CN113921719A - Silicon-based organic-inorganic perovskite heterojunction photoelectric detector and preparation method thereof - Google Patents
Silicon-based organic-inorganic perovskite heterojunction photoelectric detector and preparation method thereof Download PDFInfo
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- 238000002360 preparation method Methods 0.000 title claims abstract description 8
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 title claims abstract description 7
- 229910052710 silicon Inorganic materials 0.000 title claims abstract description 7
- 239000010703 silicon Substances 0.000 title claims abstract description 7
- 239000000758 substrate Substances 0.000 claims abstract description 34
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 20
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 18
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 claims description 16
- 238000004528 spin coating Methods 0.000 claims description 16
- 239000000243 solution Substances 0.000 claims description 14
- 239000013078 crystal Substances 0.000 claims description 12
- 238000004544 sputter deposition Methods 0.000 claims description 11
- 229910052760 oxygen Inorganic materials 0.000 claims description 9
- 239000002243 precursor Substances 0.000 claims description 9
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 8
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 8
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 8
- 239000001301 oxygen Substances 0.000 claims description 8
- 238000001755 magnetron sputter deposition Methods 0.000 claims description 7
- 238000000034 method Methods 0.000 claims description 7
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 claims description 6
- 239000012296 anti-solvent Substances 0.000 claims description 6
- 229910052738 indium Inorganic materials 0.000 claims description 6
- APFVFJFRJDLVQX-UHFFFAOYSA-N indium atom Chemical compound [In] APFVFJFRJDLVQX-UHFFFAOYSA-N 0.000 claims description 6
- 238000004519 manufacturing process Methods 0.000 claims description 6
- 238000003825 pressing Methods 0.000 claims description 6
- 230000031700 light absorption Effects 0.000 claims description 5
- 238000000137 annealing Methods 0.000 claims description 4
- 239000008367 deionised water Substances 0.000 claims description 4
- 229910021641 deionized water Inorganic materials 0.000 claims description 4
- 238000010438 heat treatment Methods 0.000 claims description 4
- 238000009832 plasma treatment Methods 0.000 claims description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 4
- 229910052786 argon Inorganic materials 0.000 claims description 3
- 238000001035 drying Methods 0.000 claims description 2
- 239000011259 mixed solution Substances 0.000 claims description 2
- 239000013077 target material Substances 0.000 claims description 2
- 238000004506 ultrasonic cleaning Methods 0.000 claims description 2
- 230000000694 effects Effects 0.000 abstract description 2
- 239000010408 film Substances 0.000 description 17
- 239000010409 thin film Substances 0.000 description 10
- QWVSXPISPLPZQU-UHFFFAOYSA-N bromomethanamine Chemical compound NCBr QWVSXPISPLPZQU-UHFFFAOYSA-N 0.000 description 4
- 238000010521 absorption reaction Methods 0.000 description 3
- 238000004140 cleaning Methods 0.000 description 3
- 230000000630 rising effect Effects 0.000 description 3
- 238000012360 testing method Methods 0.000 description 3
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- 229910052681 coesite Inorganic materials 0.000 description 2
- 229910052906 cristobalite Inorganic materials 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- ZASWJUOMEGBQCQ-UHFFFAOYSA-L dibromolead Chemical compound Br[Pb]Br ZASWJUOMEGBQCQ-UHFFFAOYSA-L 0.000 description 2
- 230000005684 electric field Effects 0.000 description 2
- 238000002474 experimental method Methods 0.000 description 2
- -1 halogen ions Chemical class 0.000 description 2
- 230000001678 irradiating effect Effects 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 238000012545 processing Methods 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- 239000004065 semiconductor Substances 0.000 description 2
- 239000000377 silicon dioxide Substances 0.000 description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- 239000002904 solvent Substances 0.000 description 2
- 229910052682 stishovite Inorganic materials 0.000 description 2
- 229910052905 tridymite Inorganic materials 0.000 description 2
- 230000005641 tunneling Effects 0.000 description 2
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 239000004020 conductor Substances 0.000 description 1
- 230000003247 decreasing effect Effects 0.000 description 1
- 238000001514 detection method Methods 0.000 description 1
- 229910052736 halogen Inorganic materials 0.000 description 1
- 238000005286 illumination Methods 0.000 description 1
- 230000007774 longterm Effects 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 230000003287 optical effect Effects 0.000 description 1
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- H10K30/10—Organic devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation comprising heterojunctions between organic semiconductors and inorganic semiconductors
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- H10K30/81—Electrodes
- H10K30/82—Transparent electrodes, e.g. indium tin oxide [ITO] electrodes
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Abstract
The invention provides a silicon-based organic-inorganic perovskite heterojunction photoelectric detector and a preparation method thereof, wherein the photoelectric detector sequentially comprises a bottom electrode layer, a substrate and perovskite MAPbBr from bottom to top3A light absorbing layer, a transparent conductive layer, and a top electrode layer. By adding the ITO transparent conductive layer, the invention greatly enhances the response signal, greatly shortens the response time and greatly improves the stability of the device. Simultaneously creatively proposes to change perovskite MAPbBr3The device performance is improved by the thickness of the film, and a good effect is achieved.
Description
Technical Field
The invention relates to the technical field of photoelectric detectors, in particular to a silicon-based organic-inorganic perovskite heterojunction photoelectric detector and a preparation method thereof.
Background
Under the action of illumination, after electrons in a valence band of a semiconductor material absorb photon energy, the forbidden band width of the semiconductor is overcome and the electrons are transited to a conduction band to generate electron-hole pairs, and the holes and the electrons respectively move to two ends of a heterojunction to generate current under the action of an internal electric field, so that an optical signal is converted into an electric signal.
Perovskite-based photodetectors have many unique advantages: for example, (1) the perovskite is a direct band gap structure and has strong absorption in both ultraviolet and visible light ranges; (2) the band gap of the perovskite can be adjusted by doping different halogen ions; (3) the perovskite material has high carrier mobility and long service life, so that the detector has high collection efficiency. However, perovskite-based photodetectors also have a significant drawback in that perovskite polycrystalline thin films are decomposed very rapidly under air conditions. This phenomenon greatly limits the application of such detectors.
Disclosure of Invention
The invention aims to provide a silicon-based organic-inorganic perovskite heterojunction photoelectric detector and a preparation method thereof, and aims to solve the problems that the conventional perovskite polycrystalline film is extremely fast to decompose under the air condition and is difficult to popularize and apply.
The technical scheme of the invention is as follows: a silicon-based organic-inorganic perovskite heterojunction photoelectric detector comprises a bottom electrode layer, a substrate and perovskite MAPBBr from bottom to top in sequence3A light absorbing layer, a transparent conductive layer, and a top electrode layer.
The substrate is a Si single crystal substrate, the transparent conducting layer is an ITO conducting layer, and the bottom electrode layer and the top electrode layer are indium layers.
The perovskite MAPbBr3The thickness of the light absorption layer is 85-590 nm, and the thickness of the transparent conducting layer is 90-110 nm.
The bottom electrode layer and the top electrode layer are both round or square in shape, and the diameter or side length of the bottom electrode layer and the top electrode layer is not more than 2 mm; the thickness of the bottom electrode layer and the top electrode layer is 0.1-0.2 mm.
The preparation method of the photoelectric detector comprises the following steps:
(a) carrying out ultrasonic cleaning on the substrate by using acetone, ethanol and deionized water in sequence, and drying for later use;
(b) reacting PbBr2And CH3NH3Br is mixed and dissolved in the mixed solution of N, N-dimethylformamide and dimethyl sulfoxide according to the molar ratio of 1:1, and the prepared solution is magnetically stirred uniformly at room temperature to obtain a perovskite precursor solution with the concentration of 0.4-1.5 mol/L;
(c) the perovskite precursor solution is dripped on the surface of a substrate by adopting a spin coating method, and toluene is taken as an anti-solvent to be dripped on the surface of a film during spin coating to form uniform and compact CH3NH3PbBr3Standing the film at room temperature after the spin coating is finished, and then placing the film on a heating table preheated to 85-95 ℃ for annealing for 5-15 min to obtain perovskite MAPBBr with the thickness of 85-590 nm3A light absorbing layer;
(d) placing the sample prepared in the step (c) in a magnetron sputtering cavity, and vacuumizing; then argon is introduced to maintain the pressure in the cavity at 0.3-0.5 Pa; then carrying out magnetron sputtering on the transparent conducting layer by taking ITO as a target material, wherein the sputtering power is 35-45W, and obtaining the transparent conducting layer with the thickness of 90-110 nm;
(e) and respectively manufacturing a bottom electrode layer and a top electrode layer on the back surface of the substrate and the surface of the transparent conducting layer by adopting an indium pressing method to obtain the photoelectric detector.
The substrate is an n-type Si single crystal substrate, the substrate is cleaned, dried and then placed in an oxygen plasma cleaning instrument, the vacuum is pumped to below 0 Pa, and O is introduced2Adjusting the pressure of the air inlet valve to be kept at 15-25 Pa, and keeping oxygen plasma treatment for 40-80 min after glow starting.
The volume ratio of the N, N-dimethylformamide to the dimethyl sulfoxide is 3-5: 1.
The spin coating is divided into two stages of low speed and high speed, wherein the low speed is 1000 r/min, the duration time is 6s, the high speed is 4000 r/min, and the duration time is 60 s; at the 26 th s from the start of spin coating, 50-70. mu.L of toluene was quickly added dropwise to the film surface as an anti-solvent.
During magnetron sputtering, pre-sputtering is carried out for 3-8 min, then the substrate baffle is removed, and formal sputtering is started for 10-25 min.
The bottom electrode layer and the top electrode layer are both round or square in shape, and the diameter or side length of the bottom electrode layer and the top electrode layer is not more than 2 mm; the thickness of the bottom electrode layer and the top electrode layer is 0.1-0.2 mm.
The photoelectric detector can realize the effects of fast response of a wide wave band, ultrahigh signal and high stability. Has the advantages that:
1. the invention utilizes ITO transparent conductive material to unexpectedly make the photoelectric detector have the characteristics of ultrahigh signal, ultrafast response time and high stability. After the ITO transparent conducting layer is added, the responsivity of the device is improved by nearly 350 times compared with that of the device without the ITO transparent conducting layer, the rising time is shortened by 16.7 times, the falling time is shortened by 2 times, and the photocurrent is only reduced by 27 percent after 15 days in an environment with the humidity of about 40 percent and the temperature of about 25 ℃.
2. Perovskite MAPbBr in the invention3And the combination with Si forms a pn junction, so that the detection range is expanded from 400 nm to 1100 nm.
3. The photoelectric detector has high responsivity and high detectivity.
4. Perovskite MAPbBr3The setting of the layer thickness is crucial, and the perovskite MAPbBr is creatively adjusted3Layer thickness, at 215 nm, compared to 85 nm and 590 nm thick perovskite MAPBBr3Response signals of the layers are respectively improved by 2.1 times and 14.3 times, ultrahigh signals are obtained, and response is better.
5. The photoresponse film layer structure of the invention comprises a Si single crystal substrate and perovskite MAPbBr in sequence3Layer, ITO layer. Perovskite MAPbBr3And Si single crystal is a light absorption layer, and the incident light is basically absorbed to generate electron-hole pairs; due to perovskite MAPbBr3Energy level matching with Si interface to form a built-in electric field, so that the light-excited electron-hole pairs are separated, the electron moves towards the Si single crystal direction, and the hole moves towards the ITO layer; the ITO is a conductive layer, can allow incident light to penetrate without absorption, has good conductive property, and collects holes separated by tunneling. The arrangement relation of each layer is determined through creative research on each structural layer, and the performance of the photoelectric detector is improved by combining the thickness of each layer.
6. Subjecting perovskite MAPbBr3The layer thickness is set to 215 nm, which can absorb almost all the incident light intensity and increase the light absorption efficiency, and when the layer thickness is larger than 215 nm, not only the economic cost is increased, but also the separation and the tunneling of the photo-electron-hole pair are not facilitated, which is obtained through long-term research summary.
7. The highest responsivity of the invention reaches 0.87A/W, the measurable wavelength range is 400-1100 nm, the rising time reaches 129 ms, and the falling time reaches 130 ms.
Drawings
FIG. 1 is a schematic diagram of the experiment of example 1.
FIG. 2 is a schematic diagram of the experiment of example 2.
FIG. 3 is a plot of responsivity versus wavelength at-1V bias for the perovskite photodetectors obtained in examples 1 and 2.
FIG. 4 is a graph showing response time test of perovskite photodetectors obtained in examples 1 and 2 under a bias of-1V.
FIG. 5 is a graph showing the time stability of the perovskite photodetectors obtained in examples 1 and 2 under a bias of-1V.
FIG. 6 is a graph showing the responsivity trend of the perovskite thin film photodetector obtained in example 3 with different thicknesses as a function of the thickness of the perovskite thin film under a bias voltage of-1V.
In the figure, 1, Si single crystal substrate, 2, perovskite MAPbBr3Light absorption layer, 3, ITO transparent conducting layer, 4, bottom electrode, 5, top electrode, 6, ammeter, 7, laser.
Detailed Description
The present invention is further illustrated by the following examples in which the procedures and methods not described in detail are conventional and well known in the art, and the starting materials or reagents used in the examples are commercially available, unless otherwise specified, and are commercially available.
Example 1
a. The n-Si single crystal substrate with the thickness of 500 mu m is sequentially treated by acetone, ethanol and deionized water for 20 min.
b. Placing the clean and dry substrate with the front side facing upwards in an oxygen plasma cleaning instrument, vacuumizing to below 0 Pa, and introducing O2Adjusting air inlet valve to maintain pressure at 20 Pa, and maintaining oxygen plasma treatment for 60 min after glow starting to oxidize surface naturally to form SiO2And (3) a layer.
c. 146.8 mg of lead bromide (PbBr)2) With 44.76 mg of bromomethylamine (CH)3NH3Br) was dissolved in a mixture of 800. mu. L N, N-Dimethylformamide (DMF) and 200. mu.L of Dimethylsulfoxide (DMSO) at a molar ratio of 1:1 (solvent volume ratio of 4: 1). The prepared solution is placed on a magnetic stirrer to be stirred for more than 8 hours at room temperatureFully dissolving to obtain the perovskite precursor solution with the concentration of 0.4 mol/L.
d.Si substrate put full of N2The glove box is fixed on a sucker of a spin coater, 50 mu L of perovskite precursor solution is slowly dripped on the surface of a Si substrate, and the spin coating is divided into two stages of low speed and high speed, wherein the low speed is 1000 r/min, the duration time is 6s, the high speed is 4000 r/min, and the duration time is 60 s. At the 26 th s from the beginning of spin coating, 60 μ L of toluene was taken as an anti-solvent and quickly dropped on the surface of the film to form more uniform and dense CH3NH3PbBr3A film. Standing at room temperature for 10 min after spin coating, and annealing on a heating table preheated to 90 deg.C for 10 min to obtain 85 nm thick perovskite MAPBBr3A polycrystalline thin film.
e. On the back of Si single crystal substrate and perovskite MAPbBr3And pressing 2 In electrodes vertically on two sides of the upper surface of the light absorption layer, namely manufacturing a circular top electrode and a circular bottom electrode with the diameter of 1 mm and the thickness of 0.15 mm by adopting an indium pressing method to obtain the perovskite photoelectric detector. And leading the bottom electrode and the top electrode out by using a lead to be connected into an ammeter.
And turning on a power supply, wherein the voltage is-1V, the bottom electrode is connected with the anode, and the top electrode is connected with the cathode. A focusing point light source is irradiated on the surface of the thin film photoresponse layer, 532nm laser spots are irradiated near the top electrode, the change of photocurrent is recorded by an ammeter, the laser wavelength is changed, and the responsivity of the detector is changed, as shown in figure 3.
A focusing point light source is irradiated on the surface of the thin film photoresponse layer, 532nm laser light spots are irradiated near the top electrode, the interval of a baffle switch is 5 s, the change of photocurrent is recorded by an ammeter, and data processing and analysis are carried out to obtain the response time of the detector, as shown in figure 4. The photocurrent time intervals were measured at 25 c and 40% humidity for 0 h, 24 h and 48 h, and the stability of the detector was recorded, as shown in fig. 5.
Example 2
a. The n-Si single crystal substrate with the thickness of 500 mu m is sequentially treated by acetone, ethanol and deionized water for 20 min.
b. Placing the clean and dry substrate with right side up in oxygen plasmaVacuumizing to below 0 Pa in daughter cleaning instrument, and introducing O2Adjusting air inlet valve to maintain pressure at 20 Pa, and maintaining oxygen plasma treatment for 60 min after glow starting to oxidize surface naturally to form SiO2And (3) a layer.
c. 146.8 mg of lead bromide (PbBr)2) With 44.76 mg of bromomethylamine (CH)3NH3Br) was dissolved in a mixture of 800. mu. L N, N-Dimethylformamide (DMF) and 200. mu.L of Dimethylsulfoxide (DMSO) at a molar ratio of 1:1 (solvent volume ratio of 4: 1). And (3) placing the prepared solution on a magnetic stirrer, and stirring for more than 8 hours at room temperature to fully dissolve the solution to obtain the perovskite precursor solution with the concentration of 0.4 mol/L.
d.Si substrate put full of N2The glove box is fixed on a sucker of a spin coater, 50 mu L of perovskite precursor solution is slowly dripped on the surface of a Si substrate, and the spin coating is divided into two stages of low speed and high speed, wherein the low speed is 1000 r/min, the duration time is 6s, the high speed is 4000 r/min, and the duration time is 60 s. At the 26 th s from the beginning of spin coating, 60 μ L of toluene was taken as an anti-solvent and quickly dropped on the surface of the film to form more uniform and dense CH3NH3PbBr3A film. Standing at room temperature for 10 min after spin coating, and annealing on a heating table preheated to 90 deg.C for 10 min to obtain 85 nm thick perovskite MAPBBr3A polycrystalline thin film.
e. After a sample is sent into a magnetron sputtering chamber, a mechanical pump is firstly used for vacuumizing the chamber, when the vacuum degree reaches below 10 Pa, the molecular pump is used for vacuumizing, and the vacuum degree in the sputtering chamber reaches 1 multiplied by 10-5 Pa. Argon is filled into the sputtering chamber at a certain flow rate through the air inlet valve, the pressure in the sputtering chamber is maintained at 0.4 Pa by adjusting the gate valve of the molecular pump, and the sputtering power is adjusted to be 40W. After the growth condition of the film is adjusted, the film is pre-sputtered for five to six minutes to ensure that the glow in the chamber is stable, the film is deposited at a certain speed, and the obtained film is compact and uniform. And after the glow is stable, removing the substrate baffle, starting formal sputtering, and timing for 15 min to obtain the ITO conductive layer with the thickness of 100 nm. Closing the baffle; after the growth is finished, the vacuum-pumping system is closed, the gate valve and the electromagnetic valve are closed, and nitrogen is filled inWhen the pressure in the cavity is atmospheric pressure due to the air, the cavity door is opened to take out the sample.
f. And pressing 2 In electrodes vertically on the back surface of the Si single crystal substrate and two sides of the upper surface of the ITO conductive layer, namely manufacturing a circular top electrode and a circular bottom electrode with the diameter of 1 mm and the thickness of 0.15 mm by adopting an indium pressing method to obtain the perovskite photoelectric detector. And leading the bottom electrode and the top electrode out by using a lead to be connected into an ammeter.
And turning on a power supply, wherein the voltage is-1V, the bottom electrode is connected with the anode, and the top electrode is connected with the cathode. A focusing point light source is irradiated on the surface of the thin film photoresponse layer, 532nm laser spots are irradiated near the top electrode, the change of photocurrent is recorded by an ammeter, the laser wavelength is changed, and the responsivity of the detector is changed, as shown in figure 3.
A focusing point light source is irradiated on the surface of the thin film photoresponse layer, 532nm laser light spots are irradiated near the top electrode, the interval of a baffle switch is 5 s, the change of photocurrent is recorded by an ammeter, and data processing and analysis are carried out to obtain the response time of the detector, as shown in figure 4. The stability of the detector was recorded at photocurrent time intervals of 0 h, 24 h, 48 h, 72 h, 96 h, 120 h, 168 h, 216 h, 264 h and 360 h at a temperature of 25 ℃ and a humidity of 40%, as shown in fig. 5.
As can be seen from FIG. 3, due to the introduction of the ITO transparent conductive layer, 6.36mW/cm at a wavelength of 532nm2Under the irradiation of the power density laser, the responsivity of the photoelectric detector is improved from 0.394mA/W to 0.135A/W.
As can be seen from FIG. 4, due to the introduction of the ITO transparent conductive layer, 6.36mW/cm at a wavelength of 532nm2Under the irradiation of the power density laser, the rising time of the photoelectric detector is shortened from 2176 ms to 130 ms, and the falling time is shortened from 257 ms to 125 ms.
As can be seen from FIG. 5, due to the introduction of the ITO transparent conductive layer, 6.36mW/cm at a wavelength of 532nm2After about 15 days of testing under the irradiation of the power density laser, the photocurrent was reduced by only 27% compared with the original device. And the device without the ITO transparent conducting layer is tested for about 15 days, and the photocurrent is reduced by 93 percent compared with the original device.
Example 3
A photodetector was fabricated in accordance with the procedure of example 2, except that the perovskite precursor solutions had concentrations of 0.4 mol/L, 0.6 mol/L, 0.8 mol/L, 1 mol/L, 1.2 mol/L and 1.5 mol/L, respectively, with respect to the perovskite MAPBBr3The thicknesses of the polycrystalline thin films are respectively 85 nm, 160 nm, 215 nm, 380 nm, 440 nm and 590 nm, the numbers are respectively 1, 2, 3, 4, 5 and 6, and the thickness of the ITO transparent conducting layer is 100 nm.
Irradiating a focusing point light source on the surface of the ITO transparent conducting layer, irradiating a 671 nm laser spot near the upper electrode, recording the change of photocurrent by using an ammeter, changing a test sample, changing the responsivity of a detector, and carrying out MAPbBr on perovskites with different thicknesses3Polycrystalline samples were tested as shown in FIG. 6.
As can be seen from FIG. 6, the responsivity of the detector is a function of the perovskite MAPbBr3The thickness of the polycrystalline film shows the trend of increasing firstly and then decreasing, and the thickness of the polycrystalline film is in the perovskite MAPbBr3When the thickness of the polycrystalline film is 215 nm, the photoelectric detector has the best performance, and the responsivity is 0.87A/W.
Claims (10)
1. The silicon-based organic-inorganic perovskite heterojunction photoelectric detector is characterized by comprising a bottom electrode layer, a substrate and perovskite MAPbBr from bottom to top in sequence3A light absorbing layer, a transparent conductive layer, and a top electrode layer.
2. The photodetector of claim 1, wherein the substrate is a Si single crystal substrate, the transparent conductive layer is an ITO conductive layer, and the bottom and top electrode layers are indium layers.
3. The photodetector of claim 1, wherein the perovskite MAPbBr3The thickness of the light absorption layer is 85-590 nm, and the thickness of the transparent conducting layer is 90-110 nm.
4. The photodetector of claim 1, wherein the bottom electrode layer and the top electrode layer are both circular or square in shape, and have a diameter or side length of not more than 2 mm; the thickness of the bottom electrode layer and the top electrode layer is 0.1-0.2 mm.
5. A method of manufacturing a photodetector as claimed in any one of claims 1 to 4, characterized by the steps of:
(a) carrying out ultrasonic cleaning on the substrate by using acetone, ethanol and deionized water in sequence, and drying for later use;
(b) reacting PbBr2And CH3NH3Br is mixed and dissolved in the mixed solution of N, N-dimethylformamide and dimethyl sulfoxide according to the molar ratio of 1:1, and the prepared solution is magnetically stirred uniformly at room temperature to obtain a perovskite precursor solution with the concentration of 0.4-1.5 mol/L;
(c) the perovskite precursor solution is dripped on the surface of a substrate by adopting a spin coating method, and toluene is taken as an anti-solvent to be dripped on the surface of a film during spin coating to form uniform and compact CH3NH3PbBr3Standing the film at room temperature after the spin coating is finished, and then placing the film on a heating table preheated to 85-95 ℃ for annealing for 5-15 min to obtain perovskite MAPBBr with the thickness of 85-590 nm3A light absorbing layer;
(d) placing the sample prepared in the step (c) in a magnetron sputtering cavity, and vacuumizing; then argon is introduced to maintain the pressure in the cavity at 0.3-0.5 Pa; then carrying out magnetron sputtering on the transparent conducting layer by taking ITO as a target material, wherein the sputtering power is 35-45W, and obtaining the transparent conducting layer with the thickness of 90-110 nm;
(e) and respectively manufacturing a bottom electrode layer and a top electrode layer on the back surface of the substrate and the surface of the transparent conducting layer by adopting an indium pressing method to obtain the photoelectric detector.
6. The method according to claim 5, wherein the substrate is an n-type Si single crystal substrate, the substrate is cleaned, dried, placed in an oxygen plasma cleaner, evacuated to a pressure of 0 Pa or less, and O is introduced2Adjusting the pressure of the air inlet valve to be kept at 15-25 Pa, and keeping oxygen plasma treatment for 40-80 min after glow starting.
7. The method according to claim 5, wherein the volume ratio of N, N-dimethylformamide to dimethylsulfoxide is 3-5: 1.
8. The preparation method according to claim 5, characterized in that the spin coating is divided into two stages of low speed and high speed, wherein the low speed is 1000 r/min, the duration is 6s, the high speed is 4000 r/min, and the duration is 60 s; at the 26 th s from the start of spin coating, 50-70. mu.L of toluene was quickly added dropwise to the film surface as an anti-solvent.
9. The preparation method of claim 5, wherein magnetron sputtering is performed by pre-sputtering for 3-8 min, removing the substrate baffle plate, and starting formal sputtering for 10-25 min.
10. The production method according to claim 5, wherein the bottom electrode layer and the top electrode layer are both circular or square in shape, and have a diameter or side length of not more than 2 mm; the thickness of the bottom electrode layer and the top electrode layer is 0.1-0.2 mm.
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