CN109585489B - Flexible photoelectric detector array and preparation method thereof - Google Patents

Flexible photoelectric detector array and preparation method thereof Download PDF

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CN109585489B
CN109585489B CN201811337468.4A CN201811337468A CN109585489B CN 109585489 B CN109585489 B CN 109585489B CN 201811337468 A CN201811337468 A CN 201811337468A CN 109585489 B CN109585489 B CN 109585489B
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CN109585489A (en
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潘曹峰
潘安练
吴文强
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Beijing Institute of Nanoenergy and Nanosystems
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Beijing Institute of Nanoenergy and Nanosystems
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Abstract

The invention discloses a flexible photoelectric detector array and a preparation method thereof, wherein the flexible photoelectric detector array comprises: a substrate; a metal circuit comprising an arrayed electrode located over a substrate; the surface hydrophobicity processing auxiliary layer is positioned on the metal circuit and is provided with a hollow area corresponding to the position of the arrayed electrode, so that the arrayed electrode is exposed; a photosensitive layer located in the hollow region of the surface hydrophobicity-treatment auxiliary layer and located on the array electrode; and an encapsulation layer on the photosensitive layer and the surface hydrophobicity-treatment auxiliary layer. The flexible photoelectric detector array has good light response performance, electrical stability and bending resistance, crosstalk does not exist among pixel points of each array unit, light response signals can be independently displayed, and the flexible photoelectric detector array can be used for real-time light tracking detection and light imaging.

Description

Flexible photoelectric detector array and preparation method thereof
Technical Field
The disclosure belongs to the technical field of optical imaging devices and nano new energy, and relates to a flexible photoelectric detector array and a preparation method thereof.
Background
With the development of the flexible optoelectronic industry, the flexible photoelectric detector is receiving more and more attention due to its application in optical communication, imaging technology, environmental monitoring, and the like. In practical applications, large-scale integrated flexible photodetector arrays can meet the increasing development requirements of emerging technologies. However, the conventional semiconductor material-based photodetector array has the problems of poor performance, incapability of being integrated on a flexible substrate and the like.
Novel perovskite materials are good candidates for assembling flexible photodetector arrays due to their outstanding optoelectronic properties. The greatest challenge in the assembly of flexible photodetector arrays based on perovskite materials is the synthesis of arrayed materials on flexible substrates using suitable methods. To date, several methods of synthesizing arrayed perovskite materials have been reported, but there are still many disadvantages: (1) some conventional synthetic methods, for example: chemical Vapor Deposition (CVD), vapor phase epitaxial growth, template methods, etc., are not suitable for the assembly of flexible devices due to the high temperatures and special substrates required; (2) the synthesis position of large-scale array materials cannot be accurately controlled, so that the assembly of devices is very difficult; (3) the process is complex, and the photoelectric characteristics of the material are inevitably influenced in the device assembling process. The above problems have all greatly limited the assembly and application of flexible photodetector arrays based on perovskite materials.
Disclosure of Invention
Technical problem to be solved
The present disclosure provides a flexible photodetector array and a method of making the same to at least partially address the above-identified problems.
(II) technical scheme
According to one aspect of the present disclosure, there is provided a flexible photodetector array comprising: a substrate; a metal circuit comprising an arrayed electrode located over a substrate; the surface hydrophobicity processing auxiliary layer is positioned on the metal circuit and is provided with a hollow area corresponding to the position of the arrayed electrode, so that the arrayed electrode is exposed; a photosensitive layer located in the hollow region of the surface hydrophobicity-treatment auxiliary layer and located on the array electrode; and an encapsulation layer on the photosensitive layer and the surface hydrophobicity-treatment auxiliary layer.
In some embodiments of the present disclosure, the metal circuit further comprises: the external positive electrodes and the external negative electrodes are correspondingly connected with each electrode in the arrayed electrodes; the external positive electrode is a common positive electrode and is connected to all the arrayed electrodes, and the external negative electrodes are independent of each other.
In some embodiments of the present disclosure, the thickness of the surface hydrophobicity-treatment auxiliary layer is between 10nm and 30nm, and/or the material of the surface hydrophobicity-treatment auxiliary layer is an insulating thin film material.
In some embodiments of the present disclosure, each array unit in the arrayed electrode has a length of 10 μm to 100 μm, and a gap between two adjacent array units is 50 μm to 300 μm.
In some embodiments of the present disclosure, the substrate is a flexible, high temperature resistant, transparent substrate; and/or the thickness of the substrate is between 50 and 200 mu m; and/or the electrodes in the arrayed electrodes are interdigital electrodes; and/or the material of the packaging layer is a transparent high molecular organic material with adhesiveness and stretchability.
In some embodiments of the present disclosure, the high temperature range of the flexible high temperature resistant substrate is: 100-300 ℃; and/or the substrate is a poly terephthalic acid plastic or polyethylene naphthalate.
In some embodiments of the present disclosure, the material of the photosensitive layer is a perovskite material, including one or more of the following materials: CH (CH)3NH3PbI3、CH3NH3PbI3-xCl or CsPbBr3A perovskite material.
According to another aspect of the present disclosure, there is provided a method of manufacturing a flexible photodetector array, the method comprising: forming a metal circuit on a substrate, the metal circuit including an arrayed electrode; depositing a surface hydrophobicity treatment auxiliary layer on the metal circuit, and carrying out hydrophobicity, patterning and hydrophilicity treatment to enable the surface hydrophobicity treatment layer to have a hollow area corresponding to the position of the arrayed electrode, so that the arrayed electrode is exposed, a hydrophilic surface is formed on the surface of the arrayed electrode, and a hydrophobic surface is formed on the surface of the surface hydrophobicity treatment auxiliary layer; forming a photosensitive layer in the hollow area of the surface hydrophobicity treatment auxiliary layer and on the surface of the arrayed electrode; and forming an encapsulation layer on the photosensitive layer and the surface hydrophobicity-treatment auxiliary layer.
In some embodiments of the present disclosure, the method of forming the photosensitive layer is: a two-step sequential deposition process, comprising: spin-coating a first precursor on the exposed surface of the arrayed electrode, wherein the solvent of the first precursor is a hydrophobic solvent, so as to obtain a first precursor array; and spin-coating a second precursor on the first precursor array, wherein the second precursor and the first precursor can jointly synthesize a perovskite material to obtain the photosensitive layer.
In some embodiments of the present disclosure, the method of hydrophobic treatment is: soaking a sample in a mixed solution of octadecyl siloxane and normal hexane for treatment; and/or the hydrophilic treatment method comprises the following steps: oxygen plasma treatment is used.
(III) advantageous effects
According to the technical scheme, the flexible photoelectric detector array and the preparation method thereof have the following beneficial effects:
forming a surface hydrophobicity treatment auxiliary layer on a metal circuit, then carrying out hydrophobicity, patterning and hydrophilic treatment on the surface hydrophobicity treatment auxiliary layer in sequence to expose an array electrode in the metal circuit, forming a hydrophilic surface on the surface of the arrayed electrode, forming a hydrophobic surface on the surface of the surface hydrophobicity treatment auxiliary layer, depositing a perovskite material on the arrayed electrode to form a photosensitive layer, wherein for the arrayed perovskite material with very harsh preparation conditions, the hydrophobicity/hydrophilic treatment provides a good growth environment for the perovskite material, the prepared perovskite film is compact and has a regular shape, the synthesis of the photosensitive layer of large-scale arrays and complex patterns is facilitated, the obtained flexible photoelectric detector array has good photoresponse performance, electrical stability and bending resistance, and no crosstalk exists among pixel points of each array unit, the optical response signals can be independently displayed, and the method can be used for real-time optical tracking detection and optical imaging.
Drawings
Fig. 1 is a schematic structural diagram of a flexible photodetector array according to an embodiment of the present disclosure.
FIG. 2 is a partial scanning electron micrograph of the flexible photodetector array shown in FIG. 1.
Fig. 3 is a flowchart illustrating a method for manufacturing a flexible photodetector array according to an embodiment of the present disclosure.
FIG. 4 illustrates the synthesis of CH by a two-step sequential deposition process according to one embodiment of the present disclosure3NH3PbI3-xClxProcess schematic for perovskite arrays.
Fig. 5 is a scanning electron microscope photograph of a perovskite array fabricated on a PET substrate surface treated for hydrophilicity/hydrophobicity by a two-step sequential deposition method according to an embodiment of the present disclosure.
Fig. 6A is an optical photograph of a large-scale perovskite array shown according to an embodiment of the present disclosure.
Fig. 6B is an optical photograph of a complex pattern of perovskite thin film shown according to an embodiment of the present disclosure.
Fig. 7 is an X-ray diffraction pattern of a synthetic perovskite material shown in accordance with an embodiment of the present disclosure.
Fig. 8 is a graph showing the current-voltage variation of a flexible photo-detector array under different intensities of light (equal illumination wavelengths) according to an embodiment of the present disclosure.
Fig. 9 is a graph of the on-off switching behavior and response time of a flexible photodetector array according to an embodiment of the present disclosure as a function of light intensity at the same voltage.
FIG. 10 is a graph showing the variation of photocurrent and responsivity of a flexible photodetector array according to an embodiment of the present disclosure as light intensity increases.
Fig. 11 is a graph showing the current-voltage variation of the flexible photo-detector array under different wavelengths of light (equal illumination intensity) according to an embodiment of the disclosure.
Fig. 12 illustrates the dark current and the current variation under illumination for a flexible photo-detector array at different bending angles according to an embodiment of the disclosure.
FIG. 13 illustrates dark current and current variations in light after different numbers of bends in a flexible photodetector array according to one embodiment of the present disclosure.
FIG. 14 illustrates the on-off switching behavior of a flexible photodetector array with varying intensity after being bent a different number of times, according to one embodiment of the present disclosure.
FIG. 15 is a schematic circuit diagram illustrating a multi-pixel point simultaneous test of a flexible photodetector array according to an embodiment of the present disclosure.
Fig. 16A shows the voltage-time variation of 10 pixels in the flexible photodetector array shown in fig. 15 under the variation of light intensity.
Fig. 16B is a voltage-time variation situation corresponding to the light intensity variation of 10 pixels (pixels other than pixels 5 and 6 are all covered) after the mask is added to the flexible photodetector array corresponding to fig. 16A.
Fig. 17 is a schematic diagram of a flexible photodetector array for real-time spot tracking according to an embodiment of the disclosure.
FIG. 18 is a schematic diagram of a flexible photodetector array for light imaging according to an embodiment of the present disclosure.
[ notation ] to show
1-a substrate;
2-metal circuitry;
21-arraying electrodes; 22-external positive electrode;
23-external negative electrode; 24-a lead;
3-surface hydrophobicity treatment auxiliary layer; 31-a hollow region;
4-a photosensitive layer; 41-perovskite arrays;
5-packaging layer.
Detailed Description
The invention provides a flexible photoelectric detector array and a preparation method thereof, wherein a patterned surface hydrophobicity treatment auxiliary layer is prepared on a metal circuit, a hydrophilic surface is formed on the surface of an array electrode of the metal circuit, a hydrophobic surface is formed on the surface of the surface hydrophobicity treatment auxiliary layer, a perovskite material is deposited on the array electrode to form a photosensitive layer, for the arrayed perovskite material with very harsh preparation conditions, the hydrophobicity/hydrophilicity treatment provides a good growth environment for the perovskite material, the prepared perovskite film is compact and has a regular shape, the synthesis of the photosensitive layer of large-scale arrays and complex patterns is facilitated, the obtained flexible photoelectric detector array has good photoresponse performance, electrical stability and bending resistance, no crosstalk exists among pixel points of each array unit, and a photoresponse signal can be independently displayed, the method can be used for real-time light tracking detection and light imaging.
For the purpose of promoting a better understanding of the objects, aspects and advantages of the present disclosure, reference is made to the following detailed description taken in conjunction with the accompanying drawings. In the present disclosure, the terms "hydrophilic/hydrophobic", "hydrophobic/hydrophilic" mean: hydrophilic and/or hydrophobic, "hydrophilic/hydrophobic treatment" means hydrophilic treatment and/or hydrophobic treatment.
In a first exemplary embodiment of the present disclosure, a flexible photodetector array is provided.
Fig. 1 is a schematic structural diagram of a flexible photodetector array according to an embodiment of the present disclosure.
Referring to fig. 1, a flexible photodetector array of the present disclosure includes: a substrate 1; a metal circuit 2 including an arrayed electrode 21 on the substrate 1; a surface hydrophobicity-treatment auxiliary layer 3 which is provided on the metal circuit 2 and has a hollow region 31 corresponding to the position of the arrayed electrode 21 so as to expose the arrayed electrode 21; a photosensitive layer 4 located in the hollow region 31 of the surface hydrophobicity-treatment auxiliary layer 3 and on the arrayed electrode 21; and an encapsulation layer 5 on the photosensitive layer 4 and the surface hydrophobicity-treatment auxiliary layer 3.
In this embodiment, the substrate 1 is a flexible high-temperature-resistant transparent substrate, and can be easily bent when an external force is applied. The material of the substrate 1 includes, but is not limited to, the following materials: poly (terephthalic) Plastic (PET) and polyethylene naphthalate (PEN).
In one example, the high temperature range of the flexible high temperature resistant substrate is: 100-300 deg.c and thickness of 50-200 microns.
FIG. 2 is a partial scanning electron micrograph of the flexible photodetector array shown in FIG. 1.
In the embodiment, the length of each array unit in the arrayed electrode 21 is between 10 μm and 100 μm, and the gap between two adjacent array units is between 50 μm and 300 μm.
Referring to fig. 1, 2 and 15, in the present embodiment, the metal circuit 2 includes: an arrayed electrode 21; a plurality of external positive electrodes 22 and external negative electrodes 23 connected to each of the arrayed electrodes 21; the external positive electrode 22 is a common positive electrode and is connected to all the arrayed electrodes, and the external negative electrodes 23 are independent from each other. In one example, each of the arrayed electrodes 21 is connected to a corresponding external positive electrode and each of the arrayed electrodes is connected to a corresponding external negative electrode by a lead 24.
In this embodiment, referring to fig. 2, the electrodes in the arrayed electrode 21 are interdigital electrodes.
The electrodes in the arrayed electrode 21 can be Ni/Au, Ni is used as an adhesion layer, the thickness range of Ni is 5nm-20nm, the thickness range of Au is 20nm-100nm, and the main function is electric conduction.
In the present embodiment, the material of the surface hydrophobicity-imparting auxiliary layer 3 is an insulating thin film material, preferably an alumina thin film (Al)2O3) And a silicon oxide film (SiO)2)。
In this embodiment, the thickness of the surface hydrophobicity-treatment auxiliary layer 3 is between 10nm and 30 nm.
In this embodiment, the photosensitive layer 4 is made of a semiconductor thin film material, and since the perovskite material has a large light absorption coefficient, an ultra-long lifetime and a diffusion length in the visible wavelength range, and can be used for assembling a high-performance photodetector array, the material of the photosensitive layer is preferably a perovskite material with excellent performance, including but not limited to one or more of the following materials: CH (CH)3NH3PbI3、CH3NH3PbI3-xCl or CsPbBr3A perovskite material.
In this embodiment, the thickness of the photosensitive layer 4 is between 500nm and 2 μm.
In this embodiment, the material of the encapsulation layer 5 is a transparent polymer organic material with adhesiveness and stretchability, and is preferably Polydimethylsiloxane (PDMS).
Each electrode in the arrayed electrodes 21 of the flexible photoelectric detector array and the photosensitive layer 4 formed by the perovskite array 41 on the electrode form a detection unit or pixel point together, each pixel point is provided with an independent negative electrode, all the pixel points are provided with a common positive electrode, namely a common positive electrode, and the pixel points are not interfered with each other, so that real-time light tracking detection and light imaging can be realized.
In this embodiment, the flexible photodetector array is prepared on the basis of not affecting the performance of the perovskite material, and it should be noted that the photosensitive layer in the flexible photodetector array of the present disclosure is not limited to the perovskite material, but is also applicable to other semiconductor thin film materials, and due to the arrangement of the surface hydrophobic treatment auxiliary layer, the photosensitive layer can be deposited on the electrode without affecting the performance of the material.
It should be noted that the shape, material, and thickness of the arrayed electrode in the metal circuit, the material, and thickness of the substrate, the surface hydrophobicity treatment auxiliary layer, the photosensitive layer, and the encapsulation layer, and the like, which are listed in this embodiment are merely examples, and do not limit the scope of the present disclosure, and those skilled in the art can also perform the adaptive setting according to actual needs.
In a second exemplary embodiment of the present disclosure, a method of fabricating a flexible photodetector array is provided.
Fig. 3 is a flowchart illustrating a method for manufacturing a flexible photodetector array according to an embodiment of the present disclosure.
Referring to fig. 3, a method for manufacturing a flexible photodetector array of the present disclosure includes:
step S31: forming a metal circuit on a substrate, the metal circuit including an arrayed electrode;
in this embodiment, the substrate 1 is a PET substrate; the metal circuit 2 comprises an array electrode 21, a plurality of external positive electrodes 22 and external negative electrodes 23, wherein each electrode in the array electrode is an interdigital electrode, the plurality of external positive electrodes 22 and the plurality of external negative electrodes 23 are correspondingly connected with each electrode in the array electrode 21, the external positive electrode 22 is a common positive electrode and is connected to all the array electrodes, and the external negative electrodes 23 are independent from each other.
In this embodiment, the metal circuit 2 is manufactured by using a photolithography technique and magnetron sputtering.
Step S32: depositing a surface hydrophobicity treatment auxiliary layer on the metal circuit, and carrying out hydrophobicity, patterning and hydrophilicity treatment to enable the surface hydrophobicity treatment layer to have a hollow area corresponding to the position of the arrayed electrode, so that the arrayed electrode is exposed, a hydrophilic surface is formed on the surface of the arrayed electrode, and a hydrophobic surface is formed on the surface of the surface hydrophobicity treatment auxiliary layer;
in step S32, performing hydrophobic, patterning, and hydrophilic treatments to make the surface hydrophobic treatment layer have a hollow area corresponding to the position of the arrayed electrode, so that the arrayed electrode is exposed, and a hydrophilic surface is formed on the surface of the arrayed electrode, and a hydrophobic surface is formed on the surface of the surface hydrophobic treatment auxiliary layer, including: carrying out hydrophobic treatment on the surface hydrophobic treatment auxiliary layer, patterning the surface hydrophobic treatment layer to enable the surface hydrophobic treatment layer to be provided with a hollow area corresponding to the position of the arrayed electrode, exposing the arrayed electrode, and carrying out hydrophilic treatment on the arrayed electrode;
in the embodiment, a magnetron sputtering mode is adopted to deposit the surface hydrophobicity treatment auxiliary layer 3 on the metal circuit, and then a sample is soaked in a mixed solution of Octadecylsiloxane (OTS) and n-hexane to perform surface hydrophobicity treatment on the surface hydrophobicity treatment auxiliary layer; depositing a photoresist mask on the surface hydrophobicity processing auxiliary layer 3 by utilizing a photoetching technology and exposing a pattern to enable the surface hydrophobicity processing layer to be provided with a hollow area corresponding to the position of the arrayed electrode, corroding the surface hydrophobicity processing auxiliary layer on the arrayed electrode by utilizing corrosive liquid to enable the arrayed electrode to be exposed, and then performing surface hydrophilicity processing by utilizing oxygen plasma.
In one example, the surface hydrophobicity-treatment auxiliary layer is Al2O3A film with a thickness of 20nm, soaking the sample in a mixed solution of OTS and n-hexane for about 20 min to form a hydrophobic surface on the surface of the auxiliary layer for surface hydrophobic treatment, and performing photolithography on Al2O3Forming a designed photoresist mask on the surface of the film to enable the surface hydrophobic treatment layer to have a hollow area corresponding to the position of the arrayed electrode, and etching the Al on the interdigital electrode by corrosive liquid2O3The film is etched off, the etching solution can be selected from saturated phosphoric acid solution, and then oxygen plasma treatment is carried outAnd (3) forming a hydrophilic surface on the interdigital electrode area finally after 2 minutes, and then removing the photoresist by using acetone.
Step S33: forming a photosensitive layer in the hollow area of the surface hydrophobicity treatment auxiliary layer and on the surface of the arrayed electrode;
in this embodiment, the method of forming the photosensitive layer includes: a two-step sequential deposition process, comprising: spin-coating a first precursor on the exposed surface of the arrayed electrode, wherein the solvent of the first precursor is a hydrophobic solvent, so as to obtain a first precursor array; and spin-coating a second precursor on the first precursor array, wherein the second precursor and the first precursor can jointly synthesize a perovskite material to obtain the photosensitive layer.
FIG. 4 illustrates the synthesis of CH by a two-step sequential deposition process according to one embodiment of the present disclosure3NH3PbI3-xClxProcess schematic for perovskite arrays.
Referring to (a), (b) and (c) of fig. 4, in one example, a method of forming a photosensitive layer is as follows:
the first step is as follows: and spin-coating the first precursor on the substrate which is subjected to surface hydrophilic/hydrophobic treatment. CH (CH)3NH3PbI3-xClxThe precursor of perovskite is lead iodide (PbI)2) And lead chloride (PbCl)2) Mixtures in Dimethylformamide (DMF) solvent. PbI after completion of spin coating2And PbCl2The array is formed in the hydrophilic region, as shown in (b) of fig. 4. Different material precursors are different and thus different solvents will be chosen. In order to obtain the desired array on the treated substrate after the spin coating is complete, the solvent of precursor one must be a hydrophobic solvent.
The second step is that: precursor II, CH for synthesizing perovskite material by spin coating3NH3PbI3-xClxPrecursor of perovskite is methyl amine iodide (CH)3NH3I) Solution, after completion of spin coating, PbI can be added2And PbCl2Array conversion to CH3NH3PbI3-xClxPerovskite array, see (c) in FIG. 4, and then washing the sample table with the solvent corresponding to precursor twoThe second precursor is made of isopropanol for cleaning redundant PbI2And PbCl2Particles; and finally, heating the sample on a drying table to improve the crystallinity of the material.
The prepared arrayed photosensitive layer was also characterized below.
Fig. 5 is a scanning electron microscope photograph of a perovskite array fabricated on a PET substrate surface treated for hydrophilicity/hydrophobicity by a two-step sequential deposition method according to an embodiment of the present disclosure. As can be seen from fig. 5, the prepared perovskite thin film in an array form is very dense and has a regular shape.
Fig. 6A is an optical photograph of a large-scale perovskite array according to an embodiment of the present disclosure, and fig. 6B is an optical photograph of a complex pattern composed of perovskite thin films according to an embodiment of the present disclosure. As can be seen from fig. 6A and 6B: the preparation method disclosed by the invention can be used for synthesizing the arrayed photosensitive layer film with large-scale arrays and complex patterns.
Fig. 7 is an X-ray diffraction pattern of a synthetic perovskite material shown in accordance with an embodiment of the present disclosure. As can be seen from fig. 7, the prepared perovskite material had a tetragonal crystal perovskite structure and had good crystallinity.
Step S34: forming an encapsulation layer on the photosensitive layer and the surface hydrophobicity-treatment auxiliary layer;
in this embodiment, the material of the encapsulation layer 5 is a transparent polymer organic material with adhesiveness and stretchability, and is preferably PDMS.
In an example, a performance test was performed on the flexible photodetector array obtained by the method for manufacturing a flexible photodetector array according to the second embodiment.
Fig. 8 is a graph showing the current-voltage variation of a flexible photo-detector array under different intensities of light (equal illumination wavelengths) according to an embodiment of the present disclosure. As can be seen from fig. 8, the current is small when there is no illumination; under illumination, the light intensity increases from 0.033, 0.46, 2.10, 4.15, 9.12, 15.1, 29.7 and 38.3 (unit: mW. cm)-2) And the current is correspondingly gradually increased.
Fig. 9 is a graph of the on-off switching behavior and response time of a flexible photodetector array according to an embodiment of the present disclosure as a function of light intensity at the same voltage. As can be seen from fig. 9, the device current is small when no light is applied; when the current of the device is increased rapidly after the light is added, the corresponding time is as follows: 0.48s, and can remain stable in this case; when the light source is turned off, the current decreases rapidly, and the recovery time is: 0.26s, and the current value when not energized can be restored.
FIG. 10 is a graph showing the variation of photocurrent and responsivity of a flexible photodetector array according to an embodiment of the present disclosure as light intensity increases. As can be seen from fig. 10, the photocurrent increases with increasing light intensity; the responsivity decreased with the increase of light intensity, and was 0.033mW cm-2The responsivity is maximum and is 9.4 multiplied by 1011Jones。
Fig. 11 is a graph showing the current-voltage variation of the flexible photo-detector array under different wavelengths of light (equal illumination intensity) according to an embodiment of the disclosure. As can be seen from fig. 11, the flexible photodetector array has a significant optical response in the visible range.
Fig. 12 illustrates the dark current and the current variation under illumination for a flexible photo-detector array at different bending angles according to an embodiment of the disclosure. As can be seen from fig. 12, at different bending angles: at 30 °, 75 °, 120 ° and 150 °, the dark current and the photocurrent of the device are substantially the same as those of the device when the device is not bent, and at a large bending angle, the dark current and the current under illumination of the device can be substantially kept unchanged, which indicates that the device has good electrical stability.
FIG. 13 illustrates dark current and current variations in light after different numbers of bends in a flexible photodetector array according to one embodiment of the present disclosure. FIG. 14 illustrates the on-off switching behavior of a flexible photodetector array with varying intensity after being bent a different number of times, according to one embodiment of the present disclosure. As can be seen from fig. 13 and 14, the dark current and the photocurrent of the device changed at different bending times in the same manner as the device without bending, and the on-off switching behavior was substantially the same, indicating that the device had excellent bending resistance.
FIG. 15 is a schematic circuit diagram illustrating a multi-pixel point simultaneous test of a flexible photodetector array according to an embodiment of the present disclosure. As shown in fig. 15, the arrayed electrodes in the flexible photodetector array and the photosensitive layer thereon form a detection unit or pixel, each pixel has an independent negative electrode, all pixels have a common positive electrode, i.e., a common positive electrode, and an external resistor is added between each external positive electrode and the external negative electrode.
Fig. 16A shows the voltage-time variation of 10 pixels in the flexible photodetector array shown in fig. 15 under the variation of light intensity. As can be seen from fig. 16A, under the illumination condition, 10 pixels of the device have approximately consistent optical responses, which indicates that the pixel performance of the device has good consistency and meets the requirements of optical imaging.
Fig. 16B is a voltage-time variation situation corresponding to the light intensity variation of 10 pixels (pixels other than pixels 5 and 6 are all covered) after the mask is added to the flexible photodetector array corresponding to fig. 16A. As can be seen from fig. 16B, the optical response signals of the pixels 5 and 6 do not affect other pixels, which indicates that there is no crosstalk between the pixels of the device, and the optical response signals can be independently displayed.
Fig. 17 is a schematic diagram of a flexible photodetector array for real-time spot tracking according to an embodiment of the disclosure. As shown in (i) of fig. 17, the position of the light spot is moved from the pixel point 1 to the pixel point 5, and when the light spot passes through a certain pixel point, the corresponding pixel point in the device generates an optical response, as shown in (ii) and (iii) of fig. 17, so that the device can realize real-time light spot tracking.
FIG. 18 is a schematic diagram of a flexible photodetector array for light imaging according to an embodiment of the present disclosure. As shown in fig. 18, when light spots are irradiated onto the device through a designed mask, the unmasked pixel points generate high voltage, the masked pixel points are still at low voltage, and a clear "H" pattern can be seen from output data, so that the device can realize light imaging.
In summary, the present disclosure provides a flexible photodetector array and a method for fabricating the same, wherein a surface hydrophobicity treatment auxiliary layer is formed on a metal circuit, and then hydrophobicity, patterning and hydrophilicity treatments are sequentially performed on the surface hydrophobicity treatment auxiliary layer to expose an array electrode in the metal circuit, form a hydrophilic surface on the surface of the array electrode, form a hydrophobic surface on the surface of the surface hydrophobicity treatment auxiliary layer, and deposit a perovskite material on the array electrode to form a photosensitive layer, for the arrayed perovskite material with very harsh preparation conditions, the hydrophobicity/hydrophilicity treatments provide a good growth environment for the perovskite material, and the prepared perovskite thin film is compact and regular in shape, which is beneficial for synthesizing a photosensitive layer with large-scale array and complex pattern, and the obtained flexible photodetector array has good photoresponse performance, good electrical performance, and good electrical performance, The photoelectric stability and the bending resistance performance are realized, crosstalk does not exist among pixel points of each array unit, the optical response signals can be independently displayed, and the optical tracking detection and the optical imaging can be used for real-time optical tracking detection and optical imaging.
It will be understood by those skilled in the art that the foregoing descriptions of materials, dimensions, etc. are exemplary only and are not intended to limit the present disclosure.
The preferred embodiments of the present disclosure are described in detail with reference to the accompanying drawings, however, the present disclosure is not limited to the specific details of the above embodiments, and various simple modifications may be made to the technical solution of the present disclosure within the technical idea of the present disclosure, and these simple modifications all belong to the protection scope of the present disclosure.
It should be noted that the various features described in the above embodiments may be combined in any suitable manner without departing from the scope of the invention. In order to avoid unnecessary repetition, various possible combinations will not be separately described in this disclosure.
In addition, any combination of various embodiments of the present disclosure can be made, and the same shall be considered as what is protected by the present disclosure, as long as it does not depart from the spirit of the present disclosure.
The above-mentioned embodiments are intended to illustrate the objects, aspects and advantages of the present disclosure in further detail, and it should be understood that the above-mentioned embodiments are only illustrative of the present disclosure and are not intended to limit the present disclosure, and any modifications, equivalents, improvements and the like made within the spirit and principle of the present disclosure should be included in the scope of the present disclosure.

Claims (9)

1. A flexible photodetector array comprising:
a substrate comprising a flexible substrate;
a metal circuit comprising an arrayed electrode located over the flexible substrate;
the surface hydrophobicity processing auxiliary layer is positioned on the metal circuit and is provided with a hollow area corresponding to the position of the arrayed electrode, so that the arrayed electrode is exposed; the surface hydrophobicity treatment auxiliary layer is made of an insulating thin film material; the surface of the arrayed electrode is a hydrophilic surface, and the surface of the surface hydrophobicity treatment auxiliary layer is a hydrophobic surface;
the photosensitive layer is positioned in the hollow area of the surface hydrophobicity treatment auxiliary layer and positioned on the array electrode, and the photosensitive layer is made of perovskite material; and
the packaging layer is positioned on the photosensitive layer and the surface hydrophobicity treatment auxiliary layer;
wherein the photosensitive layer is prepared by a two-step continuous deposition method, the two-step deposition method comprising:
spin-coating a first precursor on the exposed surface of the arrayed electrode, wherein the solvent of the first precursor is a hydrophobic solvent, so as to obtain a first precursor array; and
and spin-coating a second precursor on the first precursor array, wherein the second precursor and the first precursor can jointly synthesize a perovskite material to obtain the photosensitive layer.
2. The flexible photodetector array as claimed in claim 1, wherein the metal circuit further comprises: the external positive electrodes and the external negative electrodes are correspondingly connected with each electrode in the arrayed electrodes; the external positive electrode is a common positive electrode and is connected to all the arrayed electrodes, and the external negative electrodes are mutually independent.
3. The flexible photodetector array of claim 1,
the thickness of the surface hydrophobicity treatment auxiliary layer is between 10nm and 30 nm.
4. The flexible photodetector array as claimed in claim 1, wherein each array unit in the arrayed electrode has a length of 10 μm to 100 μm, and a gap between two adjacent array units is 50 μm to 300 μm.
5. The flexible photodetector array of any of claims 1 to 4,
the substrate is a flexible high-temperature-resistant transparent substrate; and/or the presence of a gas in the gas,
the thickness of the substrate is between 50 and 200 mu m; and/or the presence of a gas in the gas,
the electrodes in the arrayed electrodes are interdigital electrodes; and/or the presence of a gas in the gas,
the material of the packaging layer is a transparent high molecular organic material with adhesiveness and stretchability.
6. The flexible photodetector array as claimed in claim 5, wherein the flexible refractory transparent substrate has a refractory range of: 100-300 ℃;
and/or the substrate is a poly terephthalic acid plastic or polyethylene naphthalate.
7. The flexible photodetector array as claimed in any one of claims 1 to 4, wherein the material of the photosensitive layer comprises one of the following materials: CH (CH)3NH3PbI3、CH3NH3PbI3-xCl or CsPbBr3A perovskite material.
8. A method of making a flexible photodetector array as claimed in any one of claims 1 to 7, comprising:
forming a metal circuit on a substrate, the metal circuit comprising an arrayed electrode, the substrate comprising a flexible substrate;
depositing a surface hydrophobicity treatment auxiliary layer on the metal circuit, and carrying out hydrophobicity, patterning and hydrophilicity treatment to enable the surface hydrophobicity treatment layer to have a hollow area corresponding to the position of the arrayed electrode, so that the arrayed electrode is exposed, a hydrophilic surface is formed on the surface of the arrayed electrode, and a hydrophobic surface is formed on the surface of the surface hydrophobicity treatment auxiliary layer; the surface hydrophobicity treatment auxiliary layer is made of an insulating thin film material;
forming a photosensitive layer in the hollow area of the surface hydrophobicity treatment auxiliary layer and on the surface of the arrayed electrode; and
forming an encapsulation layer on the photosensitive layer and the surface hydrophobicity-treatment auxiliary layer;
the method for forming the photosensitive layer comprises the following steps: a two-step sequential deposition process, comprising:
spin-coating a first precursor on the exposed surface of the arrayed electrode, wherein the solvent of the first precursor is a hydrophobic solvent, so as to obtain a first precursor array; and
and spin-coating a second precursor on the first precursor array, wherein the second precursor and the first precursor can jointly synthesize a perovskite material to obtain the photosensitive layer.
9. The production method according to claim 8,
the method for hydrophobic treatment comprises the following steps: soaking a sample in a mixed solution of octadecyl siloxane and normal hexane for treatment; and/or the presence of a gas in the gas,
the hydrophilic treatment method comprises the following steps: oxygen plasma treatment is used.
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