CN111725337A - Method for improving photoelectric property of BLFO/ZnO heterojunction by utilizing ferroelectric and piezoelectric photoelectronic effects - Google Patents
Method for improving photoelectric property of BLFO/ZnO heterojunction by utilizing ferroelectric and piezoelectric photoelectronic effects Download PDFInfo
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Abstract
A method for improving photoelectric performance of BLFO/ZnO heterojunction by utilizing ferroelectricity and piezoelectric photoelectron effect relates to the field of ferroelectric semiconductor heterojunction device, applies pulse bias to BLFO/ZnO heterojunction device to call BLFO ferroelectricity, after BLFO/ZnO heterojunction device calls BLFO ferroelectricity, applies pressure strain to BLFO/ZnO heterojunction device to introduce piezoelectric photoelectron effect to achieve the purpose of calling ferroelectric and piezoelectric photoelectron effect simultaneously so as to enhance the total driving force of current carrier, the invention adopts sol-gel method and hydrothermal method to prepare BLFO/ZnO heterojunction device, studies the influence of piezoelectric photoelectron effect and ferroelectric effect on its photovoltaic characteristic, utilizes piezoelectric photoelectron effect to modulate carrier transport behavior, obviously improves open circuit voltage and short circuit current of BLFO/ZnO heterojunction device, external electric field polarization is introduced on the basis of compressive strain, the piezoelectric photoelectronic effect and ferroelectricity are called, and the total driving force of a heterojunction energy band structure and a current carrier is modulated, so that the photoelectric performance of the heterojunction is improved.
Description
Technical Field
The invention relates to the field of ferroelectric semiconductor heterojunction devices, in particular to a method for improving the photoelectric property of a BLFO/ZnO heterojunction by utilizing ferroelectricity and piezoelectric photoelectron effect.
Background
In recent decades, global warming and energy crisis have become increasingly severe. Much research has been devoted to the exploration of green renewable energy sources. The conversion of photo-electric energy in ferroelectric materials was proposed over 30 years ago and has attracted great interest because it can convert light directly into electricity by the photoelectric effect. The photovoltaic effect generally involves two basic processes. First, the device absorbs incident photons to excite electron-hole pairs to generate photogenerated carriers. Subsequently, the driving force within the optoelectronic device transports the carriers to the electrodes. In ferroelectric materials, the depolarization field is generally considered to be the driving force for charge carriers. A steady and powerful driving force is a key factor in determining photovoltaic performance of photovoltaic devices. In ferroelectric materials, BiFeO3(BFO) has attracted extensive attention over the past decades due to its visible photovoltaic effect, multiferroic properties at room temperature and related potential applications. In consideration of the preparation cost and process conditions of BFO, the current BFO film preparation method has more reports about chemical solution deposition method, because the method can precisely control the chemical composition, which is more beneficial to preparing high-quality BFO-based ferroelectric film with excellent ferroelectric property. To date, research on BFO has focused primarily on multiferroic and photovoltaic properties, which limits its applications. Therefore, the exploration of the coupling of ferroelectrics and other research fields has important significance for designing and researching novel photoelectric devices with unprecedented functional characteristics.
The piezoelectric photoelectronic effect is used as a novel semiconductor, piezoelectric and optical excitation characteristic coupling technology, and the performance of a photoelectric device can be adjusted by adjusting the transport process of a carrier, so that a new research field is developed. Many reports have demonstrated the great potential of strain-induced piezoelectric potentials for optoelectronic devices by applying strain in piezoelectric semiconductors, effectively regulating the separation and transport of charge carriers at the heterojunction device interface. Piezoelectric optoelectronics effects are excited by applying a static mechanical strain without changing the device materials and structure. Therefore, the one-dimensional nano material has good mechanical durability and is very suitable for the research of the piezoelectric photoelectron effect. The zinc oxide is used as a piezoelectric semiconductor material, and has wide application in the fields of piezoelectric optoelectronics effect, sensors, nanoelectronics, energy collection and the like due to the mature preparation process and the characteristics of multifunctional materials. At present, the piezoelectric photoelectronic effect is widely applied to a plurality of fields such as solar cells, photoelectric detectors, photocatalysis, nerve morphology calculation, two-dimensional materials and the like. However, the research on the piezoelectric photoelectron effect and the ferroelectric coupling mechanism is very rare, and therefore, the research on the synergistic effect between the piezoelectric photoelectron effect and the ferroelectric coupling mechanism has great significance for widening the application range of the piezoelectric photoelectron effect.
Disclosure of Invention
In order to solve the problems in the prior art, the invention provides a method for improving the photoelectric property of a BLFO/ZnO heterojunction by utilizing ferroelectricity and piezoelectric photoelectron effect.
The technical scheme is as follows: the BLFO/ZnO heterojunction device is applied with pulse bias voltage to call BLFO ferroelectricity, and after the BLFO/ZnO heterojunction device calls the ferroelectricity of BLFO, the BLFO/ZnO heterojunction device is applied with compressive strain to introduce piezoelectric optoelectronics effect, so that the purpose of calling the ferroelectricity and the piezoelectric optoelectronics effect simultaneously is achieved, the total driving force of current carriers is enhanced, and the photoelectric performance of the BLFO/ZnO heterojunction is tested.
Preferably, the BLFO ferroelectric procedure is invoked as: and (3) connecting the upper electrode ITO of the BLFO/ZnO heterojunction device through a positive terminal of a keithley2400 digital source meter, connecting a negative terminal of the BLFO/ZnO heterojunction device with a lower electrode FTO of the BLFO/ZnO heterojunction device, generating a voltage of +10V lasting for 1 second and a voltage of-10V lasting for 1 second by using the keithley2400 digital source meter, and polarizing the BLFO/ZnO heterojunction device to call the ferroelectricity of the BLFO.
Preferably, a piezoelectric optoelectronics effect process is introduced: after the BLFO/ZnO heterojunction device calls the ferroelectricity of the BLFO, a thin cover glass is placed above the BLFO/ZnO heterojunction device, the compressive stress of a piezoelectric motor is applied to the cover glass, the cover glass enables the stress to be uniformly applied to the upper portion of the BLFO/ZnO heterojunction device, and then the piezoelectric motor applies nanoscale displacement to enable the BLFO/ZnO heterojunction device to receive the compressive strain and introduce the piezoelectric photoelectronic effect.
Preferably, the open circuit voltage and short circuit current are strained from 0.379V and 0.271mA/cm at zero strain by straining the BLFO/ZnO heterojunction device2Increased to 0.397V and 0.370mA/cm at-2.3% compressive strain2Respectively increased by 4.8% and 36.4%, and the open-circuit voltage and short-circuit current are increased to 0.411V and 0.419mA/cm after applying forward electric field polarization while maintaining-2.3% of voltage strain2Compared with the test result under 0 strain, the strain is improved by 8.4 percent and 54.6 percent.
Preferably, the BLFO thin film is prepared by a sol-gel method, which comprises the following steps: the precursor liquid of the BLFO is prepared, and the BLFO ferroelectric film is prepared by adopting a spin coating method.
Preferably, the method of making a precursor liquid of BLFO: using bismuth nitrate pentahydrate [ Bi (NO)3)3·5H2O]Iron nitrate nonahydrate [ Fe (NO)3)·9H2O]Lanthanum nitrate hexahydrate La (NO)3)3·6H2O]As a raw material, bismuth nitrate pentahydrate [ Bi (NO) was weighed3)3·5H2O]Has a mass of 1.36g, lanthanum nitrate hexahydrate [ La (NO)3)3·6H2O]Weighing0.1948g iron nitrate nonahydrate [ Fe (NO)3)·9H2O]1.2120g is weighed, the medicine is put into 4ml of ethylene glycol monomethyl ether, the mixture is stirred at the rotating speed of 400r/min until the medicine is completely dissolved, then 2ml of glacial acetic acid and 3ml of acetic anhydride are added as dehydrating agents, the stirring is continued until the solution is cooled to the room temperature, finally the ethylene glycol monomethyl ether is added, the volume of the solution is adjusted to 10ml, the concentration is 0.3mol/L, the stirring is continued for 12h, and the solution is placed for 24h to be completely aged.
Preferably, the process for making the BLFO ferroelectric thin film is: performing ultrasonic treatment on FTO conductive glass with the size of 15 x 1.6mm for 20min by using deionized water, acetone and ethanol respectively, repeating the ultrasonic treatment twice, then drying the FTO conductive glass by using a nitrogen gun and placing the FTO conductive glass into a glue homogenizing machine, dropwise adding precursor liquid by using a disposable 1ml medical injector, rotating the FTO conductive glass at 800r/min for 10s to enable the precursor liquid to be paved on a substrate, then rotating the FTO conductive glass at 4000r/min for 30s to enable the solution to reach the appropriate thickness and be uniformly paved on the substrate, quickly placing the prepared sample into a 350 ℃ tubular furnace for pre-annealing for 5min to enable organic matters to be cracked, then annealing at 550 ℃ for 20min to enable a film to be crystallized, and then taking out and.
Preferably, a ZnO nanowire array is prepared: firstly, a ZnO seed crystal layer is prepared on a BLFO film by magnetron sputtering, and then a ZnO nanowire array is prepared by a hydrothermal method.
Preferably, the process for preparing the ZnO nanowire array by the hydrothermal method comprises the following steps: 2.9875g of zinc nitrate hexahydrate [ Zn (NO) was weighed out3)2·6H2O]0.7008g of hexamethylenetetramine [ (CH)2)6N4)]Respectively adding the mixture into 100ml of deionized water, stirring at the rotating speed of 400r/min for 5min to completely dissolve the medicines, then pouring the two solutions into a 200ml glass bottle for continuous stirring, adding 9ml of ammonia water to adjust the pH value of the solution, putting the ZnO side of the BLFO/ZnO sample into the solution downwards to enable the BLFO/ZnO sample to float in the solution, putting the sealed glass bottle into a thermostat at 90 ℃ for 9h, taking out the sample, washing the sample with ethanol, and drying.
The invention has the beneficial effects that:
1. the BLFO/ZnO heterojunction device is prepared by a sol-gel method and a hydrothermal method, the influence of piezoelectric optoelectronics effect and ferroelectric effect on the photovoltaic characteristics of the BLFO/ZnO heterojunction device is researched, the carrier transport behavior is modulated by utilizing the piezoelectric optoelectronics effect, the open-circuit voltage and the short-circuit current of the BLFO/ZnO heterojunction device are obviously improved, meanwhile, external electric field polarization is introduced on the basis of compressive strain, the piezoelectric optoelectronics effect and the ferroelectricity are called, the heterojunction band structure and the total driving force of carriers are modulated, and therefore the photoelectric performance of the heterojunction device is further improved, and the BLFO/ZnO heterojunction device has higher response speed and excellent mechanical stability;
2. the invention applies strain, and the open-circuit voltage and the short-circuit current are 0.379V and 0.271mA/cm under zero strain2Increased to 0.397V and 0.370mA/cm at-2.3% compressive strain2About 4.8% and 36.4% respectively, while maintaining a pressure strain of-2.3%, and after applying a forward electric field polarization, the open-circuit voltage and the short-circuit current were further increased to 0.411V and 0.419mA/cm2Compared with the test result under 0 strain, the improvement is about 8.4 percent and 54.6 percent, the improvement effect is remarkable, and after the external electric field polarization in the reverse direction is applied, the open-circuit voltage and the short-circuit current are respectively reduced to 0.385V and 0.328mA/cm2；
3. The modulation of the piezoelectric photoelectric effect and the ferroelectric coupling is higher than that under any test condition, which shows that the piezoelectric photoelectric effect and the ferroelectric are mutually enhanced, but the photoelectric performance of the heterojunction is not independently increased;
4. the invention shows that the BLFO/ZnO heterojunction device has good fatigue resistance on the basis of piezoelectric photoelectron effect and ferroelectric coupling through fatigue test.
Drawings
FIG. 1: the invention provides a structural schematic diagram of a BLFO/ZnO heterojunction device.
FIG. 2: the present invention provides surface SEM images of BLFO ferroelectric thin films.
FIG. 3: the present invention provides an SEM top view of a ZnO nanowire array.
FIG. 4: cross-sectional SEM images of BLFO/ZnO heterojunction devices of the present invention.
FIG. 5: cross-sectional EDS images of BLFO/ZnO heterojunction devices of the present invention.
FIG. 6: the experimental device schematic diagram of the BLFO/ZnO heterojunction in the invention under a series of illumination measurement.
FIG. 7: the invention discloses a schematic diagram of an experimental device of a BLFO/ZnO heterojunction under a series of illumination measurement.
FIG. 8: the J-V curve of the BLFO/ZnO heterojunction device in the invention under different optical power densities.
FIG. 9: the BLFO/ZnO heterojunction device has J-V curves in different polarization states under 40 mw/cm-2 power light.
FIG. 10: the BLFO/ZnO heterojunction device of the invention has short-circuit current and open-circuit voltage under different illumination and polarization states.
FIG. 11: the device repeatability of the BLFO/ZnO heterojunction device is tested under different optical power densities.
FIG. 12: the experimental device schematic diagram of the BLFO/ZnO heterojunction in different compressive strain and polarization states is shown in the invention.
FIG. 13: the invention discloses a schematic diagram of an experimental device of a BLFO/ZnO heterojunction under different compressive strain and polarization states.
FIG. 14: the J-V curve of the BLFO/ZnO heterojunction device in the invention under different compressive strains.
FIG. 15: the BLFO/ZnO heterojunction device of the invention has J-V curves under different polarization states under-2.3% compressive strain.
FIG. 16: the short circuit current and the open circuit voltage of the BLFO/ZnO heterojunction device in different compressive strain and polarization states are provided.
FIG. 17: the repeatability of the BLFO/ZnO heterojunction device in the invention is that the device has different compressive strains under the illumination of 405nm and the strain is 100mw/cm < -2 >.
FIG. 18: the response time and recovery time of the BLFO/ZnO heterojunction devices of the present invention were compared under three different test conditions.
FIG. 19: the invention is used for testing fatigue under the forward polarization condition when the wavelength is 405nm and the power density is 100mW/cm 2.
Detailed Description
In order to better understand the invention, the following description of the implementation of the example further illustrate the content of the invention, but the content of the invention is not limited to the following embodiments.
The method comprises the steps of applying pulse bias to a BLFO/ZnO heterojunction device, calling the BLFO ferroelectricity, applying compressive strain to the BLFO/ZnO heterojunction device after the BLFO/ZnO heterojunction device calls the ferroelectricity of the BLFO, introducing the piezoelectric photoelectronic effect, achieving the purpose of calling the ferroelectricity and the piezoelectric photoelectronic effect at the same time, enhancing the total driving force of carriers, and testing the photoelectric property of the BLFO/ZnO heterojunction.
The BLFO/ZnO heterojunction device is formed by a BLFO ferroelectric film and a ZnO nanowire array, the upper electrode of the BLFO/ZnO heterojunction device is an ITO electrode prepared by magnetron sputtering, and the background vacuum is less than 4.7 × 10 in the sputtering process-4Pa, radio-frequency sputtering power 80W, sputtering gas pressure 2.1Pa, target spacing 50mm, argon gas-oxygen gas flow rate ratio (sccm) 50: 0, substrate temperature 350 ℃. The sputtering time is 15 min.
The BLFO/ZnO heterojunction device is wiped by hydrochloric acid to remove ZnO, hydrofluoric acid is used for wiping the BLFO/ZnO heterojunction device to remove BLFO, the exposed FTO is used as a lower electrode, and silver paste and a copper lead are used for leading out the electrode.
Where the BLFO ferroelectric procedure is invoked as: and (3) connecting the upper electrode ITO of the BLFO/ZnO heterojunction device through a positive terminal of a keithley2400 digital source meter, connecting a negative terminal of the BLFO/ZnO heterojunction device with a lower electrode FTO of the BLFO/ZnO heterojunction device, generating a voltage of +10V lasting for 1 second and a voltage of-10V lasting for 1 second by using the keithley2400 digital source meter, and polarizing the BLFO/ZnO heterojunction device to call the ferroelectricity of the BLFO.
Wherein, a piezoelectric photoelectronics effect process is introduced: after the BLFO/ZnO heterojunction device calls the ferroelectricity of the BLFO, a thin cover glass is placed above the BLFO/ZnO heterojunction device, the compressive stress of a piezoelectric motor is applied to the cover glass, the cover glass enables the stress to be uniformly applied to the upper portion of the BLFO/ZnO heterojunction device, and then the piezoelectric motor applies nanoscale displacement to enable the BLFO/ZnO heterojunction device to receive the compressive strain and introduce the piezoelectric photoelectronic effect.
The method for preparing the BLFO film by adopting the sol-gel method comprises the following specific steps: preparing a precursor liquid of BLFO, and preparing a BLFO ferroelectric film by adopting a spin coating method, wherein the preparation method of the precursor liquid of BLFO comprises the following steps: using bismuth nitrate pentahydrate [ Bi (NO)3)3·5H2O]Iron nitrate nonahydrate [ Fe (NO)3)·9H2O]Lanthanum nitrate hexahydrate La (NO)3)3·6H2O]As a raw material, to prepare Bi at a concentration of 0.3mol/L0.85La0.15FeO3Weighing Bi (NO)3)3·5H2The mass of O is 1.36g, where Bi (NO) compensates for the loss of bismuth due to volatilization at high temperatures3)3·H2O weighing excess 10%, lanthanum nitrate hexahydrate [ La (NO)3)3·6H2O]0.1948g of ferric nitrate nonahydrate [ Fe (NO) ]was weighed3)·9H2O]1.2120g is weighed, the medicine is put into 4ml of ethylene glycol monomethyl ether, the mixture is stirred at the rotating speed of 400r/min until the medicine is completely dissolved, then 2ml of glacial acetic acid and 3ml of acetic anhydride are added as dehydrating agents, the stirring is continued until the solution is cooled to the room temperature, finally the ethylene glycol monomethyl ether is added, the volume of the solution is adjusted to 10ml, the concentration is 0.3mol/L, the stirring is continued for 12h, and the solution is placed for 24h to be completely aged.
Wherein, the process for preparing the BLFO ferroelectric film comprises the following steps: performing ultrasonic treatment on FTO conductive glass with the size of 15 x 1.6mm for 20min by using deionized water, acetone and ethanol respectively, repeating the ultrasonic treatment twice, then drying the FTO conductive glass by using a nitrogen gun and placing the FTO conductive glass into a glue homogenizing machine, dropwise adding precursor liquid by using a disposable 1ml medical injector, rotating the FTO conductive glass at 800r/min for 10s to enable the precursor liquid to be paved on a substrate, then rotating the FTO conductive glass at 4000r/min for 30s to enable the solution to reach the appropriate thickness and be uniformly paved on the substrate, quickly placing the prepared sample into a 350 ℃ tubular furnace for pre-annealing for 5min to enable organic matters to be cracked, then annealing at 550 ℃ for 20min to enable a film to be crystallized, and then taking out and. The above film-forming process was repeated 5 times.
Preparing ZnO nanowire array by preparing ZnO seed crystal layer on BLFO film by magnetron sputtering with background vacuum less than 4.7 × 10-4Pa, radio frequency sputtering power of 80W, sputtering pressure of 2.1Pa, target spacing of 50mm, argon gas and oxygen gasThe flow rate ratio (sccm) was 40:2, the substrate temperature was 500 ℃, and the sputtering time was 30 min.
Then, a hydrothermal method is used for preparing the ZnO nanowire array, 2.9875g of zinc nitrate hexahydrate [ Zn (NO) is weighed3)2·6H2O]0.7008g of hexamethylenetetramine [ (CH)2)6N4)]Respectively adding the mixture into 100ml of deionized water, stirring at the rotating speed of 400r/min for 5min to completely dissolve the medicines, then pouring the two solutions into a 200ml glass bottle for continuous stirring, adding 9ml of ammonia water to adjust the pH value of the solution, putting the ZnO side of the BLFO/ZnO sample into the solution downwards to enable the BLFO/ZnO sample to float in the solution, putting the sealed glass bottle into a thermostat at 90 ℃ for 9h, taking out the sample, washing the sample with ethanol, and drying.
Example two, analysis was performed on a BLFO/ZnO heterojunction device.
FIG. 1 is a schematic three-dimensional structure of a BLFO/ZnO heterojunction device. As shown in fig. 2, the BLFO thin film prepared by the sol-gel method in the present application has a compact surface, uniform grain size, and good flatness. Therefore, in the SEM top view of the ZnO nanowire array in fig. 3, the ZnO nanowire array is uniformly distributed, and as can be seen from the inset, the top surface of the ZnO nanowire has a hexagonal crystal structure, and the uniform thickness diameter is about 200nm, thus having a high c-axis orientation and good piezoelectric performance. As is evident from FIG. 4, the FTO conductive layer is about 380nm thick, the BLFO film is about 270nm thick, and the ZnO seed layer is about 1 μm thick. The ZnO nanowire array is uniform in length and about 6 μm. The interface of the FTO/BLFO/ZnO structure is clear and flat. The reasonable structure and mature process of the device are fully proved, and a solid foundation is laid for good photoelectric performance.
Example three, the J-V (current density-voltage) characteristics of the BLFO/ZnO heterojunction device were tested at a range of laser power densities to verify that it has a photovoltaic effect.
Fig. 6 shows a schematic diagram of the measurement of photovoltaic properties, and fig. 7 shows a schematic diagram of the measurement of photovoltaic properties, and the J-V properties of BLFO/ZnO under different illumination conditions were tested and recorded. As shown in fig. 7, the photovoltaic characteristics of the BLFO/ZnO heterojunction device gradually increased with increasing laser power density, and were measured after applying pulse biases of-10V (upper polarization) and +10V (lower polarization) for 1 second, respectively. When the heterojunction device is biased with a negative (positive) pulse on top of the ITO transparent electrode, it is defined as upward (downward) polarization. Fig. 9 clearly shows that there is a difference in photovoltaic characteristics in different polarization states.
FIG. 10 summarizes the dependence of the short circuit current and open circuit voltage of BLFO/ZnO heterojunction devices on illumination and polarization state. It can be seen that the photovoltaic characteristics of the BLFO/ZnO heterojunction devices are gradually enhanced as the laser power density is increased. And 100mw/cm2Compared with the photovoltaic characteristic under the optical power density, the open-circuit voltage and the short-circuit current under the upward polarization state are respectively improved by 4.2 percent and 11.3 percent. However, in the down-polarization state they are reduced by 24.3% and 15.6%, respectively, which is related to the opposite direction of the depolarization field of the BLFO film from the polarization state, which will affect the carrier transport behavior in the BLFO film, which is well documented as the opto-electronic properties of BLFO/ZnO heterojunction devices can be modulated by the ferroelectric properties of BLFO.
At the same time, the reproducibility of the BLFO/ZnO heterojunction was tested at 0V bias voltage by switching the 405nm laser at different laser power densities (fig. 11). The results show that the structural design of the device is reasonable, which means the high quality of the heterojunction, and lays a solid foundation for the follow-up study of the coupling influence of the piezoelectric photoelectric effect and the ferroelectric on the photovoltaic characteristic of the heterojunction.
Fig. 12 is a schematic view of a testing apparatus for applying light, a strain field, and an external electric field polarization to a BLFO/ZnO heterojunction device, and fig. 13 is a schematic view of a testing apparatus for applying light, a strain field, and an external electric field polarization to a BLFO/ZnO heterojunction device. At a wavelength of 405nm, the power density is 100mW/cm2Was tested by applying a strain of 0 to-2.3% to the device by a piezo motor (fig. 14). Under the condition of strain of 0, the open-circuit voltage of the BLFO/ZnO heterojunction reaches 0.379V, and the short-circuit current reaches 0.271mA/cm2。
It is clear that the stress applied to the BLFO/ZnO heterojunction device is consistent with the constant wavelength and optical power density of the laser sourceWith increasing variation, the open-circuit voltage and short-circuit current gradually increased, with the open-circuit voltage and short-circuit current being from 0.379V and 0.271mA/cm under 0 strain2Increased to 0.397V and 0.370mA/cm at-2.3% compressive strain2. Tests show that the short-circuit current improvement effect is remarkable because the piezoelectric potential of the ZnO nanowire changes an energy band structure near a heterojunction junction region, the transport behavior of a current carrier is further regulated and controlled, the transport behavior of the current carrier directly influences the short-circuit current of the device, and the photoelectric performance of the BLFO/ZnO device is successfully enhanced through the piezoelectric photoelectron effect.
Example five, the ferroelectric polarization of BLFO was used to further enhance the photoelectric properties of BLFO/ZnO heterojunction devices based on piezoelectric optoelectronics (fig. 15). Considering that the ferroelectric photovoltaic effect of the BLFO thin film is that a depolarization field plays a role, we try to increase the test condition of external electric field polarization on the basis of the original test condition of the piezoelectric photoelectronic effect to enhance the ferroelectric polarization in the BLFO thin film, thereby enhancing the depolarization field, and further enhancing the photoelectric performance of the BLFO/ZnO device on the basis of the piezoelectric photoelectronic effect. Therefore, we applied a +10V pulse voltage of 1s to the BLFO side while the BLFO/ZnO device is under-2.3% compressive strain, so that the internal ferroelectric polarization is enhanced, and a larger E is generateddpAnd the direction is the same as the built-in electric field direction inside the junction region. Thus, the driving force of carriers on the BLFO film is increased compared to BLFO/ZnO devices that are not polarized by an external electric field.
As shown in FIG. 16, by applying strain, the open-circuit voltage and short-circuit current were varied from 0.379V and 0.271mA/cm at zero strain2Increased to 0.397V and 0.370mA/cm at-2.3% compressive strain2About 4.8% and 36.4% respectively, while maintaining a pressure strain of-2.3%, and after applying a forward electric field polarization, the open-circuit voltage and the short-circuit current were further increased to 0.411V and 0.419mA/cm2Compared with the test result under 0 strain, the improvement is about 8.4 percent and 54.6 percent, and the improvement effect is obvious. To verify the carrier transport effect of the depolarization field, we also applied a reversed external field polarization, an open-circuit voltage and a short-circuit currentRespectively reduced to 0.385V and 0.328mA/cm2. And figure 16 shows that the device has good repeatability and uniformity under different compressive strains.
TABLE 1 output Performance for different test conditions
To further study the relationship between piezoelectric-photoelectric effect and ferroelectricity, we compared the V of BLFO/ZnO heterojunction devices under different test conditionsOCAnd Jsc, and the tunability for the different test conditions are listed in table 1. Table 1 shows that the modulation of the photovoltaic characteristics in the polarization state is smaller than that in the strain compression state, which is caused by the electric field formed by the piezoelectric charges being larger than the depolarization field. In addition, the modulation of the piezoelectric photoelectric effect and ferroelectric coupling is higher than that of any test condition, which indicates that the piezoelectric photoelectric effect and the ferroelectric are mutually enhanced, rather than increasing the photoelectric performance of the heterojunction alone.
Example six, an on-off test was conducted in three different states, BLFO/ZnO heterojunction device compressive strain, and BLFO/ZnO heterojunction compressive strain and forward polarization (fig. 18). Through tests, the photoelectric property of the BLFO/ZnO heterojunction device is effectively improved by applying strain and positive external electric field polarization, and by contrast, tau r and tau f are obviously shortened, wherein tau r is shortened by 59% and tau f is shortened by 31%. And the fatigue test in fig. 19 shows that the device has good fatigue resistance based on piezoelectric optoelectronics effect and ferroelectric coupling.
In conclusion, the BLFO/ZnO heterojunction device is prepared by adopting a sol-gel method and a hydrothermal method, the influence of piezoelectric optoelectronics effect and ferroelectric effect on the photovoltaic characteristics of the BLFO/ZnO heterojunction device is researched, the carrier transport behavior is modulated by utilizing the piezoelectric optoelectronics effect, the open-circuit voltage and the short-circuit current of the BLFO/ZnO heterojunction are obviously improved, meanwhile, external electric field polarization is introduced on the basis of compressive strain, the piezoelectric optoelectronics effect and the ferroelectricity are called, and the total driving force of a heterojunction energy band structure and carriers is modulated, so that the photoelectric performance of the heterojunction is further improved.
The above description is only for the preferred embodiment of the present invention, but the scope of the present invention is not limited thereto, and any person skilled in the art should be able to cover the technical scope of the present invention by equivalent replacement or change according to the technical solution and the inventive concept of the present invention within the technical scope of the present invention.
Claims (9)
1. A method for improving photoelectric performance of a BLFO/ZnO heterojunction by utilizing ferroelectricity and piezoelectric photoelectronic effect is characterized in that a BLFO/ZnO heterojunction device is applied with pulse bias voltage to call the ferroelectricity of the BLFO, and after the BLFO/ZnO heterojunction device calls the ferroelectricity of the BLFO, the BLFO/ZnO heterojunction device is applied with compressive strain to introduce the piezoelectric photoelectronic effect, so as to achieve the purpose of calling the ferroelectricity and the piezoelectric photoelectronic effect simultaneously, so as to enhance the total driving force of current carriers and test the photoelectric performance of the BLFO/ZnO heterojunction, wherein the BLFO/ZnO heterojunction device is formed by adopting a BLFO ferroelectric film and a ZnO nanowire array, an upper electrode of the BLFO/ZnO heterojunction device is an ITO electrode prepared by magnetron sputtering, the BLFO/ZnO heterojunction device is wiped to remove ZnO by utilizing hydrochloric acid, and the BLFO is wiped on the BLFO/ZnO heterojunction device by utilizing hydrofluoric acid to remove the BLFO, the exposed FTO is used as a lower electrode, and silver paste and a copper lead are used for leading out the electrode.
2. The method for improving the photoelectric property of the BLFO/ZnO heterojunction as claimed in claim 1, wherein the BLFO ferroelectric process is called as follows: and (3) connecting the upper electrode ITO of the BLFO/ZnO heterojunction device through a positive terminal of a keithley2400 digital source meter, connecting a negative terminal of the BLFO/ZnO heterojunction device with a lower electrode FTO of the BLFO/ZnO heterojunction device, generating a voltage of +10V lasting for 1 second and a voltage of-10V lasting for 1 second by using the keithley2400 digital source meter, and polarizing the BLFO/ZnO heterojunction device to call the ferroelectricity of the BLFO.
3. The method for improving the photoelectric property of the BLFO/ZnO heterojunction by utilizing the ferroelectric and piezoelectric optoelectronic effects as claimed in claim 2, is characterized in that the piezoelectric optoelectronic effect process is introduced: after the BLFO/ZnO heterojunction device calls the ferroelectricity of the BLFO, a thin cover glass is placed above the BLFO/ZnO heterojunction device, the compressive stress of a piezoelectric motor is applied to the cover glass, the cover glass enables the stress to be uniformly applied to the upper portion of the BLFO/ZnO heterojunction device, and then the piezoelectric motor applies nanoscale displacement to enable the BLFO/ZnO heterojunction device to receive the compressive strain and introduce the piezoelectric photoelectronic effect.
4. The method of claim 3 for improving the optoelectronic performance of a BLFO/ZnO heterojunction using the ferroelectric and piezoelectric optoelectronic effects as described in claim 3 wherein the open circuit voltage and short circuit current are varied from 0.379V and 0.271mA/cm at zero strain by straining the BLFO/ZnO heterojunction device2Increased to 0.397V and 0.370mA/cm at-2.3% compressive strain2Respectively increased by 4.8% and 36.4%, and the open-circuit voltage and short-circuit current are increased to 0.411V and 0.419mA/cm after applying forward electric field polarization while maintaining-2.3% of voltage strain2Compared with the test result under 0 strain, the strain is improved by 8.4 percent and 54.6 percent.
5. The method for improving the photoelectric property of the BLFO/ZnO heterojunction by utilizing the ferroelectric and piezoelectric photoelectronic effects as claimed in claim 1, is characterized in that the BLFO film is prepared by a sol-gel method, and the specific steps are as follows: the precursor liquid of the BLFO is prepared, and the BLFO ferroelectric film is prepared by adopting a spin coating method.
6. The method for improving the photoelectric property of the BLFO/ZnO heterojunction as claimed in claim 5, wherein the method for preparing the precursor liquid of the BLFO comprises the following steps: using bismuth nitrate pentahydrate [ Bi (NO)3)3·5H2O]Iron nitrate nonahydrate [ Fe (NO)3)·9H2O]Lanthanum nitrate hexahydrate La (NO)3)3·6H2O]As a raw material, bismuth nitrate pentahydrate [ Bi (NO) was weighed3)3·5H2O]Has a mass of 1.36g, lanthanum nitrate hexahydrate [ La (NO)3)3·6H2O]0.1948g of ferric nitrate nonahydrate [ Fe (NO) ]was weighed3)·9H2O]1.2120g is weighed, the medicine is put into 4ml of ethylene glycol monomethyl ether, the mixture is stirred at the rotating speed of 400r/min until the medicine is completely dissolved, then 2ml of glacial acetic acid and 3ml of acetic anhydride are added as dehydrating agents, the stirring is continued until the solution is cooled to the room temperature, finally the ethylene glycol monomethyl ether is added, the volume of the solution is adjusted to 10ml, the concentration is 0.3mol/L, the stirring is continued for 12h, and the solution is placed for 24h to be completely aged.
7. The method for improving the photoelectric property of the BLFO/ZnO heterojunction as claimed in claim 6, wherein the BLFO ferroelectric thin film is prepared by the following steps: performing ultrasonic treatment on FTO conductive glass with the size of 15 x 1.6mm for 20min by using deionized water, acetone and ethanol respectively, repeating the ultrasonic treatment twice, then drying the FTO conductive glass by using a nitrogen gun and placing the FTO conductive glass into a glue homogenizing machine, dropwise adding precursor liquid by using a disposable 1ml medical injector, rotating the FTO conductive glass at 800r/min for 10s to enable the precursor liquid to be paved on a substrate, then rotating the FTO conductive glass at 4000r/min for 30s to enable the solution to reach the appropriate thickness and be uniformly paved on the substrate, quickly placing the prepared sample into a 350 ℃ tubular furnace for pre-annealing for 5min to enable organic matters to be cracked, then annealing at 550 ℃ for 20min to enable a film to be crystallized, and then taking out and.
8. The method for improving the photoelectric property of the BLFO/ZnO heterojunction as claimed in claim 7, wherein the method comprises the following steps: firstly, a ZnO seed crystal layer is prepared on a BLFO film by magnetron sputtering, and then a ZnO nanowire array is prepared by a hydrothermal method.
9. The method for improving the photoelectric property of the BLFO/ZnO heterojunction as claimed in claim 8, wherein the process for preparing the ZnO nanowire array by the hydrothermal method comprises the following steps: 2.9875g of zinc nitrate hexahydrate [ Zn (NO) was weighed out3)2·6H2O]0.7008g of hexamethylenetetramine [ (CH)2)6N4)]Respectively added into 100ml of deionized water and rotated at 400r/minStirring rapidly for 5min to completely dissolve the medicine, pouring the two solutions into a 200ml glass bottle, stirring continuously, adding 9ml ammonia water to adjust the pH value of the solution, placing the BLFO/ZnO sample into the solution with the ZnO side facing downwards to float in the solution, placing the sealed glass bottle into a thermostat at 90 ℃ for 9h, taking out the sample, washing the sample with ethanol, and drying.
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