CN114958336B - Perovskite quantum dot, deep ultraviolet photoelectric detector and preparation method thereof - Google Patents

Perovskite quantum dot, deep ultraviolet photoelectric detector and preparation method thereof Download PDF

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CN114958336B
CN114958336B CN202210385496.3A CN202210385496A CN114958336B CN 114958336 B CN114958336 B CN 114958336B CN 202210385496 A CN202210385496 A CN 202210385496A CN 114958336 B CN114958336 B CN 114958336B
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perovskite quantum
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CN114958336A (en
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李明杰
陈逸帆
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Shenzhen Research Institute HKPU
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Abstract

The invention discloses a perovskite quantum dot, a deep ultraviolet photoelectric detector and a preparation method thereof, wherein the perovskite quantum dot prepared by adopting a solution method is FAPb 1‑x Sn x I 3 The perovskite quantum dot has the characteristics of MEG effect, high quantum efficiency, high stability, surface modification and film preparation, so that the perovskite quantum dot is used as a photosensitive material of a deep ultraviolet photoelectric detector, the photocurrent of the perovskite quantum dot reaches 117% at the highest under deep ultraviolet light, and the quantum dot exceeds the nanomaterial photoelectric detector prepared by all the solution methods reported at present, and the energy conversion internal quantum efficiency of the deep ultraviolet photoelectric detector is effectively improved.

Description

Perovskite quantum dot, deep ultraviolet photoelectric detector and preparation method thereof
Technical Field
The invention relates to the technical field of semiconductor deep ultraviolet photoelectric detectors, in particular to a perovskite quantum dot, a deep ultraviolet photoelectric detector and a preparation method thereof.
Background
A photodetector is a device that converts a photoelectric signal into an electrical signal. The high-efficiency deep ultraviolet light detector is important in the fields of scientific research, industry and the like: for example, semiconductor chip detection, medicine detection, optical communication, space detection and the like are in high-speed growth in demand year by year, so that development of the high-efficiency and low-cost deep ultraviolet photoelectric detector has important value. When the incident light is absorbed by the semiconductor photosensitive material in the detector, if the photon energy (hv) is greater than the semiconductor forbidden bandwidth (E g ) The material may be excited to generate electron-hole carrier pairs, which when extracted by the electrodes of the device generate a current. Photoelectric conversion internal quantum in deep ultraviolet photoelectric detectorEfficiency IQE (internal quantum efficiency) refers to the fact that the absorption of a photon by a photosensitive material can produce several electron-hole pairs that contribute to the photocurrent. General IQE due to losses during photoelectric conversion<100%. High IQE is important for improving the sensitivity of deep ultraviolet photodetectors, especially weak signal detection, and therefore development of photoelectric conversion materials with high efficiency IQE is required. The multi-carrier generation (carrier multiplication) is defined as a high energy photon (hv. Gtoreq.2E) g ) After absorption by the semiconductor, photons with energies greater than the material forbidden band can be excited by inter-carrier impact ionization (impact ionization) to generate additional carriers, so that one photon may generate more than one electron hole pair. In current commercial uv detectors, silicon is mainly used as the photosensitive material, with a photon energy hv=4.88 eV, about 4.5 times Si E under 254nm deep uv light g ) Although there is a multi-carrier generation effect, due to the small penetration depth, deep ultraviolet light can only excite the surface of Si, and a large number of crystal defects on the surface of Si cause electrons/holes excited by ultraviolet light to be captured by the defects and cannot generate photocurrent, so that the IQE under 254nm light excitation can only reach about 80-90% (Wan et al, npj 2D Mater Appl 1,2017,4) at most, and the photoelectric conversion efficiency of the commercial Si deep ultraviolet photoelectric detector is far lower than 50%.
Accordingly, the prior art is still in need of improvement and development.
Disclosure of Invention
In view of the shortcomings of the prior art, the invention aims to provide perovskite quantum dots, a deep ultraviolet photoelectric detector and a preparation method thereof, and aims to solve the problem that the existing deep ultraviolet photoelectric detector is low in photocurrent conversion efficiency.
The technical scheme of the invention is as follows:
the preparation method of the perovskite quantum dot comprises the following steps:
mixing formamidine acetate and propionic acid together, heating and stirring to obtain formamidine propionic acid precursor solution, and cooling to a first temperature for standby;
PbI is prepared 2 、SnI 2 Mixing with octadecene under vacuumHeating to a second temperature under the condition to perform drying treatment to obtain a first mixed solution;
injecting a second mixed solution composed of oleic acid and olaquindox into the first mixed solution under the condition of inert gas until PbI is reached 2 And SnI 2 Cooling to the first temperature after complete dissolution to obtain a third mixed solution for standby;
adding the formamidine propionic acid precursor solution into the third mixed solution, and placing the mixed solution into an ice water bath for cooling to obtain FAPb 1-x Sn x I 3 The method comprises the steps of (1) preparing a quantum dot crude solution, wherein FA is formamidine, and x is less than or equal to 0.11;
adding a methyl acetate solution to the FAPb 1-x Sn x I 3 And (3) in the quantum dot crude solution, uniformly mixing, performing centrifugal treatment, removing supernatant, and drying precipitate to obtain the perovskite quantum dot.
In the preparation method of the perovskite quantum dot, in the step of mixing formamidine acetate and propionic acid together and performing heating and stirring treatment, the heating temperature is 80-90 ℃, and the heating and stirring treatment time is 20-40min.
The preparation method of the perovskite quantum dot comprises the step of preparing the perovskite quantum dot, wherein the first temperature is 65-75 ℃.
The preparation method of the perovskite quantum dot comprises the following steps of 2 、SnI 2 Mixing with octadecene, and heating to a second temperature under vacuum condition for drying at 110-130deg.C for 0.5-1.5 hr.
The preparation method of the perovskite quantum dot comprises the steps of adding a methyl acetate solution to the FAPb 1-x Sn x I 3 In the step of the quantum dot crude solution, methyl acetate solution and FAPb 1-x Sn x I 3 The volume ratio of the quantum dot crude solution is 1:1.
The perovskite quantum dot is prepared by adopting the preparation method of the perovskite quantum dot, and the perovskite quantum dot is FAPb 1-x Sn x I 3 And the quantum dots, wherein FA is formamidine, and x is less than or equal to 0.11.
The preparation method of the deep ultraviolet photoelectric detector comprises the following steps:
dispersing perovskite quantum dots of the invention into an organic solvent in advance to obtain sol perovskite quantum dots for later use;
preparing an interdigital electrode on a substrate, wherein the interdigital electrode comprises two electrodes which are arranged in parallel and a patterned electrode which is arranged between the two electrodes and communicates the two electrodes;
spin-coating a titanium dioxide solution on the patterned electrode of the interdigital electrode, and forming a mesoporous carbon dioxide film after annealing treatment;
immersing the mesoporous carbon dioxide film into the sol perovskite quantum dots, so that the perovskite quantum dots are combined on the mesoporous carbon dioxide film to generate a quantum dot sensitized titanium dioxide film;
and connecting the two electrodes by using a probe connected with a wire to prepare the deep ultraviolet photoelectric detector.
The preparation method of the deep ultraviolet photoelectric detector comprises the step of preparing an organic solvent from one of n-hexane, n-propane, ethyl acetate and methylene dichloride.
The preparation method of the deep ultraviolet photoelectric detector comprises the steps of spin-coating a titanium dioxide solution on a patterned electrode of an interdigital electrode, and forming a mesoporous carbon dioxide film after annealing treatment, wherein the annealing treatment temperature is 450-550 ℃ and the annealing treatment time is 20-40min.
The invention relates to a deep ultraviolet photoelectric detector, which is prepared by adopting the preparation method of the deep ultraviolet photoelectric detector.
The beneficial effects are that: the perovskite quantum dot material with high efficiency and multiple exciton generation and high stability is provided by the invention, and the perovskite quantum dot is used as a photosensitive material of a deep ultraviolet photoelectric detector, so that the photocurrent reaches 117% at the highest under deep ultraviolet light, which exceeds the nano material photoelectric detector prepared by all the solution methods reported at present, and the energy conversion internal quantum efficiency of the deep ultraviolet photoelectric detector is effectively improved.
Drawings
Fig. 1 is a flow chart of a preparation method of perovskite quantum dots provided by the invention.
FIG. 2 is a schematic diagram of multi-exciton generation and electron transport in an ultraviolet light detector according to the present invention.
Fig. 3 is a schematic structural view of the ultraviolet photodetector of the present invention.
FIG. 4 is a schematic diagram of FAPb in an embodiment 1-x Sn x I 3 (x=4%, 7%, 11%) of the light emission spectrum of the quantum dot.
FIG. 5 is a schematic diagram of FAPb in an embodiment 1-x Sn x I 3 (x=4%, 7%, 11%) quantum dot X-ray diffraction spectrum.
FIG. 6 is a diagram of FAPb in an embodiment 1-x Sn x I 3 (x=7%) quantum dot Transmission Electron Microscopy (TEM) and elemental EDS profiles.
FIG. 7 is a diagram of FAPb in an embodiment 1-x Sn x I 3 (x=7%) quantum dot sol solution photographs.
FIG. 8 is a diagram of FAPb in an embodiment 1-x Sn x I 3 (x=7%) quantum dot device IV curve, excitation light wavelength 254nm.
FIG. 9 is a diagram of FAPb in an embodiment 1-x Sn x I 3 (x=4%, 7%, 11%) absorbance of light by the quantum dots in the quantum dot device.
FIG. 10 is a diagram of FAPb in an embodiment 1-x Sn x I 3 (x=4%, 7%, 11%) quantum dot photodetector device.
Detailed Description
The invention provides a perovskite quantum dot, a deep ultraviolet photoelectric detector and a preparation method thereof, and the invention is further described in detail below in order to make the purposes, technical schemes and effects of the invention clearer and more definite. It should be understood that the specific embodiments described herein are for purposes of illustration only and are not intended to limit the scope of the invention.
The quantum dot is a nanocrystal with a finite field effect in three spatial directions, the diameter is about several to tens of nanometers, and the forbidden band width can be continuously and adjustably covered with components and sizes. In quantum dot materials, multi-carrier generation under high energy uv photon excitation is more likely to occur due to enhanced inter-carrier interactions, which phenomenon is referred to as multi-exciton generation in quantum dots (multiple exciton generation, MEG; bound together electron-hole pairs are referred to as excitons, exiton), and thus quantum dots can be used as photoactive materials to increase the photocurrent conversion efficiency IQE. Selenized (PbSe) quantum dots have been used as photosensitizing materials to achieve MEG induced photocurrent IQE >100% in solar devices under 400nm light irradiation (Science 334,1530,2011). However, no quantum dot-based deep ultraviolet photodetectors have yet had >100% IQE. In the reported ultraviolet light detector based on sol graphene quantum dots prepared by the solution method, the IQE under 254nm deep ultraviolet illumination is only 5.9% due to low-efficiency MEG (Zhang et al ACS Nano 9,1561,2015).
Based on the above, the invention provides a preparation method of perovskite quantum dots, as shown in fig. 1, comprising the following steps:
s10, mixing formamidine acetate and propionic acid together, heating and stirring to obtain formamidine propionic acid precursor solution, and cooling to a first temperature for standby;
s20, pbI is taken 2 、SnI 2 Mixing with octadecene, heating to a second temperature under vacuum condition, and drying to obtain a first mixed solution;
s30, injecting a second mixed solution composed of oleic acid and olaquindox into the first mixed solution under the condition of inert gas until PbI is reached 2 And SnI 2 Cooling to the first temperature after complete dissolution to obtain a third mixed solution for standby;
s40, adding the formamidine propionic acid precursor solution into the third mixed solution, and cooling in an ice water bath to obtain FAPb 1-x Sn x I 3 The method comprises the steps of (1) preparing a quantum dot crude solution, wherein FA is formamidine, and x is less than or equal to 0.11;
s50, adding methyl acetate solution to the FAPb 1-x Sn x I 3 And (3) in the quantum dot crude solution, uniformly mixing, performing centrifugal treatment, removing supernatant, and drying precipitate to obtain the perovskite quantum dot.
The perovskite quantum dots prepared by adopting the solution method in the embodiment areFAPb 1-x Sn x I 3 The quantum dot has the characteristics of MEG effect, high quantum efficiency, high stability, surface modification and film preparation, so that the perovskite quantum dot is used as a photosensitive material of a deep ultraviolet photoelectric detector, the photocurrent of the perovskite quantum dot reaches 117% at the highest under deep ultraviolet light, and the quantum dot exceeds the nanomaterial photoelectric detector prepared by all the solution methods reported at present, and the energy conversion internal quantum efficiency of the deep ultraviolet photoelectric detector is effectively improved.
In some embodiments, formamidine acetate and propionic acid are mixed together and stirred at 80-90 ℃ for 20-40min to obtain formamidine propionic acid precursor solution, and then cooled to 65-75 ℃ for later use.
In some embodiments, pbI is used 2 、SnI 2 Mixing with octadecene, heating to 110-130deg.C under vacuum, and drying for 0.5-1.5 hr to obtain first mixed solution.
In some embodiments, the methyl acetate solution is added to the FAPb at a ratio of 1:1 by volume 1- x Sn x I 3 And (3) in the quantum dot crude solution, uniformly mixing and then carrying out centrifugal treatment.
In some embodiments, there is also provided a perovskite quantum dot prepared by the method of preparing a perovskite quantum dot of the present invention, the perovskite quantum dot being FAPb 1-x Sn x I 3 And the quantum dots, wherein FA is formamidine, and x is less than or equal to 0.11. In this embodiment, if x is too large, defects may be introduced due to too high Sn doping, resulting in a decrease in device efficiency IQE.
In some embodiments, the present invention further provides a method for preparing a deep ultraviolet photodetector, which includes the steps of:
dispersing perovskite quantum dots of the invention into an organic solvent in advance to obtain sol perovskite quantum dots for later use;
preparing an interdigital electrode on a substrate, wherein the interdigital electrode comprises two electrodes which are arranged in parallel and a patterned electrode which is arranged between the two electrodes and communicates the two electrodes;
spin-coating a titanium dioxide solution on the patterned electrode of the interdigital electrode, and forming a mesoporous carbon dioxide film after annealing treatment;
immersing the mesoporous carbon dioxide film into the sol perovskite quantum dots, so that the perovskite quantum dots are combined on the mesoporous carbon dioxide film to generate a quantum dot sensitized titanium dioxide film;
and connecting the two electrodes by using a probe connected with a wire to prepare the deep ultraviolet photoelectric detector.
Specifically, the working principle of the deep ultraviolet photoelectric detector prepared by the invention is shown in figure 2, when the deep ultraviolet photoelectric detector is irradiated by ultraviolet light, after the ultraviolet light is absorbed by the perovskite quantum dots, when the photon energy is more than twice the energy band width E of the perovskite quantum dots g When the electron beam is used, the multi-exciton MEG is generated, the multi-electrons are transmitted to the mesoporous carbon dioxide film, and finally, the electron beam flows to the electrode to generate photocurrent. The photoelectric conversion efficiency is improved by utilizing the multi-exciton generation process in the perovskite quantum dot, and the photocurrent IQE of the photoelectric detector reaches 117% at the highest under 254nm ultraviolet irradiation, which exceeds that of the photoelectric detector made of the nano material prepared by all the solution methods reported at present.
In this embodiment, the organic solvent is one of n-hexane, n-propane, ethyl acetate and methylene chloride, but is not limited thereto.
In the embodiment, the titanium dioxide solution is spin-coated on the patterned electrode of the interdigital electrode, and the mesoporous carbon dioxide film is formed after annealing treatment, wherein the annealing treatment temperature is 450-550 ℃ and the annealing treatment time is 20-40min.
In some embodiments, there is also provided a deep ultraviolet photodetector manufactured using the method of manufacturing a deep ultraviolet photodetector of the present invention. As shown in fig. 3, the deep ultraviolet photoelectric detector comprises a substrate 1, an interdigital electrode 2 arranged on the substrate, a mesoporous titanium dioxide film 3 arranged on a patterned electrode in the interdigital electrode 2, and perovskite quantum dots combined on the mesoporous titanium dioxide film 3, wherein the perovskite quantum dots are FAPb 1-x Sn x I 3 And the quantum dots, wherein FA is formamidine, and x is less than or equal to 0.11.
The invention is further illustrated by the following examples:
example 1
1) Preparation of an amidinopropionic acid precursor solution (FA-PA): a25 ml round bottom flask was purged with acetone, isopropanol, ethanol, secondary water, blow-dried with nitrogen, oven dried at 80℃for 1h and cooled for use. In a fume hood, weigh 0.13g formamidine acetate and 2.5mL propionic acid in a 25mL round bottom flask and mix in N 2 Heating to 80deg.C under atmospheric condition for 30min. After complete dissolution, the temperature was reduced to 75 ℃ and maintained at that temperature for later use.
2) Tin lead iodide solution (PbI) 2 -SnI 2 ) Preparation: and (3) cleaning a 25ml three-bottom flask by using acetone, isopropanol, ethanol and secondary water, drying by nitrogen, drying at 80 ℃ for 1 hour, and cooling for later use. Weigh 0.086g PbI in glove box 2 ，0.005g SnI 2 And 5mL ODE were mixed in a 25mL three-bottom flask and dried under vacuum heated to 120℃for 1h. Thereafter at N 2 The mixed 1mL OA and 0.55mL OLA solution was injected into the above solution by a syringe under an atmosphere. After complete dissolution, it is kept at this temperature for subsequent use.
3)FAPb 1-x Sn x I 3 (x=4%) perovskite quantum dot preparation: 1mL of FA-PA solution was rapidly injected into PbI using a syringe 2 -SnI 2 In solution and immediately cooled in an ice-water bath (0deg.C) to obtain FAPb 1-x SnxI 3 Quantum dot crude solution. In a glove box, meOAc solution was added to FAPb 1-x Sn x I 3 (x=4%) in the crude solution of quantum dots (volume ratio 1:1), shaking repeatedly to mix thoroughly, centrifuging at 12000rpm in a centrifuge for 10 min to obtain precipitate of quantum dots, removing supernatant, adding 10mL of n-hexane, and redispersing to obtain FAPb 1-x Sn x I 3 (x=4%) sol perovskite quantum dots. FAPb 1-x Sn x I 3 (x=4%) quantum dot sample luminescence spectrum (from 1240/luminescence spectrum peak wavelength position can obtain the quantum dot band width E g 1.57 eV) and X-ray diffraction (XRD) spectra are shownFig. 4 and 5.
4) Preparation of Cr/Au interdigital electrode: washing 200nm-SiO with acetone, isopropanol, ethanol, and secondary water 2 Si substrate, N 2 Purging and drying, and then photoetching the pattern of the interdigital electrode. And then depositing Cr/Au (5/40 nm) by using a magnetron sputtering method to obtain the interdigital electrode. Wherein the channel between the electrodes has a length of 4 μm and a width of 1mm. In a size of 0.1mm 2 In the device of (2), the total channel area was 0.05mm 2 . Prepared interdigital electrode is arranged at O 2 The plasma treatment was carried out for 15min for subsequent use.
5) Preparing a quantum dot ultraviolet light detector: commercially available TiO 2 The homogenate was diluted 4-fold (mass ratio 1:4) by adding ethanol to prepare TiO 2 Spin coating liquid. 0.2mL TiO was applied using a spin coater 2 Spin-coating the spin-coating liquid at 2000rpm for 30s to form mesoporous TiO on the interdigital electrode 2 (m-TiO 2 ) The film thickness was 300nm. Then the prepared m-TiO 2 The film was placed in a tube furnace and annealed at 500℃for 30min. After which the m-TiO is directly reacted 2 Electrode placement FAPb 1-x Sn x I 3 Sensitization in sol perovskite quantum dots for 3 days (x=4%) to finally obtain FAPb 1-x Sn x I 3 (x=4%) quantum dot ultraviolet light detector.
6) The photocurrent IQE is obtained according to the following calculation formula
Where h is the planck constant (h= 6.626 ×10 -34 J·s), e is the electron constant (e=1.6x10 -19 C) Lambda is the wavelength (nm) of the incident light, I ph For the photocurrent of the device (the photocurrent of the device under the illumination is subtracted by the photocurrent under the dark environment without illumination), po is the incident light power, eta ab Is the absorption efficiency of light by the quantum dots in the device, and a is the absorbance of the photosensitive material in the device (as shown in fig. 9).
7) Photoelectric performance test: the photoelectric performance test of the quantum dot ultraviolet light detector is carried out by utilizing a monochromatic light source and a probe station, wherein monochromatic light is generated by a mercury lamp light source through filters (254 nm,310nm,365nm,405nm,435nm and 490 nm) with different wavelengths, and the probe station is composed of 2 Au probes and 4200 Ji-time data logger. The internal quantum efficiency IQE of photocurrent is as shown in FIG. 10, and the IQE reaches 108% at 254nm (4.88 eV).
Example 2
1) Preparation of an amidinopropionic acid precursor solution (FA-PA): a25 ml round bottom flask was purged with acetone, isopropanol, ethanol, secondary water, blow-dried with nitrogen, oven dried at 80℃for 1h and cooled for use. In a fume hood, weigh 0.13g formamidine acetate and 2.5mL propionic acid in a 25mL round bottom flask and mix in N 2 Heating to 80deg.C under atmospheric condition for 30min. After complete dissolution, the temperature was reduced to 75 ℃ and maintained at that temperature for later use.
2) Tin lead iodide solution (PbI) 2 -SnI 2 ) Preparation: and (3) cleaning a 25ml three-bottom flask by using acetone, isopropanol, ethanol and secondary water, drying by nitrogen, drying at 80 ℃ for 1 hour, and cooling for later use. Weigh 0.086g PbI in glove box 2 ，0.022g SnI 2 And 5mL ODE were mixed in a 25mL three-bottom flask and dried under vacuum heated to 120℃for 1h. Thereafter at N 2 The mixed 1mL OA and 0.55mL OLA solution was injected into the above solution by a syringe under an atmosphere. After complete dissolution, it is kept at this temperature for subsequent use.
3)FAPb 1-x Sn x I 3 (x=7%) perovskite quantum dot preparation: 1mL of FA-PA solution was rapidly injected into PbI using a syringe 2 -SnI 2 In solution and immediately cooled in an ice-water bath (0deg.C) to obtain FAPb 1-x Sn x I 3 Quantum dot crude solution. In a glove box, meOAc solution was added to FAPb 1-x Sn x I 3 (x=7%) in the crude solution of quantum dots (volume ratio 1:1), shaking repeatedly to mix thoroughly, centrifuging at 12000rpm in centrifuge for 10 min to obtain precipitate of quantum dots, removing supernatant, adding 10mL of n-hexane, and redispersing to obtain FAPb 1-x Sn x I 3 (x=7%) sol perovskite quantum dots. FAPb 1-x Sn x I 3 (x=7%) quantum dot luminescence spectrum (from 1240/luminescenceThe bandwidth E of the quantum dot band can be obtained by the spectral peak wavelength position g 1.56 eV) and X-ray diffraction (XRD) spectra are shown in fig. 4 and 5.FAPb 1-x Sn x I 3 (x=7%) quantum dot sample transmission electron microscopy and elemental analysis are shown in fig. 6, and photographs in glass vials are shown in fig. 7. The quantum dot size is about 15nm as seen in fig. 6.
4) Preparation of Cr/Au interdigital electrode: washing 200nm-SiO with acetone, isopropanol, ethanol, and secondary water 2 Si substrate, N 2 Purging and drying, and then photoetching the pattern of the interdigital electrode. And then depositing Cr/Au (5/40 nm) by using a magnetron sputtering method to obtain the interdigital electrode. Wherein the channel between the electrodes has a length of 4 μm and a width of 1mm. In a size of 0.1mm 2 In the device of (2), the total channel area was 0.05mm 2 . Prepared interdigital electrode is arranged at O 2 The plasma treatment was carried out for 15min for subsequent use.
5) Preparing a quantum dot ultraviolet light detector: commercially available TiO 2 The homogenate was diluted 4-fold (mass ratio 1:4) by adding ethanol to prepare TiO 2 Spin coating liquid. 0.2mL TiO was applied using a spin coater 2 Spin-coating the spin-coating liquid at 2000rpm for 30s to form mesoporous TiO on the interdigital electrode 2 The film thickness was 300nm. Then the prepared m-TiO 2 The film was placed in a tube furnace and annealed at 500℃for 30min. After which the m-TiO is directly reacted 2 Electrode placement FAPb 1-x Sn x I 3 Sensitization in sol perovskite quantum dots for 3 days (x=7%) to finally obtain FAPb 1-x Sn x I 3 (x=7%) quantum dot ultraviolet light detector.
6) The photocurrent IQE is obtained according to the following calculation formula
Where h is the planck constant (h= 6.626 ×10 -34 J·s), e is the electron constant (e=1.6x10 -19 C) Lambda is the wavelength (nm) of the incident light, I ph For the photocurrent of the device (the device current under illumination minus the photocurrent under no illumination dark environment, see fig. 8), po is the incident light power, η ab Is the absorption efficiency of light by the quantum dots within the device, and a is the absorbance of the photoactive material in the device (fig. 9).
7) Photoelectric performance test: the photoelectric performance test of the quantum dot ultraviolet light detector is carried out by utilizing a monochromatic light source and a probe station, wherein monochromatic light is generated by a mercury lamp light source through filters (254 nm,310nm,365nm,405nm,435nm and 490 nm) with different wavelengths, and the probe station is composed of 2 Au probes and 4200 Ji-time data logger. The internal quantum efficiency IQE of photocurrent is as shown in FIG. 10, and IQE reaches 117% at 254nm (4.88 eV).
Example 3
1) Preparation of an amidinopropionic acid precursor solution (FA-PA): a25 ml round bottom flask was purged with acetone, isopropanol, ethanol, secondary water, blow-dried with nitrogen, oven dried at 80℃for 1h and cooled for use. In a fume hood, weigh 0.13g formamidine acetate and 2.5mL propionic acid in a 25mL round bottom flask and mix in N 2 Heating to 80deg.C under atmospheric condition for 30min. After complete dissolution, the temperature was reduced to 75 ℃ and maintained at that temperature for later use.
2) Tin lead iodide solution (PbI) 2 -SnI 2 ) Preparation: and (3) cleaning a 25ml three-bottom flask by using acetone, isopropanol, ethanol and secondary water, drying by nitrogen, drying at 80 ℃ for 1 hour, and cooling for later use. Weigh 0.086g PbI in glove box 2 ，0.043g SnI 2 And 5mL ODE were mixed in a 25mL three-bottom flask and dried under vacuum heated to 120℃for 1h. Thereafter at N 2 The mixed 1mL OA and 0.55mL OLA solution was injected into the above solution by a syringe under an atmosphere. After complete dissolution, it is kept at this temperature for subsequent use.
3)FAPb 1-x Sn x I 3 (x=11%) perovskite quantum dot preparation: 1mL of FA-PA solution was rapidly injected into PbI using a syringe 2 -SnI 2 In solution and immediately cooled in an ice-water bath (0deg.C) to obtain FAPb 1-x Sn x I 3 (x=11%) quantum dot crude solution. In a glove box, meOAc solution was added to FAPb 1-x Sn x I 3 (x=11%) quantum dot crude solution (volume ratio 1:1), repeatedly shaking to mix well, and in centrifuge at 12000rpm centrifuging for 10 min to obtain quantum dot precipitate, removing supernatant, adding 10mL n-hexane, and re-dispersing to obtain FAPb 1-x Sn x I 3 (x=11%) sol perovskite quantum dots. FAPb 1-x Sn x I 3 (x=11%) quantum dot luminescence spectrum (quantum dot bandwidth E is obtainable from 1240/luminescence spectrum peak wavelength position g 1.55 eV) and X-ray diffraction (XRD) spectra are shown in fig. 4 and 5.
4) Preparation of Cr/Au interdigital electrode: washing 200nm-SiO with acetone, isopropanol, ethanol, and secondary water 2 Si substrate, N 2 Purging and drying, and then photoetching the pattern of the interdigital electrode. And then depositing Cr/Au (5/40 nm) by using a magnetron sputtering method to obtain the interdigital electrode. Wherein the channel between the electrodes has a length of 4 μm and a width of 1mm. In a size of 0.1mm 2 In the device of (2), the total channel area was 0.05mm 2 . Prepared interdigital electrode is arranged at O 2 The plasma treatment was carried out for 15min for subsequent use.
5) Preparing a quantum dot ultraviolet light detector: commercially available TiO 2 The homogenate was diluted 4-fold (mass ratio 1:4) by adding ethanol to prepare TiO 2 Spin coating liquid. 0.2mL TiO was applied using a spin coater 2 Spin-coating the spin-coating liquid at 2000rpm for 30s to form mesoporous TiO on the interdigital electrode 2 (m-TiO 2 ) The film thickness was 300nm. Then the prepared m-TiO 2 The film was placed in a tube furnace and annealed at 500℃for 30min. After which the m-TiO is directly reacted 2 Electrode placement FAPb 1-x Sn x I 3 Sensitization in sol perovskite quantum dots for 3 days (x=11%) to finally obtain FAPb 1-x Sn x I 3 (x=11%) quantum dot ultraviolet light detector.
6) The photocurrent IQE is obtained according to the following calculation formula
Where h is the planck constant (h= 6.626 ×10 -34 J·s), e is the electron constant (e=1.6x10 -19 C) Lambda is the wavelength (nm) of the incident light, I ph Is the devicePhoto current (device current under illumination minus photo current under no illumination dark environment), po is incident light power, η ab Is the absorption efficiency of light by the quantum dots in the device, and a is the absorbance of the photosensitive material in the device (as shown in fig. 9).
7) Photoelectric performance test: the photoelectric performance test of the quantum dot ultraviolet light detector is carried out by utilizing a monochromatic light source and a probe station, wherein monochromatic light is generated by a mercury lamp light source through filters (254 nm,310nm,365nm,405nm,435nm and 490 nm) with different wavelengths, and the probe station is composed of 2 Au probes and 4200 Ji-time data logger. The internal quantum efficiency IQE of photocurrent is as shown in FIG. 10, and the IQE reaches 99% at 254nm (4.88 eV).
It is to be understood that the invention is not limited in its application to the examples described above, but is capable of modification and variation in light of the above teachings by those skilled in the art, and that all such modifications and variations are intended to be included within the scope of the appended claims.

Claims (9)

1. The preparation method of the perovskite quantum dot is characterized by comprising the following steps:
mixing formamidine acetate and propionic acid together, heating and stirring at 80-90 ℃ to obtain formamidine propionic acid precursor solution, and cooling to a first temperature for standby;
PbI is prepared 2 、SnI 2 Mixing with octadecene, heating to a second temperature under vacuum condition, and drying to obtain a first mixed solution;
injecting a second mixed solution composed of oleic acid and olaquindox into the first mixed solution under the condition of inert gas until PbI is reached 2 And SnI 2 Cooling to the first temperature after complete dissolution to obtain a third mixed solution for standby;
adding the formamidine propionic acid precursor solution into the third mixed solution, and placing the mixed solution into an ice water bath for cooling to obtain FAPb 1-x Sn x I 3 The coarse solution of the quantum dots, wherein FA is formamidine, x is more than or equal to 0.04 and less than or equal to 0.11;
adding a methyl acetate solution to the FAPb 1-x Sn x I 3 Coarse dissolution of quantum dotsIn the solution, after uniformly mixing, carrying out centrifugal treatment, removing supernatant, and drying precipitate to obtain the perovskite quantum dot;
wherein the first temperature is 65-75 ℃; the second temperature is 110-130 ℃.
2. The method for preparing perovskite quantum dots according to claim 1, wherein in the step of mixing formamidine acetate and propionic acid together and performing heating and stirring treatment at 80-90 ℃, the heating and stirring treatment time is 20-40min.
3. The method for preparing perovskite quantum dots according to claim 1, wherein PbI is prepared by 2 、SnI 2 Mixing with octadecene, and heating to a second temperature under vacuum condition for drying for 0.5-1.5h.
4. The method of claim 1, wherein a methyl acetate solution is added to the fatb 1-x Sn x I 3 In the step of the quantum dot crude solution, methyl acetate solution and FAPb 1-x Sn x I 3 The volume ratio of the quantum dot crude solution is 1:1.
5. A perovskite quantum dot is characterized in that the perovskite quantum dot is prepared by adopting the preparation method of the perovskite quantum dot according to any one of claims 1-4, wherein the perovskite quantum dot is FAPb 1-x Sn x I 3 And the quantum dots, wherein FA is formamidine, and x is more than or equal to 0.04 and less than or equal to 0.11.
6. The preparation method of the deep ultraviolet photoelectric detector is characterized by comprising the following steps of:
dispersing the perovskite quantum dots according to claim 5 into an organic solvent in advance to obtain sol perovskite quantum dots for later use;
preparing an interdigital electrode on a substrate, wherein the interdigital electrode comprises two electrodes which are arranged in parallel and a patterned electrode which is arranged between the two electrodes and communicates the two electrodes;
spin-coating a titanium dioxide solution on the patterned electrode of the interdigital electrode, and forming a mesoporous titanium dioxide film after annealing treatment;
immersing the mesoporous titanium dioxide film into the sol perovskite quantum dots, so that the perovskite quantum dots are combined on the mesoporous titanium dioxide film, and generating a quantum dot sensitized titanium dioxide film;
and connecting the two electrodes by using a probe connected with a wire to prepare the deep ultraviolet photoelectric detector.
7. The method for preparing the deep ultraviolet photoelectric detector according to claim 6, wherein the organic solvent is one of n-hexane, n-propane, ethyl acetate and methylene dichloride.
8. The method for preparing a deep ultraviolet photoelectric detector according to claim 6, wherein in the step of spin-coating a titanium dioxide solution on the patterned electrode of the interdigital electrode and forming a mesoporous titanium dioxide film after annealing treatment, the annealing treatment is performed at a temperature of 450-550 ℃ for 20-40min.
9. A deep ultraviolet photodetector, characterized in that it is manufactured by the manufacturing method of the deep ultraviolet photodetector according to any one of claims 6 to 8.
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