CN117956812A - Preparation method of composite perovskite thick film X-ray detector - Google Patents
Preparation method of composite perovskite thick film X-ray detector Download PDFInfo
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Abstract
The invention relates to the technical field of photoelectric detectors, and provides a preparation method of a composite perovskite thick film X-ray detector. The invention has the advantages that: the thick film obtained by the method is not easy to fall off and crack, has few crystal boundary defects, and the obtained perovskite X-ray detector based on the ITO substrate has excellent sensitivity and extremely low X-ray detection lower limit, and has excellent spatial resolution.
Description
Technical Field
The invention relates to the technical field of photoelectric detectors, in particular to a preparation method of a composite perovskite thick film X-ray detector.
Background
With the rapid development of modern technology, the importance of X-ray detection in the fields of industrial detection, security inspection, medical diagnosis and the like is increasingly remarkable. The direct X-ray detector can directly convert high-energy radiation into current signals based on the internal semiconductor absorption layer, and the simple conversion mode ensures that the direct X-ray detector has the characteristics of wider linear response range, faster pulse rising time, high spatial resolution and the like, and has very high working efficiency. Organic-inorganic hybrid perovskite is an ideal material for a semiconductor absorption layer of a direct type X-ray detector due to the characteristics of adjustable band gap, high X-ray absorption capacity, longer carrier life, excellent charge carrier transmission and the like.
The preparation of high-performance X-ray detector based on perovskite material first produces a high-quality thin film or crystal with sufficient X-ray absorption thickness and excellent photoelectric performance, and has high compatibility with the requirement of back-end electronic readout circuit.
Currently, perovskite materials are used in X-ray predominantly monocrystalline as well as polycrystalline devices. The perovskite monocrystal is complex and harsh in preparation requirements, is difficult to prepare a large-area device, and is difficult to integrate with a rear-end readout circuit. The polycrystalline thin film prepared based on the traditional spin coating, vapor deposition, knife coating and other methods also has the common problems of insufficient thickness (easy falling off and cracking after the thickness is increased), multiple grain boundary defects and the like, and seriously influences the performance of the detection device.
Disclosure of Invention
The invention aims to solve the technical problems of providing a preparation method of a composite perovskite thick film X-ray detector, wherein thick films obtained based on the method are not easy to fall off and crack, and have few crystal boundary defects, and the corresponding ITO substrate detector has excellent sensitivity and extremely low X-ray detection lower limit, and the corresponding TFT substrate detector has excellent spatial resolution.
The invention adopts the following technical scheme to solve the technical problems:
A preparation method of a composite perovskite thick film X-ray detector comprises the following steps:
(1) Dissolving a random copolymer into an organic solvent to obtain a copolymer precursor solution;
(2) Spreading the copolymer precursor liquid obtained in the step (1) on clean ITO conductive glass or TFT thin film transistor, and then annealing to obtain a pretreated ITO or TFT substrate;
(3) Dissolving polycrystalline perovskite precursor powder into the copolymer precursor liquid in the step (1) to obtain perovskite suspension precursor slurry;
(4) Coating the perovskite suspension precursor slurry obtained in the step (3) on the ITO or TFT substrate pretreated in the step (2) by adopting a blade coating method, and annealing to form a perovskite absorption layer;
(5) And (3) placing the device obtained in the step (4) into a vacuum evaporator, evaporating an Au common electrode at the top end, and obtaining the perovskite X-ray detector based on the ITO or TFT substrate.
In the step (1), a random copolymer with a mass concentration of 5-30 mg/mL is specifically weighed and dissolved in an organic solvent, and stirred for 5-10 min at normal temperature to obtain a copolymer precursor solution.
As one of the preferable modes of the present invention, in the step (1), the random copolymer is one of N-butyl acrylate-co- [ N- (hydroxymethyl) -acrylamide ] } (PBA-NMA), N-butyl acrylate-co-acrylamide (PBA-MA), and N-butyl acrylate-co-butenamide (PBA-BM); the polymer copolymer with polar hydrophilic groups and long-chain hydrophobic groups is selected as an additive, so that the dual functions of the adhesive and the surfactant can be achieved.
In the step (1), the organic solvent is one of Gamma Butyrolactone (GBL) and dimethoxy ethanol (2-Me); the solvent residue in the perovskite thick film is reduced by selecting a solvent with high vapor pressure and low coordination.
In the step (2), the thickness of the doctor blade and the substrate is 10-50 μm when the copolymer precursor liquid is scraped on the ITO and TFT.
As a preferred embodiment of the present invention, in the step (2), the annealing condition is 100 ℃.
In the step (3), 3-10 m of the polycrystalline perovskite precursor powder is specifically weighed and dissolved in the copolymer precursor liquid, and the mixture is fully stirred for 30-60 min to obtain perovskite suspension precursor slurry.
As a preferred embodiment of the present invention, in the step (3), the polycrystalline perovskite precursor is one of methylamine lead-iodine perovskite (MAPbI 3), formamidine lead-iodine perovskite (FAPbI 3), cesium lead-bromine perovskite (CsPbBr 3), and triple-cation perovskite (FAMACs).
In the step (4), when the perovskite suspension precursor slurry is scraped onto the corresponding substrate, the distance between the scraper and the substrate is 100-1000 μm; the thickness of the final polycrystalline film is controlled by the distance of the doctor blade.
In the step (4), the annealing condition is that the annealing is performed at 60-100 ℃ for 30-60 min; the lower annealing temperature helps to reduce the residual tensile stress in the thick film.
In the step (4), the thickness of the top Au common electrode deposited by evaporation is 80-120 nm; the absorption loss of the Au electrode to X rays is reduced while the top electrode and perovskite form good ohmic contact.
Compared with the prior art, the invention has the advantages that:
(1) The thick film is not easy to fall off: the ITO and TFT substrates are pretreated by adopting the random copolymer, and bidirectional coordination connection is formed between the perovskite absorption layer and the substrate, so that the adhesion force of perovskite and the substrate is enhanced, and the perovskite polycrystalline thick film is effectively prevented from falling off;
(2) Thick films are not easy to crack: the random copolymer is crosslinked in the polycrystalline thick film, so that the thermal expansion caused in the thick film annealing process can be effectively treated, the thermal residual tensile stress is reduced, the cracking of the thick film is effectively prevented, the mechanical strength of the polycrystalline thick film is improved, and the service life of the polycrystalline thick film is prolonged;
(3) Reducing grain boundary defects, imparting extremely low dark current and extremely low X-ray detection lower limit: preparing perovskite suspension precursor slurry compounded by perovskite and random copolymer, wherein the amphiphilic copolymer effectively reduces the surface tension of a precursor solution, increases nucleation sites and nucleation rate, effectively eliminates pinhole problems caused by slower nucleation and solvent shrinkage in the formation of a perovskite thick film, and greatly improves the density of the thick film; meanwhile, after the perovskite polycrystalline thick film is formed, the copolymer at the grain boundary can effectively passivate perovskite grain boundary defects, and effectively reduce defect density, so that ion migration is inhibited, and the final wafer device has extremely low dark current and extremely low X-ray detection lower limit;
(4) Extremely high detection sensitivity: the compact structure and proper thickness of the prepared perovskite thick film ensure that an ITO substrate-based detection device effectively absorbs X rays, and meanwhile, the low defect density in a polycrystal thick film phase also ensures the effective extraction of photo-generated carriers, so that the detection sensitivity of the device to the X rays is obviously improved;
(5) Size area is adjustable, and the compatibility is good: compared with perovskite monocrystal and film detectors, the polycrystalline thick film device prepared by the method is convenient, the size and the area are adjustable, and the polycrystalline thick film device and the rear end substrate have excellent compatibility;
(6) The applicability is strong: the mechanical stability of the composite polycrystalline thick film is increased, so that the controllable preparation of the thickness from nanometer to micrometer level can be realized based on the process, and the multi-field application of large-area detection imaging from soft X-rays to hard X-rays can be further realized;
(7) Excellent spatial resolution: based on the preparation process with excellent compatibility, the prepared high-quality polycrystalline thick film TFT substrate shows excellent suitability after being integrated, and good interface contact ensures that the photo-generated electric signals of the perovskite absorption layer can be effectively read by a back-end circuit, and ensures that an imaging system of an X-ray detector has good uniformity and excellent spatial resolution.
Drawings
FIG. 1 is a schematic representation of a perovskite thick film of example 2;
FIG. 2 is a diagram of the bonding state of the bottom of the perovskite thick film of example 2 to the ITO substrate;
FIG. 3 is a graph of the microtopography of the perovskite thick film X-ray detector of example 2;
FIG. 4 is a graph of the sensitivity test results of the perovskite thick film X-ray detector of example 2;
FIG. 5 is a graph of the detection limit test results of the perovskite thick film X-ray detector of example 2;
FIG. 6 is a physical view of a perovskite thick film X imager of example 5;
FIG. 7 is a graphical representation of the physical imaging results of a perovskite thick film X imager of example 5;
FIG. 8A is a graphical representation of the upper interface of the perovskite thick film prepared by comparative example 1;
FIG. 8B is a graphical representation of the lower interface of the perovskite thick film prepared by comparative example 1;
FIG. 9 is a graph of the microtopography of comparative example 1 perovskite thick films;
FIG. 10 is a graph of the sensitivity test results of comparative example 1 perovskite thick film X-ray detector;
FIG. 11 is a graphical representation of comparative example 2 perovskite thick films.
Detailed Description
The following describes in detail the examples of the present invention, which are implemented on the premise of the technical solution of the present invention, and detailed embodiments and specific operation procedures are given, but the scope of protection of the present invention is not limited to the following examples.
Example 1
The preparation method of the composite perovskite thick film X-ray detector (based on ITO) comprises the following steps:
(1) And weighing PBA-NMA with the mass concentration of 5mg/mL in a glove box, dissolving the PBA-NMA in GBL solution, and stirring the PBA-NMA at normal temperature for 5min to obtain copolymer precursor liquid.
(2) And (2) taking the copolymer precursor liquid obtained in the step (1), scraping and coating the copolymer precursor liquid on clean ITO conductive glass by using a scraper, coating the ITO conductive glass to a thickness of 10 mu m, and then annealing at 100 ℃ to obtain the pretreated ITO substrate.
(3) And (3) weighing 3M MAPbI 3 perovskite precursor powder, dissolving the powder into the copolymer precursor liquid in the step (1), and fully stirring for 30min to obtain perovskite suspension precursor slurry.
(4) And on a slit coater, regulating the distance between a scraper and an ITO substrate to 100 mu m, uniformly coating the perovskite suspension precursor slurry on the pretreated ITO by adopting a scraper coating method, and annealing at 60 ℃ for 30min to form a compact perovskite absorption layer.
(5) And (3) placing the device obtained in the step (4) into a vacuum evaporator, evaporating an Au common electrode with the thickness of 80nm at the top end, and obtaining the perovskite X-ray detector based on the ITO substrate.
Example 2
The preparation method of the composite perovskite thick film X-ray detector (based on ITO) comprises the following steps:
(1) And weighing PBA-NMA with the mass concentration of 5mg/mL in a glove box, dissolving the PBA-NMA in a 2-Me solution, and stirring the solution at normal temperature for 10min to obtain a copolymer precursor solution.
(2) And (2) taking the copolymer precursor liquid obtained in the step (1), scraping and coating the copolymer precursor liquid on clean ITO conductive glass by using a scraper, coating the ITO conductive glass to a thickness of 10 mu m, and then annealing at 100 ℃ to obtain the pretreated ITO substrate.
(3) And (3) weighing and dissolving FAMACs M perovskite precursor powder into the copolymer precursor liquid in the step (1), and fully stirring for 60min to obtain perovskite suspension precursor slurry.
(4) And on a slit coater, regulating the distance between a scraper and an ITO substrate to 600 mu m, uniformly coating the perovskite suspension precursor slurry on the pretreated ITO by adopting a scraper coating method, and annealing at 80 ℃ for 40min to form a compact perovskite absorption layer.
(5) And (3) placing the device obtained in the step (4) into a vacuum evaporator, evaporating an Au common electrode with the thickness of 100nm at the top end, and obtaining the perovskite X-ray detector based on the ITO substrate.
Example 3
The preparation method of the composite perovskite thick film X-ray detector (based on ITO) comprises the following steps:
(1) And (3) weighing PBA-MA with the mass concentration of 20mg/mL in a glove box, dissolving the PBA-MA in a 2-Me solution, and stirring the solution at normal temperature for 8min to obtain a copolymer precursor solution.
(2) And (2) taking the copolymer precursor liquid obtained in the step (1), scraping and coating the copolymer precursor liquid on clean ITO conductive glass by using a scraper, coating the ITO conductive glass to a thickness of 20 mu m, and then annealing at 100 ℃ to obtain the pretreated ITO substrate.
(3) And (3) weighing 8M FAPbI 3 perovskite precursor powder, dissolving the powder into the copolymer precursor liquid in the step (1), and fully stirring for 50min to obtain perovskite suspension precursor slurry.
(4) On a slit coater, the distance between a scraper and an ITO or TFT substrate is adjusted to 800 mu m, and a perovskite suspension precursor slurry is uniformly coated on the pretreated ITO or TFT by adopting a scraper coating method and annealed at 80 ℃ for 50min to form a compact perovskite absorption layer.
(5) And (3) placing the device obtained in the step (4) into a vacuum evaporator, evaporating an Au common electrode with the thickness of 100nm at the top end, and obtaining the perovskite X-ray detector based on the ITO substrate.
Example 4
The preparation method of the composite perovskite thick film X-ray detector (based on ITO) comprises the following steps:
(1) And (3) weighing PBA-BM with the mass concentration of 30mg/mL in a glove box, dissolving the PBA-BM in the GBL solution, and stirring the PBA-BM at normal temperature for 10min to obtain a copolymer precursor solution.
(2) And (2) taking the copolymer precursor liquid obtained in the step (1), scraping and coating the copolymer precursor liquid on clean ITO conductive glass by using a scraper, coating the ITO conductive glass to a thickness of 50 mu m, and then annealing at 100 ℃ to obtain the pretreated ITO substrate.
(3) And (3) weighing 10M CsPbBr 3 perovskite precursor powder, dissolving the perovskite precursor powder into the copolymer precursor liquid in the step (1), and fully stirring for 60min to obtain perovskite suspension precursor slurry.
(4) And on a slit coater, regulating the distance between a scraper and an ITO substrate to 1000 mu m, uniformly coating the perovskite suspension precursor slurry on the pretreated ITO by adopting a scraper coating method, and annealing at 100 ℃ for 60min to form a compact perovskite absorption layer.
(5) And (3) placing the device obtained in the step (4) into a vacuum evaporator, evaporating an Au common electrode with the thickness of 120nm at the top end, and obtaining the perovskite X-ray detector based on the ITO substrate.
Example 5
The preparation method (based on TFT) of the composite perovskite thick film X-ray detector comprises the following steps:
(1) And weighing PBA-NMA with the mass concentration of 5mg/mL in a glove box, dissolving the PBA-NMA in a 2-Me solution, and stirring the solution at normal temperature for 10min to obtain a copolymer precursor solution.
(2) And (2) taking the copolymer precursor liquid obtained in the step (1), scraping and coating the copolymer precursor liquid on a clean TFT film transistor by using a scraper, coating the film transistor to a thickness of 10 mu m, and then annealing at 100 ℃ to obtain the pretreated TFT substrate.
(3) And (3) weighing and dissolving FAMACs M perovskite precursor powder into the copolymer precursor liquid in the step (1), and fully stirring for 60min to obtain perovskite suspension precursor slurry.
(4) And on a slit coater, regulating the distance between a scraper and a TFT substrate to 600 mu m, uniformly coating the perovskite suspension precursor slurry on the pretreated TFT by adopting a scraper coating method, and annealing at 80 ℃ for 40min to form a compact perovskite absorption layer.
(5) And (3) placing the device obtained in the step (4) into a vacuum evaporator, evaporating an Au common electrode with the thickness of 100nm at the top end, and obtaining the perovskite X-ray detector based on the TFT substrate.
Comparative example 1
The preparation method (based on ITO) of the composite perovskite thick film X-ray detector of the comparative example is basically the same as that of the embodiment 2, and mainly differs in that: in step (3), 5M FAMACs perovskite precursor powder is weighed and dissolved in 2-Me solvent instead of copolymer precursor liquid.
Comparative example 2
The preparation method (based on ITO) of the composite perovskite thick film X-ray detector of the comparative example is basically the same as that of the embodiment 2, and mainly differs in that: the pretreatment step of the ITO substrate is not performed, and in the step (3), the FAMACs M perovskite precursor powder is weighed and dissolved in a 2-Me solvent instead of the copolymer precursor liquid.
Experimental example 1
The experimental example is used for testing the performance of two composite perovskite thick film X-ray detectors:
1. ITO-based composite perovskite thick film X-ray detector:
Taking example 2 as an example, the perovskite thick film is as shown in fig. 1, the surface is flat and compact, and fig. 2 shows that the bottom of the perovskite thick film forms good adhesion contact with the ITO substrate.
The perovskite X-ray detector of example 2 was placed in a field emission scanning electron microscope and further observed for microscopic morphology, as shown in fig. 3, indicating: dense nucleation sites and accelerated crystallization process promote the formation of dense thick films with few grain boundary defects.
The perovskite X-ray detector of example 2 was placed in a test bench in a shielded box and a related photo-electric performance test was performed using a keithley6517b electrometer. The sensitivity is shown in FIG. 4 as 3410 mu C G yair -1cm-2, which shows that: the high quality perovskite thick film has excellent optoelectronic properties. Meanwhile, in combination with fig. 3, the repair of pinholes in the thick film and the passivation of the grain boundary surface are performed, so that the thick film has higher resistivity and lower dark current, the detection limit of the detector can be greatly reduced, and fig. 5 shows that the detection limit of the prepared X-ray detector reaches 19.4 nGyairS -1.
2. TFT-based composite perovskite thick film X-ray detector (i.e. perovskite thick film X-imager):
Taking example 5 as an example, the appearance of a perovskite thick film X-ray imager prepared based on a TFT substrate is shown in FIG. 6, and the thickness of the perovskite absorption layer coated on the TFT reaches 600 μm, and the thickness is enough to ensure effective absorption of X-rays. Fig. 7 shows the physical imaging of the perovskite imager, and the components in the tested remote controller can be clearly distinguished based on the excellent performance of the perovskite absorption layer, and the surface has excellent spatial resolution.
Experimental example 2
This experimental example, in combination with comparative examples 1,2, verifies the effect of "ITO substrate pretreatment" and "polycrystalline perovskite precursor composite random copolymer" on the perovskite thick film X-ray detector of the present invention:
The perovskite thick film prepared in comparative example 1 has an upper interface as shown in fig. 8A, a lower interface as shown in fig. 8B, and a microstructure as shown in fig. 9 (grain boundary defects and a large number of pin holes are present): on the one hand, due to the adhesive action of the copolymer which is not contained in the single perovskite polycrystalline thick film phase, after annealing and cooling, the residual shear stress enables the surface and the bottom surface of the perovskite thick film to generate cracks; on the other hand, due to the serious signal noise and signal drift caused by more grain boundary defects and pinholes, the detection performance of the detector is greatly affected, and the sensitivity of the detector is only 950 mu C G yair -1cm-2 as shown in fig. 10.
As shown in fig. 11, the perovskite thick film prepared in comparative example 2 was not effectively detected because the perovskite thick film was cracked and completely detached from the substrate after annealing due to the lack of adhesion and interfacial effects of the copolymer.
In conclusion, the steps of pretreatment of the ITO substrate and the step of compounding the polycrystalline perovskite precursor with the random copolymer have important influence on the performance of the perovskite thick film X-ray detector, and the thick film obtained by the method is not easy to fall off and crack, has few crystal boundary defects, and has excellent sensitivity, extremely low X-ray detection lower limit and excellent spatial resolution.
The foregoing description of the preferred embodiments of the invention is not intended to be limiting, but rather is intended to cover all modifications, equivalents, and alternatives falling within the spirit and principles of the invention.
Claims (10)
1. The preparation method of the composite perovskite thick film X-ray detector is characterized by comprising the following steps of:
(1) Dissolving a random copolymer into an organic solvent to obtain a copolymer precursor solution;
(2) Spreading the copolymer precursor liquid obtained in the step (1) on clean ITO conductive glass or TFT thin film transistor, and then annealing to obtain a pretreated ITO or TFT substrate;
(3) Dissolving polycrystalline perovskite precursor powder into the copolymer precursor liquid in the step (1) to obtain perovskite suspension precursor slurry;
(4) Coating the perovskite suspension precursor slurry obtained in the step (3) on the ITO or TFT substrate pretreated in the step (2) by adopting a blade coating method, and annealing to form a perovskite absorption layer;
(5) And (3) placing the device obtained in the step (4) into a vacuum evaporator, evaporating an Au common electrode at the top end, and obtaining the perovskite X-ray detector based on the ITO or TFT substrate.
2. The method for preparing the composite perovskite thick film X-ray detector according to claim 1, wherein in the step (1), the random copolymer with the mass concentration of 5-30 mg/mL is weighed and dissolved in an organic solvent, and the copolymer precursor liquid is obtained by stirring for 5-10 min at normal temperature.
3. The method for preparing a composite perovskite thick film X-ray detector according to claim 1, wherein in the step (1), the random copolymer is one of N-butyl acrylate-co- [ N- (hydroxymethyl) -acrylamide ] }, N-butyl acrylate-co-acrylamide and N-butyl acrylate-co-butenamide.
4. The method for preparing a composite perovskite thick film X-ray detector according to claim 1, wherein in the step (1), the organic solvent is one of gamma butyrolactone and dimethoxy ethanol.
5. The method for preparing a composite perovskite thick film X-ray detector according to claim 1, wherein in the step (2), the thickness of the scraper and the substrate is 10-50 μm when the copolymer precursor liquid is scraped on the ITO and the TFT.
6. The method of manufacturing a composite perovskite thick film X-ray detector as claimed in claim 1, wherein in step (2), the annealing condition is 100 ℃.
7. The method for preparing the composite perovskite thick film X-ray detector according to claim 1, wherein in the step (3), 3-10M of polycrystalline perovskite precursor powder is weighed and dissolved in the copolymer precursor liquid, and the mixture is fully stirred for 30-60 min to obtain perovskite suspension precursor slurry.
8. The method of claim 1, wherein in the step (3), the polycrystalline perovskite precursor is one of methylamine lead-iodine perovskite MAPbI 3, formamidine lead-iodine perovskite FAPbI 3, cesium lead-bromine perovskite CsPbBr 3, and triple-cation perovskite FAMACs.
9. The method for preparing a composite perovskite thick film X-ray detector according to claim 1, wherein in the step (4), when the perovskite suspension precursor slurry is scraped on the corresponding substrate, the distance between the scraper and the substrate is 100-1000 μm.
10. The method for manufacturing a composite perovskite thick film X-ray detector according to claim 1, wherein in the step (4), the annealing condition is that the annealing is performed at 60-100 ℃ for 30-60 min.
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