescence oscillation peak is obtained by fitting the multi-quantum well quadratic function. x PbI 2+x (x>1)Perovskite.
[0035] Example 2
[0036] Based on the tube furnace equipment, 3 mg of FAI drug carrier was placed in the middle of the evaporation zone, and 0.03 mg of PbI2 nanosheet sample on Si / SiO2 substrate was placed in the middle of the deposition zone; Ar gas flow rate of 150 sccm was introduced, and the evaporation temperature T1 = 175 ° C and time t1 = 4 h of FAI drug in the evaporation zone, and the deposition temperature T2 = 85 ° C and time t2 = 5 h of PbI2 nanosheet sample in the deposition zone were set; after the sintering was completed, the tube furnace was cooled to room temperature for 2.5 h, and the FAI drug carrier and the FAI on Si / SiO2 substrate were taken out. x PbI 2+x Perovskite samples, recording optical photographs and scanning electron micrographs such as Figure 3 As shown, the test fluorescence spectrum is as follows Figure 4 As shown, the FA with the multi-quantum well fluorescence oscillation peak is obtained by fitting the multi-quantum well quadratic function. x PbI 2+x (x>1)Perovskite.
[0037] Example 3
[0038] Based on the tube furnace equipment, 4 mg of FAI drug carrier was placed in the middle of the evaporation zone, and 0.02 mg of PbI2 nanosheet sample on Si / SiO2 substrate was placed in the middle of the deposition zone; Ar gas flow rate of 100 sccm was introduced, and the evaporation temperature T1 = 165 ° C and time t1 = 5h of FAI drug in the evaporation zone, and the deposition temperature T2 = 75 ° C and time t2 = 6h of PbI2 nanosheet sample in the deposition zone were set; after the sintering was completed, the tube furnace was cooled to room temperature for 2 h, and the FAI drug carrier and the FAI on Si / SiO2 substrate were taken out.x PbI 2+x Perovskite samples, test fluorescence spectra such as Figure 4 , the FA with the multi-quantum well fluorescence oscillation peak is obtained by fitting the multi-quantum well quadratic function. x PbI 2+x (x>1)Perovskite.
[0039] Example 4
[0040] Based on the tube furnace equipment, 5 mg of FAI drug carrier was placed in the middle of the evaporation zone, and 0.01 mg of PbI2 nanosheet sample on Si / SiO2 substrate was placed in the middle of the deposition zone; Ar gas flow rate of 50 sccm was introduced, and the evaporation temperature T1 = 155 ° C and time t1 = 6 h of FAI drug in the evaporation zone, and the deposition temperature T2 = 65 ° C and time t2 = 7 h of PbI2 nanosheet sample in the deposition zone were set; after the sintering was completed, the tube furnace was cooled to room temperature for 2 h, and the FAI drug carrier and the FAI on Si / SiO2 substrate were taken out. x PbI 2+x Perovskite samples, test fluorescence spectra such as Figure 4 As shown, the multi-quantum well quadratic function is used to fit Figure 5 , and obtain FA with multiple quantum well fluorescence oscillation peaks x PbI 2+x (x>1)Perovskite.
[0041] The present invention provides a simple, low-cost, and reproducible preparation process. By controlling chemical dosage, sample position, gas flow rate, sintering temperature, and sintering time in a tube furnace, the growth of formamidinium-lead-iodine perovskite with multiple quantum well fluorescence oscillation peaks is achieved.
[0042] Comparative Example 1
[0043] Based on the tube furnace equipment, 2 mg of FAI drug was placed in the middle of the evaporation zone with a carrier, and 0.04 mg of PbI2 nanosheet sample on Si / SiO2 substrate was placed in the middle of the deposition zone; Ar gas flow rate of 200 sccm was introduced, and the evaporation temperature T1 = 185 ° C and time t1 = 0 h of FAI drug in the evaporation zone, and the deposition temperature T2 = 95 ° C and time t2 = 1 h of PbI2 nanosheet sample in the deposition zone were set; after the sintering was completed, the tube furnace was cooled to room temperature for 2 h, and the FAI drug carrier and the FAPbI2 on the Si / SiO2 substrate were taken out. 2+x Perovskite samples, recording optical photographs and scanning electron micrographs such as Figure 3 As shown, the test fluorescence spectrum is as follows Figure 4 As shown, it is found that there is only one main peak M, but no multi-quantum well fluorescence oscillation peak, and the sample is FA x PbI2+x (x=1) perovskite.
[0044] Conclusion: Due to insufficient evaporation time and deposition time, it is impossible to prepare FA with multiple quantum well fluorescence oscillation peaks. x PbI 2+x (x>1)Perovskite.
[0045] Comparative Example 2
[0046] Based on the tubular furnace equipment, 2 mg of FAI drug was placed in the middle of the evaporation zone using a carrier, and 0.04 mg of PbI2 nanosheet sample on Si / SiO2 substrate was placed in the middle of the deposition zone; Ar gas with a flow rate of 200 sccm was introduced, and the evaporation temperature T1=105 ℃ and time t1=6 h of the FAI drug in the evaporation zone, and the deposition temperature T2=45 ℃ and time t2=7 h of the PbI2 nanosheet sample in the deposition zone were set; after the sintering was completed, the tubular furnace was cooled to room temperature for 1 h, and the FAI drug carrier and the sample on the Si / SiO2 substrate were taken out. It was found that there was no fluorescence oscillation peak, but only a single fluorescence peak of PbI2.
[0047] Conclusion: Due to insufficient evaporation temperature and deposition temperature, the reaction cannot proceed and FA with multi-quantum well fluorescence oscillation peak cannot be prepared. x PbI 2+x (x>1) perovskite, the sample is still PbI2.
[0048] Comparative Example 3
[0049] Based on the tube furnace equipment, 2 mg of FAI drug was placed in the middle of the evaporation zone using a carrier, and 0.04 mg of PbI2 nanosheet sample on Si / SiO2 substrate was placed 8 cm to the right of the middle of the deposition zone; an Ar gas flow rate of 200 sccm was introduced, and the evaporation temperature T1=205 ℃ and time t1=6 h of the FAI drug in the evaporation zone, and the deposition temperature T2=45 ℃ and time t2=7 h of the PbI2 nanosheet sample in the deposition zone were set; after the sintering was completed, the tube furnace was cooled to room temperature for 3 h, and the FAI drug carrier and the sample on the Si / SiO2 substrate were taken out, and no fluorescence oscillation peak was found.
[0050] Conclusion: Due to the high evaporation temperature and low deposition temperature, too much FAI was deposited, and it was impossible to prepare FA with multiple quantum well fluorescence oscillation peaks. x PbI 2+x (x>1) perovskite, the sample surface is covered with too much FAI.
[0051] The above is only a preferred embodiment of the present invention. It should be pointed out that for ordinary technicians in this technical field, several improvements and modifications can be made without departing from the principles of the present invention. These improvements and modifications should also be regarded as within the scope of protection of the present invention.
Claims
1. A method for growing formamidinium lead iodide perovskite with multiple quantum well fluorescence oscillation peaks, characterized in that: The method comprises the following steps: placing formamidinium iodine in an evaporation zone of a tubular furnace, and placing a lead iodide nanosheet substrate in a deposition zone adjacent to the evaporation zone; introducing an inert gas into the tubular furnace cavity and maintaining a negative pressure environment; controlling the temperature and sintering time of the evaporation zone and the deposition zone in stages to achieve directional transmission and controllable film formation of the gaseous precursor, and obtaining formamidinium lead iodide perovskite with a multi-quantum well fluorescence oscillation peak after cooling.
2. The method for growing formamidinium lead iodide perovskite with multi-quantum well fluorescence oscillation peaks according to claim 1, characterized in that: The deposition time in the deposition zone is greater than the evaporation time in the evaporation zone, and the difference between the two is 1~5h.
3. The method for growing formamidinium lead iodide perovskite with multi-quantum well fluorescence oscillation peaks according to claim 1, characterized in that: The evaporation temperature in the evaporation zone is 120~195℃, and the evaporation time is 1~6 h; the deposition temperature in the deposition zone is 60~95℃, and the evaporation time is 2~7 h.
4. The method for growing formamidinium lead iodide perovskite with multi-quantum well fluorescence oscillation peaks according to claim 1, characterized in that: The base of the lead iodide nanosheet is a flat substrate of Si / SiO2, mica or a glass slide.
5. The method for growing formamidinium lead iodide perovskite with multiple quantum well fluorescence oscillation peaks according to claim 1, characterized in that: The mass ratio of formamidinium iodide to lead iodide nanosheets is greater than 1:
1.
6. The method for growing formamidinium lead iodide perovskite with multiple quantum well fluorescence oscillation peaks according to claim 1, characterized in that: The inert gas is argon.
7. The method for growing formamidinium lead iodide perovskite with multiple quantum well fluorescence oscillation peaks according to claim 1, characterized in that: The inert gas flow rate is 10-200 sccm.
8. The method for growing formamidinium lead iodide perovskite with multiple quantum well fluorescence oscillation peaks according to claim 1, characterized in that: Negative pressure environment pressure is 10 -4 ~10 -2 Pa.
9. The method for growing formamidinium lead iodide perovskite with multiple quantum well fluorescence oscillation peaks according to claim 1, characterized in that: The time for cooling to room temperature after sintering is 1 to 3 hours.
10. A formamidinium lead iodide perovskite with a multiple quantum well fluorescence oscillation peak, characterized in that: The method according to any one of claims 1 to 9 is used for preparation.