CN115020530B - Self-driven polarized light detector composed of ferroelectric heterojunction, and preparation method and application thereof - Google Patents

Self-driven polarized light detector composed of ferroelectric heterojunction, and preparation method and application thereof Download PDF

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CN115020530B
CN115020530B CN202210710824.2A CN202210710824A CN115020530B CN 115020530 B CN115020530 B CN 115020530B CN 202210710824 A CN202210710824 A CN 202210710824A CN 115020530 B CN115020530 B CN 115020530B
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李岚
周雪
徐建萍
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Tianjin University of Technology
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Abstract

The invention relates to a self-driven polarization detector formed by a ferroelectric heterojunction, and a preparation method and application thereof. The detector comprises a transparent glass substrate, an FTO bottom electrode, a ferroelectric film layer, a photovoltaic material layer and an upper electrode from bottom to top in sequence; in the preparation process, a sol-gel method is adopted to prepare a three-dimensional netlike BFO precursor solution, and then a BFO ferroelectric film layer with fewer defects and better quality is obtained by adopting a layer-by-layer annealing mode; the obtained device is provided with two different polarization states of a heterojunction device under the polarization adjustment of voltages in different directions, so that the OR logic conversion and AND logic conversion application is realized. The invention utilizes the ferroelectric material to be sensitive to polarized light, and realizes self-driven polarized light detection without an external electric field.

Description

Self-driven polarized light detector composed of ferroelectric heterojunction, and preparation method and application thereof
Technical Field
The invention belongs to the field of optoelectronic devices, and particularly relates to a self-driven polarization photodetector formed by a ferroelectric heterojunction, and a preparation method and application thereof.
Background
The polarized light detector generates light response to the polarized information in the light source, has the advantages of being capable of acquiring multidimensional polarized information from the light source, shielding stray light, having high signal-to-noise ratio and imaging definition and expanding information quantity, and has wide application in the fields of integrated circuits, navigation, aerospace, military, medicine and the like.
Polarization sensitive materials are currently focused mainly on two-dimensional (2D) materials with in-plane anisotropic crystal structures, such as black phosphorus, geSe, etc. However, the polarization ratio of the materials is limited by the absorption anisotropy of the materials/device structures, and an external power supply is required to sense the polarized signals, so that the low-power-consumption, high-sensitivity and high-integration polarized light detector is difficult to realize. The photovoltaic effect of the ferroelectric material originates from the asymmetry of the crystal structure of the material, the polarization ratio is not limited by the absorption anisotropy of the material, and the photoelectric response can be regulated and controlled under the action of an external electric field, so that the ferroelectric material is an ideal material for realizing high-sensitivity self-driven polarized light detectors.
In the prior art, the self-driven polarized light detector based on the ferroelectric photovoltaic effect and the preparation method (CN 114023885A) and the ferroelectric circularly polarized light photovoltaic effect and the preparation method (CN 114034387A) realize self-driven polarized light detection by utilizing the device structure of the single-layer organic-inorganic hybrid perovskite ferroelectric, and the limitation of lower photocurrent and poor stability of the device exists due to the fact that the device structure of the single-layer organic-inorganic halide perovskite is utilized, and the preparation method relates to a large amount of organic alcohol chemicals, has complex process and lower yield, can cause serious environmental pollution and restricts the development of the materials in the polarized light detector.
Disclosure of Invention
The invention aims at overcoming the defects of the prior art and provides a self-driven polarization detector formed by a ferroelectric heterojunction, and a preparation method and application thereof. The detector is made of inorganic ferroelectric film BiFeO 3 And the photovoltaic material layer BiOCl form the main structure of the device; in the preparation process, a sol-gel method is adopted to prepare a three-dimensional netlike BFO precursor solution, and then a BFO ferroelectric film layer with fewer defects and better quality is obtained by adopting a layer-by-layer annealing mode; the obtained device is provided with two different polarization states of a heterojunction device under the polarization adjustment of voltages in different directions, so that the OR logic conversion and AND logic conversion application is realized. The invention utilizes the ferroelectric material to be sensitive to polarized light, and realizes self-driven polarized light detection without an external electric field.
The technical scheme of the invention is as follows:
a self-driven polarized light detector composed of ferroelectric heterojunction comprises a transparent glass substrate, an FTO bottom electrode, a ferroelectric film layer, a photovoltaic material layer and an upper electrode from bottom to top;
the ferroelectric film layer is made of BiFeO 3 The thickness of the film is 200-600nm;
the photovoltaic material layer is made of a BiOCl layer, and the thickness of the photovoltaic material layer is 100-300nm;
the ferroelectric film layer BFO and the photovoltaic material layer BiOCL jointly form a heterojunction structure;
the upper electrode is an Au, ag or Pt electrode layer.
The preparation method of the self-driven polarized light detector formed by the ferroelectric heterojunction comprises the following steps:
step one, forming an FTO lower electrode on a transparent glass substrate;
step two, preparing BFO precursor liquid:
bi (NO) 3 ) 3 ·5H 2 O is dissolved in glycol methyl ether and mechanically stirred for 10 to 20 minutes; adding Fe (NO) 3 ) 3 ·9H 2 Continuously mechanically stirring O for 10-20min, then adding glacial acetic acid, adding ethanolamine as a stabilizer in a water bath at 25-30 ℃ under magnetic stirring, taking out after stirring for 4-8 h, and standing at 15-25 ℃ for 12-24 h to obtain BFO precursor liquid;
wherein, each 16ml of ethylene glycol monomethyl ether is added with 2.5 to 3.5g of Bi (NO) 3 ) 3 ·5H 2 O, 3-5 ml of glacial acetic acid and 0.3-0.5 ml of ethanolamine;
the molar ratio is Bi (NO 3 ) 3 ·5H 2 O：Fe(NO 3 ) 3 ·9H 2 O=1.03 to 1.10:1; preferably 1.05:1, a step of;
the rotating speed of the mechanical stirring is 200-450rpm;
step three, spin coating BFO precursor liquid on the FTO lower electrode to prepare a BFO ferroelectric film layer:
pre-spin-coating the prepared BFO precursor solution on an FTO lower electrode at a rotating speed of 300-600r/min for 5-10 s, and then spin-coating the BFO precursor solution at a high speed of 2000-3500 r/min for 10-20s to prepare a precursor solution film; then placing the precursor film into a muffle furnace for annealing at 500-600 ℃ for 10-20min to obtain a BFO film; repeating the process of pre-spin coating-high-speed spin coating-annealing for 2-5 cycles, and then annealing at 500-600 ℃ for 20-40min to obtain the BFO ferroelectric film attached on the FTO substrate;
step four, growing a BiOCl nano-sheet film on the BFO ferroelectric film by a solvothermal method:
bi (NO) 3 ) 3 ·5H 2 Adding O into ethylene glycol, performing ultrasonic treatment for 5-10min, and stirring for 10-20min until the solution is clear; adding KCl into the mixed solution, stirring for 20-40min until the solution is clear, and obtaining a growth solution; adding the growth solution into a high-pressure reaction kettle, immersing the BFO film therein, and growing for 1-3h at 150-180 ℃ after sealing to obtain the BiOCl nano-sheet film growing on the BFO ferroelectric film, namely the photovoltaic materialA material layer;
wherein, 0.40 to 0.55g of Bi (NO) is added into every 40mL of glycol 3 ) 3 ·5H 2 O, 0.05-0.10 g KCl;
and fifthly, sputtering Au, ag or Pt electrodes on the BiOCl nano-sheet film to obtain the self-driven polarization detector formed by the ferroelectric heterojunction.
When the wavelength is 375nm and the illumination intensity is 1-3mW/cm 2 When the detector is irradiated by polarized light; the detector displays a current value of 1×10 -8 -1×10 -6 A, turning off polarized light and eliminating no light current;
when the wavelength is 475nm and the illumination intensity is 1-3mW/cm 2 When the detector is irradiated by polarized light, the detector displays a current value of 1X 10 -8 -1×10 -8 A, turning off polarized light and eliminating no light current;
when the wavelength is 375nm and the illumination intensity is 1-3mW/cm 2 Has a polarized light and wavelength of 475nm and an illumination intensity of 1-3mW/cm 2 When the polarized light of the detector is jointly irradiated; the detector shows a current value of 2×10 as the sum of the currents obtained by the two light-emitting devices -8 -1.01×10 -6 And A, turning off polarized light and eliminating light current.
The application of the self-driven polarized light detector formed by the ferroelectric heterojunction comprises the following steps:
step one: setting the current value of the detector output, when the current value of the output end is more than 2 multiplied by 10 -8 -6×10 -8 A is defined as logic "1", and the output end current value is smaller than 2×10 -8 -6×10 -8 A is defined as logic "0";
step two:
the detector is polarized by negative voltage of-3-8V for 10-20min, so that the overall resistance of the detector is reduced, and the photocurrent of the detector is increased compared with the original photocurrent no matter 375nm illumination, 475nm illumination or polarized light of two wave bands are illuminated at the same time, and the current value exceeds 2 multiplied by 10 -8 -6×10 -8 A, the logic of the output end is enabled to be 1, when polarized light is turned off, no current exists, and the current value is lower than 2 multiplied by 10 -8 -6×10 -8 A, the logic of the output end is 0, and the detector presents OR gate logic at the moment;
the detector is polarized by using 3-8V bias voltage for 10-20min forward voltage, so that the overall resistance of the detector is increased, the photocurrent of the detector is reduced no matter under 375nm illumination or 475nm illumination, and the current value is smaller than 2 multiplied by 10 as the same as no-light current when the polarized light is turned off -8 -6×10 -8 A, the logic of the output end is 0, and the photocurrent of the detector exceeds 2×10 only when the polarized lights of two wave bands are simultaneously turned on -8 -6×10 -8 A, the logic of the output end is 1, and the detector presents AND gate logic at the moment;
the detection of ultraviolet-visible light wide spectrum light and the logic operation conversion by ferroelectric polarization modulation are realized through the determination of OR gate logic and AND gate logic.
The invention has the substantial characteristics that:
the invention adopts a sol-gel method to prepare three-dimensional reticular BFO precursor liquid, and then adopts a layer-by-layer annealing mode to obtain a BFO ferroelectric film layer with fewer defects and better quality; the obtained ferroelectric heterojunction polarized light detector realizes polarized light detection of the ferroelectric heterojunction device by utilizing the characteristic that the ferroelectric film is sensitive to polarized light. During testing, natural light is changed into polarized light through the polaroid to irradiate the detector, and the direction of the polarized light is changed by rotating the polaroid, so that photocurrents of the detector under the polarized light irradiation in different directions are obtained, and the detection of the polarized light is realized.
The implementation method of the logic application of the ferroelectric heterojunction polarized light detector is shown in fig. 5, polarized light pulses with different wavebands are used as two independent input ends, photocurrent of each input end when the light is on can be used as binary code '1', dark current of the light is used as binary code '0', current value of the device shown in fig. 1 is used as an output end, and two different polarization states of the heterojunction device are set under the polarization adjustment of voltages in different directions, so that the conversion of OR logic and AND logic is realized. Setting positive-pressure polarization of the device, realizing the logic function of an AND gate at the output end, reducing the separation capability of the device to photo-generated carriers due to the opposite direction of a generated depolarization field and the built-in electric field of the heterojunction, weakening the optical response of the device, and obtaining logic 1 only when two polarized light pulses at the input end are simultaneously opened, otherwise obtaining logic 0; on the contrary, negative-pressure polarization of the device is arranged, the output end realizes the logic function of an OR gate, and the generated depolarization field direction is the same as the direction of the built-in electric field of the heterojunction, so that the separation capability of the device on photon-generated carriers is improved, the optical response of the device is enhanced, and logic 0 is obtained only when two polarized light pulses at the input end are closed at the same time, otherwise, the logic 1 is obtained. Thus, the device can effectively switch logic algorithms by setting different polarization states.
The beneficial effects of the invention are as follows:
the invention relates to a self-driven polarization detector formed by a ferroelectric heterojunction, a preparation method and application thereof, wherein the self-driven polarization detector comprises a transparent glass substrate, an FTO bottom electrode, an inorganic ferroelectric film layer and a heterojunction structure formed by a photovoltaic material layer from bottom to top, and an upper electrode. The photocurrent of the ferroelectric heterojunction device was improved by a factor of 25 compared to a single layer ferroelectric thin film device (fig. 3). The ferroelectric film layer with fewer defects and better compactness is obtained by adopting a sol-gel method through a layer-by-layer annealing mode. By utilizing the characteristics that the ferroelectric material is sensitive to polarized light and can be polarized by an external electric field, the self-driven polarized light detection without an external electric field is realized, the logic algorithm (table 1) can be effectively switched by setting different polarization states, the multifunctional photoelectric device integrating detection and logic calculation is realized, a programmable logic circuit is simplified, and the application range of the ferroelectric device is widened.
Drawings
FIG. 1 is a schematic diagram of the structure of a self-driven polarization detector of the present invention composed of ferroelectric heterojunction; wherein, the glass substrate is 1-transparent, the bottom electrode of 2-FTO; 3-inorganic ferroelectric thin film layer BFO; 4-a layer of photovoltaic material BiOCl; 5-upper electrode Au;
fig. 2 is a band gap fit map of the BFO ferroelectric thin film layer and the BiOCl thin film layer, wherein fig. 2 (a) is a band gap fit of the BiOCl thin film layer and fig. 2 (b) is a band gap fit of the BFO ferroelectric thin film layer.
FIG. 3 is a graph of I-t for a BFO monolayer device and a BFO/BiOCl heterojunction device, wherein FIG. 3 (a) is a graph of BFO monolayer device at λ=405 nm, P=2 mW/cm 2 An I-t curve measured at 0V bias, fig. 3 (b) is a BFO/BiOCl heterojunction polarized light detector at λ=405 nm, p=2 mW/cm 2 I-t curve measured at 0V bias.
Fig. 4 is an I-t curve and a photocurrent fitting curve of the BFO/BiOCl heterojunction device in different ferroelectric polarization states, wherein fig. 4 (a) is an I-t curve of the BFO/BiOCl heterojunction polarization photodetector in different ferroelectric polarization states, and fig. 4 (b) is a photocurrent fitting curve of the heterojunction device in different polarization voltages.
FIG. 5 is a diagram of an apparatus for implementing logic operations for a polarized light detector of the present invention.
Figure 6 is an XRD pattern for BFO films with 5% Bi excess and 10% Bi excess.
Figure 7 is an XRD pattern of a BFO precursor liquid film prepared with three solvents, ethylene glycol methyl ether, and acetic acid.
Detailed Description
The ferroelectric heterojunction polarized light detector structure of the invention is shown in figure 1, and comprises a transparent glass substrate 1, an FTO bottom electrode 2 and a heterojunction structure from bottom to top in sequence: a ferroelectric thin film layer 3 and a photovoltaic material layer 4, an upper electrode 5. Preferably, the ferroelectric thin film layer in the present invention is BiFeO 3 The photovoltaic material layer is a BiOCl layer, and the upper electrode is a sputtered Au electrode layer.
The self-driven polarization photodetector formed by the ferroelectric heterojunction improves the light response of the device by constructing an inorganic ferroelectric film layer BFO and a photovoltaic material layer BiOCl heterojunction composite layer with a vertical structure. The inorganic ferroelectric film layer is prepared by a sol-gel method, the preparation method is simple, and the film has good stability. The ferroelectric heterojunction device not only can realize the polarized light detection function, but also can realize the logic conversion function of the device by setting different polarization states of the device, thereby simplifying the logic circuit and widening the application of the ferroelectric device.
The invention will be described in detail below with reference to the drawings in connection with embodiments.
Example 1
As shown in figure 1, the ferroelectric heterojunction detector structure is shown in figure 1, and comprises a transparent glass substrate 1, an FTO bottom electrode 2, a ferroelectric film layer 3 and a photovoltaic material layer 4, and an upper electrode 5 from bottom to top.
The preparation method of the heterojunction polarized light detector based on ferroelectric polarization regulation comprises the following steps of;
step one, a commercially available transparent glass substrate 1 with an FTO 250nm lower electrode 2 is wiped with a detergent to wipe the FTO lower electrode 2 until the cleaning is finished, so that dust adsorbed on the surface of the transparent glass substrate is removed; ultrasonically cleaning the FTO lower electrode 2 by using a detergent to remove surface organic matters and impurity particles, cleaning for 10min each time, vacuum drying for 30min at 80 ℃, and then treating the surface of the substrate by using oxygen plasma to improve the work function;
and step two, preparing BFO precursor liquid.
Will 3.0559gBi (NO) 3 ) 3 ·5H 2 O was dissolved in 16ml of ethylene glycol methyl ether and stirred at 450rpm for 20min. 2.424g (i.e. 0.006 mol) of Fe (NO 3 ) 3 ·9H 2 O is put into dissolved Bi (NO) 3 ) 3 ·5H 2 O (i.e. 0.0063mol compared to Fe (NO) 3 ) 3 ·9H 2 O,Bi(NO 3 ) 3 ·5H 2 O5%) was added with 4ml of glacial acetic acid and stirred magnetically for 30min after stirring at 450rpm for 10 min. The beaker is moved into a water bath kettle to be magnetically stirred at 30 ℃, 0.4ml of ethanolamine is added as a stabilizer, the mixture is taken out after stirring for 6 hours, and then the mixture is kept stand for 24 hours at 18 ℃ in a refrigerator to obtain clear, transparent and dark red BFO precursor liquid.
And thirdly, spin-coating BFO precursor liquid on the FTO lower electrode 2 to prepare the BFO ferroelectric film 3.
And sucking 0.5ml of the prepared BFO precursor solution by a dropper, dripping the solution on the FTO conductive glass, pre-spin-coating the solution on the FTO at a transfer speed of 600r/min for 5s to fully spread the solution on the FTO, and then starting high-speed rotation at a rotational speed of 3500r/min for 20s to prepare a uniform precursor solution film. Putting a precursor film into a muffle furnace for annealing at 550 ℃ for ten minutes, and naturally cooling to room temperature to obtain a BFO film; then continuously repeating spin coating of the next layer; repeating the process of 'pre-spin coating-high-speed spin coating-annealing-cooling' for 4 times, and finally, putting the spin-coated film into a muffle furnace for annealing crystallization for 30min at 550 ℃ to obtain the spin-coated BFO ferroelectric film with the thickness of 270nm on the FTO substrate.
And step four, growing the BiOCl nano-sheet film 4 on the BFO ferroelectric film 3 by a solvothermal method.
1mmol of Bi (NO) 3 ) 3 ·5H 2 Placing O into 40ml of ethylene glycol, performing ultrasonic treatment for 5min, and stirring for 20min until the solution is clear; then, 1mmol of KCl is put into the mixed solution, and the mixed solution is stirred for 40min until the solution is clear, so as to obtain the growth solution. The BFO film is put into a 100ml high-pressure reaction kettle liner, the BFO film faces downwards, and is put into a growth solution, and the growth is carried out for 3 hours at 160 ℃ after sealing. And after the reaction is finished, taking out the reaction kettle, cooling to normal temperature, washing the reaction kettle with absolute ethyl alcohol and deionized water for several times, and drying the reaction kettle at 80 ℃ for 30min to obtain the BFO/BiOCl heterojunction film.
And fifthly, sputtering an Au electrode array 5 on the BiOCl nano-sheet film 4 by using an ion sputtering instrument, wherein the diameter is 2mm, the distance is 4mm, and the thickness is 100nm, and finally obtaining the ferroelectric heterojunction detector.
The absorption coefficient of the film and the corresponding wavelength can calculate the corresponding light wave energy, and by utilizing Tauc formula (1), we can calculate the optical band gap of the BFO ferroelectric film and the BiOCl film,
(αh) 2 ＝A(hv-Eg) (1)
where α represents the absorption coefficient, h is the Planckian constant, v represents the frequency of the light wave, i.e., hv is the photon energy, and A is a constant. Since BiOCl thin film is an indirect bandgap semiconductor, it is based on (. Alpha.h) 1/2 The relationship between photon energy was plotted and fitted as in fig. 2 (a) to give a BiOCl film with an optical bandgap of 3.4eV. BFO film is a direct bandgap semiconductor, according to (. Alpha.h) 2 The relationship between the energy of photons is plotted and fitting calculation is performed, and the optical band gap of the BFO film obtained in the step (b) of fig. 2 is 2.34eV, which is consistent with the previous reported result.
As shown in FIG. 3 (a), the irradiance was 2mW/cm under light conditions of 405nm 2 I-t curve measured for BFO monolayer devices at 0V bias. The switching ratio of the device was only 40, and the value of the photo current of the BFO monolayer device was low due to the weak light absorption capability and low carrier mobility of the ferroelectric material. In order to improve the optical response of the visible light detector, a layer of BiOCl film is grown on the BFO ferroelectric film to form a heterojunction built-in electric field, so that the separation capability of the photo-generated carriers is enhanced. As shown in FIG. 3 (b), the irradiance was 2mW/cm under light conditions of 405nm 2 I-t curve measured at 0V bias for heterojunction polarized light detector. The switching ratio of the BFO/BiOCl heterojunction device can reach 1 multiplied by 10 3 This is a 25-fold increase over the switching ratio of a BFO single layer device. The BFO ferroelectric film BiOCl forms heterojunction contact, and a built-in electric field is formed in the heterojunction region, so that the driving force of photo-generated carriers is improved, and the photoelectric response of the heterojunction polarized light detector is improved.
In order to realize the OR and AND logic conversion, the principle that the ferroelectric film can be regulated and controlled by an external electric field is utilized, the ferroelectric film is polarized by applying voltages with different directions/magnitudes to the two end electrodes of the heterojunction device, and then I-t curves under different ferroelectric polarization states are tested under the same test condition. As shown in fig. 4, the photocurrent of the device decreases compared to the current value in the initial state as the positive voltage polarization is applied and decreases as the applied polarization voltage decreases, and increases compared to the current value in the initial state as the negative voltage polarization is applied and increases as the applied polarization voltage increases.
Due to the ferroelectric photovoltaic effect of the BFO film, the photoresponse of the BFO/BiOCl heterojunction device is regulated and controlled through ferroelectric polarization, polarized electrons can be generated in the ferroelectric film under the action of an external electric field, and when depolarization voltage is removed, a depolarization field E opposite to the direction of the polarized voltage can be generated in the film dp . When polarized by a forward voltage, the BFO film generates a depolarization field E opposite to the positive voltage dp At this time, build-in electric field E bi And E is d The direction of p is opposite: e (E) all ＝E bi -E dp ，E all Is the driving force for the separation of photo-generated electron-hole pairs, and E all ＜E bi The driving force for the photogenerated carriers is reduced, so that after positive voltage polarization is applied, the photocurrent of the device is reduced compared to the current in the unpolarized state. When negative pressure polarization is applied, the BFO film generates a depolarization field E opposite to the negative pressure direction dp At this time E bi And E is dp Is consistent in the direction of: e (E) all ＝E bi +E dp ，E all Is the driving force for the separation of photo-generated electron-hole pairs, and E all ＞E bi The driving force of the photogenerated carriers increases, so that after negative polarization is applied, the photocurrent of the device increases compared to the current in the unpolarized state.
From fig. 4, it can be known that we can realize the regulation of the optical response of the heterojunction polarized light detector by using ferroelectric polarization, so we build a device diagram of the polarized light detector to realize the reconstruction of the or and logic by using the different polarization states of the ferroelectric as shown in fig. 5. This device diagram has two independent inputs: two polarized lights (composed of two LED light sources with different wave bands and two polaroids, natural light passes through the polaroids to become polarized light), photocurrent of the device is used as an output end, and the source meter can regulate and control different polarization states of the device.
As shown in table 1, the photocurrent at the time of optical on for each input terminal can be used as a binary code of "1", and the dark current at the time of optical off can be used as a binary code of "0". The device is set to be polarized at the bias voltage of 5V for 15min under positive pressure, the logic function of an AND gate is realized, and the photoelectric response of the device is reduced because the direction of the generated depolarization field is opposite to the direction of the built-in electric field of the heterojunction. The optical response of the single wave band and the optical response of the double wave band are reduced, but the optical current of the double wave band optical response is the linear superposition value of two single wave band currents, and logic '1' can be obtained only when two polarized optical pulses at the input end are simultaneously opened and the optical current at the output end is larger than a preset current value, otherwise, the optical current at the output end is logic '0'; on the contrary, the negative pressure polarization of the device is set at the bias voltage of-5V for 15min, the logic function of an OR gate is realized, the optical response of the device is enhanced because the direction of the generated depolarization field is the same as the direction of the built-in electric field of the heterojunction, no matter whether the single-band optical pulse of the input end is opened or the double-band optical pulse is opened, the photocurrent of the output end is larger than the preset current value, the output end can display logic '1', and logic '0' can be obtained only when the two polarized optical pulses of the input end are closed at the same time. Through the voltage setting, the OR and AND logic conversion function can be realized on the ferroelectric heterojunction device, and the multifunctional intelligent device integrating sensing and calculation is realized. In the current intelligent sensing system, a corresponding processing unit is required for sensing optical signals and transmitting and processing electric signals, and the conversion efficiency and the delay time are low in the process. The intelligent photoelectric device integrating sensing and calculation is successfully designed by utilizing the characteristic that the ferroelectric heterojunction device can be polarized by an external field, the light detection of ultraviolet-visible light wide spectrum and the logic operation conversion by utilizing ferroelectric polarization modulation are realized, the power consumption and time delay generated by sensing and calculation separation in the existing intelligent system are broken through, the design of a logic circuit is simplified, and a new thought is realized for a future multifunctional sensing device.
As shown in FIG. 6, XRD patterns of the BFO film with 5% Bi excess and 10% Bi excess show that the film has higher diffraction peak intensity, better crystallinity and better performance when the Bi is 5% excess than when the Bi is 10% excess. As shown in fig. 7, the crystallinity of the BFO film obtained using ethylene glycol methyl ether and acetic acid as the BFO precursor liquid is best and the film quality is best compared to using ethylene glycol methyl ether or ethylene glycol as the solvent.
Table 1 is a graph of inputs and outputs for implementing a logical OR to AND under different polarization states of the present invention.
Example 2
Other steps are the same as in example 1 except that Bi (NO 3 ) 3 ·5H 2 The O content was determined to be 3.0559g (Bi (NO 3 ) 3 ·5H 2 5% excess O) was replaced by 3.2014g (Bi (NO) 3 ) 3 ·5H 2 O10% excess);
example 3
Other steps are the same as in example 1 except that when BFO precursor liquid is prepared, the solvent is replaced by 20ml of ethylene glycol methyl ether by 16ml of ethylene glycol methyl ether and 4ml of glacial acetic acid;
example 4
Other steps are the same as in example 1 except that when BFO precursor liquid is prepared, the solvent is replaced by 20ml of ethylene glycol from 16ml of ethylene glycol methyl ether and 4ml of glacial acetic acid;
the products obtained in examples 2 to 4 were similar to example 1 in terms of crystallinity of the films of FIGS. 6 and 7.
Comparative example 1:
the other steps are the same as in example 1, except that the selective annealing is a one-time annealing. The obtained BFO film has more holes, larger particles on the surface of the film and weaker photoelectric performance of the heterojunction device.
The invention is not a matter of the known technology.

Claims (4)

1. A self-driven polarized light detector formed by ferroelectric heterojunction is characterized in that the detector comprises a transparent glass substrate, an FTO bottom electrode, a ferroelectric film layer, a photovoltaic material layer and an upper electrode from bottom to top in sequence;
the ferroelectric film layer is made of BiFeO 3 The thickness of the film is 200-600nm;
the photovoltaic material layer is made of a BiOCl layer, and the thickness of the photovoltaic material layer is 100-300nm;
the ferroelectric film layer BFO and the photovoltaic material layer BiOCL jointly form a heterojunction structure;
the upper electrode is an Au, ag or Pt electrode layer;
the preparation method of the self-driven polarized light detector formed by the ferroelectric heterojunction comprises the following steps:
step one, forming an FTO lower electrode on a transparent glass substrate;
step two, preparing BFO precursor liquid:
bi (NO) 3 ) 3 ·5 H 2 O is dissolved in ethylene glycol methyl ether, and is mechanically stirred for 10-20 min; adding Fe (NO) 3 ) 3 ·9H 2 Continuously mechanically stirring O for 10-20min, then adding glacial acetic acid, adding ethanolamine as a stabilizer in a water bath at 25-30 ℃ under magnetic stirring, taking out after stirring for 4-8 h, and standing at 15-25 ℃ for 12-24 h to obtain BFO precursor liquid;
wherein, each 16. 16ml ethylene glycol monomethyl ether is added with 2.5-3.5 g Bi (NO) 3 ) 3 ·5 H 2 O, 3-5 ml of glacial acetic acid and 0.3-0.5 ml of ethanolamine;
the molar ratio is Bi (NO 3 ) 3 ·5 H 2 O：Fe(NO 3 ) 3 ·9H 2 O=1.03~1.10:1；
Step three, spin coating BFO precursor liquid on the FTO lower electrode to prepare a BFO ferroelectric film layer:
pre-spin-coating the prepared BFO precursor solution on an FTO lower electrode at a rotating speed of 300-600r/min for 5-10 s, and then spin-coating at a high speed of 2000-3500 r/min for 10-20s to prepare a precursor solution film; then, putting the precursor film into a muffle furnace for annealing at 500-600 ℃ for 10-20min to obtain a BFO film; repeating the process of pre-spin coating, high-speed spin coating and annealing for 2-5 cycles, and then annealing at 500-600 ℃ for 20-40min to obtain a BFO ferroelectric film attached to the FTO substrate;
step four, growing a BiOCl nano-sheet film on the BFO ferroelectric film by a solvothermal method:
bi (NO) 3 ) 3 ·5H 2 Adding O into ethylene glycol, performing ultrasonic treatment for 5-10min, and stirring for 10-20min until the solution is clear; adding KCl into the mixed solution, stirring for 20-40min until the solution is clear, and obtaining a growth solution; adding the growth solution into a high-pressure reaction kettle, immersing the BFO film therein, and growing 1-3h at 150-180 ℃ after sealing to obtain a BiOCl nano-sheet film growing on the BFO ferroelectric film, namely a photovoltaic material layer;
wherein, 0.40-0.55 g Bi (NO) is added into each 40mL glycol 3 ) 3 ·5H 2 O, 0.05-0.10 g of KCl;
and fifthly, sputtering Au, ag or Pt electrodes on the BiOCl nano-sheet film to obtain the self-driven polarization detector formed by the ferroelectric heterojunction.
2. A self-driven polarized light detector consisting of a ferroelectric heterojunction as claimed in claim 1, wherein the mechanical stirring speed in the preparation method is 200-450 rpm.
3. Use of a self-driven polarized light detector consisting of a ferroelectric heterojunction as claimed in claim 1, characterized in that
When the wavelength is 375nm and the illumination intensity is 1-3mW/cm 2 When the detector is irradiated by polarized light; the detector displays a current value of 1×10 -8 -1×10 -6 A, turning off polarized light and eliminating no light current;
when the wavelength is 475nm and the illumination intensity is 1-3mW/cm 2 When the detector is irradiated by polarized light, the detector displays a current value of 1X 10 -8 -1×10 -8 A, turning off polarized light and eliminating no light current;
when the wavelength is 375nm and the illumination intensity is 1-3mW/cm 2 Has a polarized light and wavelength of 475nm and an illumination intensity of 1-3mW/cm 2 When the polarized light of the detector is jointly irradiated; the current value displayed by the detector is the sum of currents obtained by two light-emitting devices: 2X 10 -8 -1.01×10 -6 And A, turning off polarized light and eliminating light current.
4. Use of a self-driven polarized light detector consisting of a ferroelectric heterojunction as claimed in claim 3, characterized in that it comprises the steps of:
step one: setting the current value of the detector output, when the current value of the output end is more than 2 multiplied by 10 -8 -6×10 -8 A is defined as logic "1", and the output end current value is smaller than 2×10 -8 -6×10 -8 A is defined as logic "0";
step two:
negative bias of-3-8V for 10-20minThe voltage polarization detector is polarized, so that the overall resistance of the detector is reduced, the photocurrent of the detector is increased compared with the original photocurrent of the detector no matter 375nm illumination, 475nm illumination or polarized light of two wave bands are illuminated at the same time, and the current value exceeds 2 multiplied by 10 -8 -6×10 -8 A, the logic of the output end is enabled to be 1, when polarized light is turned off, no current exists, and the current value is lower than 2 multiplied by 10 -8 -6×10 -8 A, the logic of the output end is 0, and the detector presents OR gate logic at the moment;
the detector is polarized by using 3-8V bias voltage for 10-20min forward voltage, so that the overall resistance of the detector is increased, the photocurrent of the detector is reduced no matter under 375nm illumination or 475nm illumination, and the current value is smaller than 2 multiplied by 10 as the same as no-light current when the polarized light is turned off -8 -6×10 -8 A, the logic of the output end is 0, and the photocurrent of the detector exceeds 2×10 only when the polarized lights of two wave bands are simultaneously turned on -8 -6×10 -8 A, the logic of the output end is 1, and the detector presents AND gate logic at the moment;
the detection of ultraviolet-visible light wide spectrum light and the logic operation conversion by ferroelectric polarization modulation are realized through the determination of OR gate logic and AND gate logic.
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