Nanowire orientation method, prepared thin film and application of thin film in polarized electric device

Abstract

The invention relates to a nanowire orientation method, a prepared thin film and application of the thin film in a polarized electric device. The nanowire orientation method comprises the steps that (1) an orientation component and a substrate are provided, the orientation component comprises at least one orientation unit, and each orientation unit comprises a fixing piece and at least two conical flexible components fixed to the fixing piece and arranged side by side; the conical flexible component is divided into a main orientation area, an auxiliary orientation area and a liquid supply area from the root to the tip. (2) the orientation component stores a nanowire dispersion liquid to be oriented; and (3) enabling the orientation component and the substrate to move relatively, and enabling the conical flexible component to deform. By arranging the orientation component, orientation of the one-dimensional nanowire is achieved, especially orientation of the ultra-long one-dimensional nanowire can be achieved, and the orientation half-peak width can reach 3.16-16 degrees.

Description

Technical Field

[0001] The invention belongs to the technical field of one-dimensional material orientation, and in particular relates to a nanowire orientation method, a prepared film and an application thereof in a polarized photoelectric device. Background Art

[0002] Semiconductor nanowires with highly anisotropic transition dipole moments are important materials for preparing polarized optoelectronic devices. In particular, nanowires with high aspect ratios are more conducive to improving light absorption and carrier migration along the long axis, and have broad application prospects. Various strategies have been developed to prepare oriented nanowire structures, including scraping, dip coating, and LB interface assembly technology. However, there are still problems such as large deviations in nanowire orientation and the difficulty of uniformity in ultra-long nanowires being easily entangled with each other, resulting in low polarization of the device.

[0003] For example, it is difficult to precisely control the orientation of nanowires at the micrometer scale using the blade coating and dip coating methods, and the orientation degree of the prepared nanowire film is low. Although the LB interface assembly technology is suitable for the oriented assembly of ultra-long nanowires, it is difficult to further improve the orientation degree because ultra-long nanowires are prone to entangle with each other.

[0004] Therefore, how to achieve highly oriented assembly of nanowires, especially ultra-long nanowires, through simple methods is an urgent problem that researchers in this field need to solve. Summary of the invention

[0005] In view of the shortcomings of the prior art, one of the purposes of the present invention is to provide a nanowire alignment method, the nanowire alignment method comprising the following steps:

[0006] (1) providing an orientation component and a substrate, wherein the orientation component comprises at least one orientation unit, wherein the orientation unit comprises a fixing member and at least two conical flexible members fixed on the fixing member and arranged side by side, wherein along the length direction D1 of the conical flexible member, the conical bottom of the conical flexible member is fixed on the fixing member, the conical tip is a free end, and the axes of the conical flexible members are arranged parallel to each other in a natural state;

[0007] The conical flexible member is divided into a main orientation area, an auxiliary orientation area and a liquid supply area from the root to the tip;

[0008] (2) The alignment component stores the nanowire dispersion to be aligned and outputs the nanowire dispersion;

[0009] (3) The orientation component and the substrate are caused to move relative to each other, and the relative movement direction is D2. The conical flexible member is deformed, and the angle between the outer surface of the portion of the conical flexible member in the main orientation area and the surface of the substrate is α, α≤2°; the angle between the outer surface of the portion of the conical flexible member in the auxiliary orientation area and the surface of the substrate is β, and β>α; during the relative movement, the angle between the portion of the conical flexible member in the main orientation area and the surface of the substrate is maintained at ≤α; the arrangement direction of the conical flexible members of the same orientation unit is a first arrangement direction D3, the first arrangement direction D3 is perpendicular to the relative movement direction D2, and the first arrangement direction D3 is parallel to the surface of the substrate.

[0010] The deformation of the conical flexible component described in the present application is usually bending deformation; the outer surface of the conical flexible component is a curved surface, and the angle between it and the base surface can be understood as the angle between any element line of the outer surface of the conical flexible component and the base surface.

[0011] The present application arranges at least two parallel conical flexible members and makes them move relative to a substrate, thereby controlling the positional relationship between the conical flexible members and the substrate. The parallel conical flexible members present an arc shape in an auxiliary orientation region and transition to a main orientation region. The nanowire dispersion is initially combed and oriented in the auxiliary orientation region, and then reaches the main orientation region under the combined force of gravity and capillary action, and maintains a state in which the conical flexible members and the substrate are nearly parallel or overlapped in the main orientation region. At this time, the liquid film between adjacent conical flexible members forms a shear flow, combs the one-dimensional nanowires, and achieves orientation.

[0012] The present application does not specifically limit the material of the tapered flexible member, as long as it can be brought into contact with the substrate in the area near the end under the action of an external force to form a main orientation zone. Exemplarily, the material of the tapered flexible member described in the present application can be biological new hair (such as wolf hair, sheep hair, purple hair, rat tail hair, horse hair, etc.), PDMS, glass, copper, PET, polybutylene terephthalate (PBT) and / or polytetrafluoroethylene, etc. When non-biological new hair is selected, the shape of the tapered flexible member is considered to have a similar appearance to biological new hair, such as a tapered structure at the tip.

[0013] The conical flexible member described in the present application can be understood as a structure including biological new hair or a structure abstracted from the structure, generally referring to at least a conical end portion and a conical or cylindrical tail portion transitionally connected to the end portion. The present application does not specifically limit the length ratio of the end portion and the tail portion.

[0014] Preferably, the speed of the relative movement in step (3) is 2 mm / s to 15 mm / s, for example, 3 mm / s, 5 mm / s, 8 mm / s, 10 mm / s, 13 mm / s, etc.

[0015] Preferably, the output speed of the nanowire dispersion is 0.5 to 100 μL / s, for example, 1 μL / s, 5 μL / s, 10 μL / s, 18 μL / s, 25 μL / s, 35 μL / s, 46 μL / s, 58 μL / s, 75 μL / s, 94 μL / s, etc.

[0016] The relative movement of the orientation component and the substrate can make an appropriate amount of the nanowire dispersion liquid form a liquid film, and use the surface tension to align the one-dimensional nanowires. If the relative movement speed is too high, the output of the nanowire dispersion liquid is too low, the liquid film is easy to break, and the orientation of the one-dimensional nanowires is reduced. If the relative speed is low and the output of the nanowire dispersion liquid is high, the one-dimensional nanowires are easy to accumulate, which will also reduce the orientation of the one-dimensional nanowires.

[0017] It should be noted that as long as the orientation component moves relative to the substrate and continuously outputs the nanowire dispersion, the one-dimensional nanowires can be oriented. The relative movement speed of 2 mm / s to 15 mm / s and the output speed of the nanowire dispersion of 0.5 to 100 μL / s are only the preferred ranges for improving the orientation.

[0018] Generally, the more the number of tapered flexible components of the orientation unit is, the greater the speed at which the nanowire dispersion can be outputted, and the one-dimensional material can be oriented in a wider plane.

[0019] Preferably, in the main orientation area, the distance between the conical flexible member and the substrate is 0, and the area between adjacent conical flexible members is defined as a liquid bridge area; along the length direction of the conical flexible member, the length of the liquid bridge area is 1.5 to 12 mm, preferably 3 to 8 mm; the width of the liquid bridge area is 2 μm to 500 μm, preferably 2 μm to 70 μm.

[0020] The length of the liquid bridge region can be understood as the length of the main orientation region. In the liquid bridge region, sufficient length and appropriate width can improve the orientation of the one-dimensional nanowires and can broaden the applicable length of the orientation method, so as to orient longer one-dimensional nanowires.

[0021] Generally, when there are more than 2 orientation units, such as 3, 4, 5, 6, etc., the width of the liquid bridge zone will be appropriately reduced, and a liquid bridge zone width of 2 to 70 μm can be obtained; when there is 1 orientation unit, the liquid bridge zone width is usually larger.

[0022] The orientation component described in the present application may include one orientation unit, or may include two or more orientation units.

[0023] Preferably, the orientation component includes at least two orientation units, and the roots of the orientation units are staggered along the direction of the relative movement direction D2; in the liquid supply area, a liquid storage space is formed between the conical flexible components of the orientation component for storing the nanowire solution to be oriented; in the auxiliary orientation area, an orientation transition space is formed between the conical flexible components of the orientation component, and along the relative movement direction D2, the width of the orientation transition space gradually decreases to the width of the liquid bridge area, and the staggered conical flexible components of adjacent orientation units gradually tend to be coplanar.

[0024] When the orientation component includes two or more orientation units, when it moves relative to the substrate, in the main orientation area, the conical flexible components of different orientation units will be inserted into the substrate to form a narrower liquid bridge area, thereby improving the orientation of the one-dimensional material and broadening the size range of the one-dimensional material of the orientation method.

[0025] The staggered arrangement means that the tapered flexible components of the orientation units in the second row are located in the region extending along the D2 direction of the gaps between the tapered flexible components of the orientation units in the first row; the tapered flexible components of the orientation units in the third row are located in the region extending along the D2 direction of the gaps between the tapered flexible components of the orientation units in the second row, and so on, the orientation units of the orientation components are staggered. It should be noted that the tapered flexible components of the orientation units in the third row are preferably aligned with the tapered flexible components of the orientation units in the first row.

[0026] Preferably, the number of tapered flexible members in different orientation units is the same or different, and preferably the number of tapered flexible members in different orientation units is the same.

[0027] Preferably, the number of the orientation units in the orientation component is 1 to 20, for example, 2, 5, 9, 14, 18, etc.

[0028] Preferably, the number of the tapered flexible members of the orientation unit is 2 to 200,000, for example, 3, 6, 10, 20, 60, 80, 100, 300, 500, 700, 1000, 2000, 4000, 8000, 10000, 40000, 70000, 90000, etc.

[0029] Preferably, the length of the nanowire is 5μm to 300μm, for example, 10μm, 15μm, 20μm, 25μm, 30μm, 32μm, 45μm, 50μm, 65μm, 70μm, 80μm, 88μm, 96μm, 100μm, 125μm, 134μm, 150μm, 157μm, 169μm, 188μm, 195μm, 200μm, 234μm, 260μm, 275μm, 282μm, 295μm, etc., preferably 30μm to 300μm, preferably 100μm to 300μm.

[0030] The present application does not specifically limit the material of the nanowires to be oriented. Preferably, the nanowires to be oriented include any one of perovskite nanowires, silver nanowires, copper nanowires, silicon nanowires, and oxide nanowires, or a combination of at least two thereof.

[0031] The radial dimension of the nanowire is usually less than or equal to 500 nm, preferably less than or equal to 200 nm.

[0032] Preferably, the surface tension of the nanowire solution to be oriented is 15 mN / m to 30 mN / m, for example, 16 mN / m, 19 mN / m, 22 mN / m, 25 mN / m, 28 mN / m, etc.

[0033] Preferably, the solvent of the nano-solution to be oriented includes any one of n-octane, n-hexane, toluene, isopropanol, and ethanol, or a combination of at least two thereof.

[0034] The second object of the present application is to provide a film prepared by the nanowire orientation method described in the first object, comprising a substrate and an oriented one-dimensional nanomaterial attached to the surface of the substrate.

[0035] The film can also be understood as a layered structure, or an oriented nanowire array. The film can also be understood as a layered structure of a one-dimensional nanomaterial parallel array formed by oriented one-dimensional nanomaterials.

[0036] Preferably, the orientation statistical half-peak width of the one-dimensional nanomaterial is 3.16° to 16°, for example, 3.5°, 4.0°, 4.5°, 5.0°, 5.5°, 6.0°, 6.5°, 7.0°, 7.5°, 8.0°, 8.5°, 9.0°, 9.5°, 10.0°, 10.5°, 11.0°, 11.5°, etc.

[0037] Preferably, the length of the one-dimensional nanomaterial is 5μm to 300μm, preferably 30μm to 300μm (for example, 32μm, 45μm, 57μm, 65μm, 74μm, 88μm, 96μm, 106μm, 125μm, 134μm, 148μm, 157μm, 169μm, 188μm, 195μm, 224μm, 234μm, 264μm, 275μm, 282μm, 295μm, etc.), preferably 50μm to 300μm.

[0038] Preferably, the substrate is any one of a glass substrate, a silicon substrate, PDMS (polydimethylsiloxane), PET (polyethylene terephthalate), and polyurethane, or a combination of at least two thereof.

[0039] The third object of the present application is to provide a use of the film as described in the second object, wherein the film is used to make a polarized photoelectric device, preferably used as a functional layer of a polarized photoelectric device, and further preferably used as a light-emitting layer of a light-emitting diode or a photosensitive layer of a light detector.

[0040] The fourth object of the present application is to provide a polarized light-emitting diode, comprising the thin film as described in the second object, wherein a hole transport layer, a hole injection layer and an anode layer are arranged in sequence from near to far on one side of the thin film, and an electron transport layer and a cathode layer are arranged in sequence from near to far on the other side of the thin film.

[0041] The fifth object of the present application is to provide a polarized light detector, characterized in that the light detector includes the film as described in the third object, and conductive electrodes are respectively arranged at both ends along the extension direction of the one-dimensional nanomaterial in the film.

[0042] Typically, the conductive electrode is deposited on a thin film by evaporating an electrode block through a mask, and the electrode block is designed to be disposed at both ends of the one-dimensional nanomaterial.

[0043] Compared with the prior art, this application has the following beneficial effects:

[0044] The present application achieves orientation of one-dimensional nanowires by setting an orientation component, especially can orient ultra-long one-dimensional nanowires, and the orientation half-peak width can reach 3.16° to 16°. BRIEF DESCRIPTION OF THE DRAWINGS

[0045] Figure 1 A schematic diagram of the structure of a nanowire orientation device of Equipment Example 2;

[0046] Figure 2 The fluorescence microscope optical image and half-peak width statistics of the ultra-long perovskite nanowire layer provided in Example 1;

[0047] Figure 3The fluorescence microscope optical image and half-peak width statistical results of the ultra-long perovskite nanowire layer provided for Comparative Example 1. DETAILED DESCRIPTION

[0048] The technical solution of the present invention is further explained below in conjunction with specific implementation methods. However, it should be noted that the specific implementation methods are only a specific implementation and explanation of the essence of the technical solution of the present invention, and should not be understood as a limitation on the protection scope of the present invention.

[0049] The reagents and instruments used in the examples can all be purchased from commercial products, and the detection methods are conventional methods well known in the art.

[0050] Device instance 1

[0051] like Figure 1 ( Figure 1 Schematic diagram of the structure of the nanowire orientation device of device example 1) is shown, a nanowire orientation device, the orientation device comprises:

[0052] An orientation component, the orientation component includes 6 orientation units, each of which includes a fixing part and 60 conical flexible members (wolf hair) fixed on the fixing part and arranged side by side, and the distribution width of the 60 conical flexible members is 5 mm; along the length direction D1 of the conical flexible member, the cone bottom of the conical flexible member is fixed on the fixing part, the cone tip is a free end, and the axis of the conical flexible member is arranged in parallel in a natural state; the length of the conical flexible member is 18 mm, and the cone bottom diameter is 60 μm; the conical flexible member is divided into a main orientation area, an auxiliary orientation area and a liquid supply area from the root to the tip; the arrangement direction of the conical flexible members in the orientation unit is a first arrangement direction D3;

[0053] The liquid supply component is arranged on the top of the orientation component and can supply liquid to the tapered flexible member.

[0054] Device instance 2

[0055] A nanowire alignment device, such as Figure 1 ( Figure 1 Schematic diagram of the structure of the nanowire orientation device of device example 2), the orientation device comprises:

[0056] An orientation component, the orientation component includes an orientation unit, each of which includes a fixing member 200 and 20 conical flexible members 100 (wolf hair) fixed on the fixing member 200 and arranged side by side, and the distribution width W of the 20 conical flexible members 100 is 1.4 mm; along the length direction D1 of the conical flexible member 100, the cone bottom 102 of the conical flexible member is fixed on the fixing member 200, and the cone tip 101 is a free end, and the axis of the conical flexible member 100 is arranged in parallel in a natural state; the length of the conical flexible member 100 is 12 mm, and the diameter of the cone bottom 102 is 60 μm; the conical flexible member 100 is divided into a main orientation area 110, an auxiliary orientation area 120 and a liquid supply area 130 from the root to the tip;

[0057] The liquid supply component is arranged on the top of the orientation component and can supply liquid to the tapered flexible member.

[0058] Device instance 3

[0059] A nanowire orientation device, comprising:

[0060] An orientation component, the orientation component includes 4 orientation units, each of the orientation units includes a fixing part and 60 conical flexible members (wolf hair) fixed on the fixing part and arranged side by side, the distribution width of the 60 conical flexible members is 1.3mm; along the length direction D1 of the conical flexible member, the cone bottom of the conical flexible member is fixed on the fixing part, the cone tip is a free end, and the axis of the conical flexible member is arranged in parallel in a natural state; the length of the conical flexible member is 15mm, and the cone bottom diameter is 20μm; the conical flexible member is divided into a main orientation area, an auxiliary orientation area and a liquid supply area from the root to the tip; the arrangement direction of the conical flexible members in the orientation unit is a first arrangement direction D3;

[0061] The liquid supply component is arranged on the top of the orientation component and can supply liquid to the tapered flexible member.

[0062] Comparison equipment example 1

[0063] A nanowire orientation device, comprising:

[0064] An orientation component, the orientation component includes 6 orientation units, each of which includes a fixing part and 60 conical flexible members (wolf hair) fixed on the fixing part and arranged side by side, and the distribution width of the 60 conical flexible members is 5 mm; along the length direction D1 of the conical flexible member, the cone bottom of the conical flexible member is fixed on the fixing part, the cone tip is a free end, and the axis of the conical flexible member is arranged in parallel in a natural state; the length of the conical flexible member is 1.5 mm, and the cone bottom diameter is 100 μm;

[0065] The liquid supply component is arranged on the top of the orientation component and can supply liquid to the tapered flexible member.

[0066] In Comparative Device Example 1, the tapered flexible member is too short to form an effective main orientation region.

[0067] Example 1

[0068] A polarized light detector is prepared by the following method:

[0069] (1) The glass substrate was sequentially placed in a cleaning solution, deionized water, ethanol, acetone, and isopropanol for 15 minutes each, and then dried for later use;

[0070] (2) a dispersion of ultra-long perovskite nanowires (length 200 μm) in n-hexane solvent, with a surface tension of 18.4 mN / m;

[0071] (3) Using the nanowire orientation device provided in Equipment Example 1, supply liquid (the dispersion prepared in step 2) to the orientation component, and output the nanowire dispersion at a speed of 4 μL / s; then adjust the position of the orientation component and the substrate, and control the distance between the orientation component and the substrate so that the length of the main orientation area is 12 mm; at this time, the distance between the conical flexible component and the substrate in the main orientation area is 0, and the angle is less than 2°; the angle between the auxiliary orientation area and the substrate is greater than 2°; in the main orientation area, the length of the liquid bridge area is 12 mm, and the width is 55-65 μm;

[0072] (4) along the direction of D2, the alignment component and the substrate are moved relative to each other at a relative movement speed of 15 mm / s; D2 is perpendicular to D3, and D2 is perpendicular to D1; and an aligned ultra-long perovskite nanowire layer is obtained.

[0073] The half-peak width of the oriented ultra-long perovskite nanowire layer was measured by using the plug-in OrientationJ of ImageJ (image processing software) to calculate the orientation information of the characteristic pixels; the measurement result was 3.54°, such as Figure 2 ( Figure 2 The fluorescence microscope optical image and half-peak width statistical results of the ultra-long perovskite nanowire layer provided in Example 1 are shown as follows.

[0074] (5) A patterned mask is attached to the obtained array of ultra-long perovskite nanowire layers; then, gold / chromium electrodes (the thickness of the gold electrode and the chromium electrode are 100 nm and 10 nm, respectively) are sequentially evaporated to obtain conductive electrodes, and a photoconductive polarization photodetector is obtained, and the photocurrent anisotropy ratio can reach (I max / I min )2.79.

[0075] Example 2

[0076] A polarized light detector is prepared by the following method:

[0077] (1) The glass substrate was sequentially placed in a cleaning solution, deionized water, ethanol, acetone, and isopropanol for 15 minutes each, and then dried for later use;

[0078] (2) a dispersion of ultra-long perovskite nanowires (length 200 μm) in n-hexane solvent, with a surface tension of 18.4 mN / m;

[0079] (3) Using the nanowire orientation device provided in Equipment Example 1, supply liquid (the dispersion prepared in step 2) to the orientation component, and output the nanowire dispersion at a speed of 4 μL / s; then adjust the position of the orientation component and the substrate, and control the distance between the orientation component and the substrate so that the length of the main orientation area is 12 mm; at this time, the distance between the conical flexible component and the substrate in the main orientation area is 0, and the angle is less than 2°; the angle between the auxiliary orientation area and the substrate is greater than 2°; in the main orientation area, the length of the liquid bridge area is 12 mm, and the width is about 55-65 μm;

[0080] (4) along the direction of D2, the alignment component and the substrate are moved relative to each other at a relative movement speed of 10 mm / s; D2 is perpendicular to D3, and D2 is perpendicular to D1; and an aligned ultra-long perovskite nanowire layer is obtained.

[0081] The half-peak width of the oriented ultra-long perovskite nanowire layer was measured by using the plug-in OrientationJ of ImageJ (image processing software) to calculate the direction information of the characteristic pixels; the half-peak width was measured to be 4.75°.

[0082] (5) A patterned mask is attached above the array of the obtained ultra-long perovskite nanowire layer; then, chromium / gold electrodes (the thickness of the chromium electrode and the gold electrode are 10 nm and 100 nm, respectively) are evaporated in sequence to obtain conductive electrodes, thereby obtaining a photoconductive polarization photodetector.

[0083] Example 3

[0084] A polarized light detector, which differs from Example 1 only in adjusting the position of the orientation component and the substrate, controlling the distance between the orientation component and the substrate, so that the length of the main orientation area is 3mm, the corresponding liquid bridge area length is also 3mm, the width is 53-64μm, and the half-peak width is 9.4°.

[0085] Example 4

[0086] A polarized light detector, which differs from Example 1 only in adjusting the position of the orientation component and the substrate, controlling the distance between the orientation component and the substrate, so that the length of the main orientation area is 1 mm, the corresponding liquid bridge area length is also 1 mm, the width is 51-63 μm, and the half-peak width is 14.8°.

[0087] Example 5

[0088] A polarized light detector is prepared by the following method:

[0089] (1) The glass substrate was sequentially placed in a cleaning solution, deionized water, ethanol, acetone, and isopropanol for 15 minutes each, and then dried for later use;

[0090] (2) a dispersion of ultra-long perovskite nanowires (length 200 μm) in n-hexane solvent, with a surface tension of 18.4 mN / m;

[0091] (3) Using the nanowire orientation device provided in Equipment Example 3, supply liquid (the dispersion prepared in step 2) to the orientation component, and output the nanowire dispersion at a speed of 4 μL / s; then adjust the position of the orientation component and the substrate, and control the distance between the orientation component and the substrate so that the length of the main orientation area is 12 mm; at this time, the distance between the conical flexible component and the substrate in the main orientation area is 0, and the angle is less than 2°; the angle between the auxiliary orientation area and the substrate is greater than 2°; in the main orientation area, the length of the liquid bridge area is 12 mm, and the width is 2-10 μm;

[0092] (4) along the direction of D2, the alignment component and the substrate are moved relative to each other at a relative movement speed of 10 mm / s; D2 is perpendicular to D3, and D2 is perpendicular to D1; and an aligned ultra-long perovskite nanowire layer is obtained.

[0093] The half-peak width of the oriented ultra-long perovskite nanowire layer was measured by using the plug-in OrientationJ of ImageJ (image processing software) to calculate the direction information of the characteristic pixels; the measurement result was 3.3°.

[0094] (5) A patterned mask was attached to 12 squares of the obtained ultra-long perovskite nanowire layer array; then, gold / chromium electrodes (the thickness of the gold electrode and the chromium electrode were 100 nm and 10 nm, respectively) were evaporated in sequence to obtain a photoconductive polarization photodetector.

[0095] Example 6

[0096] A polarized light detector is prepared by the following method:

[0097] (1) The glass substrate was sequentially placed in a cleaning solution, deionized water, ethanol, acetone, and isopropanol for 15 minutes each, and then dried for later use;

[0098] (2) a dispersion of ultra-long perovskite nanowires (length 100 μm) in n-octane solvent, with a surface tension of 21.8 mN / m;

[0099] (3) Using the nanowire orientation device provided in Equipment Example 3, supply liquid (the dispersion prepared in step 2) to the orientation component, and output the nanowire dispersion at a speed of 2 μL / s; then adjust the position of the orientation component and the substrate, and control the distance between the orientation component and the substrate so that the length of the main orientation area is 3 mm; at this time, the distance between the conical flexible component and the substrate in the main orientation area is 0, and the angle is less than 2°; the angle between the auxiliary orientation area and the substrate is greater than 2°; in the main orientation area, the length of the liquid bridge area is 3 mm, and the width is 2-7 μm;

[0100] (4) along the direction of D2, the alignment component and the substrate are moved relative to each other at a relative movement speed of 2 mm / s; D2 is perpendicular to D3, and D2 is perpendicular to D1; and an aligned ultra-long perovskite nanowire layer is obtained.

[0101] The half-peak width of the oriented ultra-long perovskite nanowire layer was measured by using the plug-in OrientationJ of ImageJ (image processing software) to calculate the direction information of the characteristic pixels; the measurement result was 6.6°.

[0102] (5) A patterned mask is attached above the array of the obtained ultra-long perovskite nanowire layer; then, gold / chromium electrodes (the thickness of the gold electrode and the chromium electrode are 100 nm and 10 nm, respectively) are evaporated in sequence to obtain a photoconductive polarization photodetector.

[0103] Example 7

[0104] A polarized light detector is prepared by the following method:

[0105] (1) The silicon substrate was sequentially placed in a cleaning solution, deionized water, ethanol, acetone, and isopropanol for 15 minutes each, and then dried for later use;

[0106] (2) a dispersion of ultra-long perovskite nanowires (length 200 μm) in n-hexane solvent, with a surface tension of 18.4 mN / m;

[0107] (3) Using the nanowire orientation device provided in Equipment Example 2, supply liquid (the dispersion prepared in step 2) to the orientation component, and output the nanowire dispersion at a speed of 0.5 μL / s; then adjust the position of the orientation component and the substrate, and control the distance between the orientation component and the substrate so that the length of the main orientation area is 12 mm; at this time, the distance between the conical flexible component and the substrate in the main orientation area is 0, and the angle is less than 2°; the angle between the auxiliary orientation area and the substrate is greater than 2°; in the main orientation area, the length of the liquid bridge area is 12 mm, and the width is 95-105 μm;

[0108] (4) along the direction of D2, the alignment component and the substrate are moved relative to each other at a relative movement speed of 10 mm / s; D2 is perpendicular to D3, and D2 is perpendicular to D1; and an aligned ultra-long perovskite nanowire layer is obtained.

[0109] The half-peak width of the oriented ultra-long perovskite nanowire layer was measured by using the plug-in OrientationJ of ImageJ (image processing software) to calculate the direction information of the characteristic pixels; the measurement result was 7.5°.

[0110] (5) A patterned mask is attached above the array of the obtained ultra-long perovskite nanowire layer; then, gold / chromium electrodes (the thickness of the gold electrode and the chromium electrode are 100 nm and 10 nm, respectively) are evaporated in sequence to obtain a photoconductive polarization photodetector.

[0111] Example 8

[0112] A method for preparing a linearly polarized light emitting diode:

[0113] (1) Place the ITO glass substrate in washing liquid, deionized water, ethanol, acetone, and isopropanol in turn for 15 minutes each, blow dry and set aside; place the above substrate into a plasma cleaning machine for plasma treatment for 1 minute. Then place it on the glue chuck of the glue spreader, set the speed to 3000 rpm, then drop 60μL of PEDOT:PSS solution in a static state, rotate for 45s, and then place the prepared film on a hot plate at 130°C (front side up), thermally anneal for 20min, and obtain a PEDOT:PSS film; place the obtained PEDOT:PSS film on the glue spreader chuck, set the speed to 3000 rpm, time 45s, drop PVK solution, and then place the substrate on a hot plate at 130° (front side up), thermally anneal for 20min, and obtain a substrate to be patterned;

[0114] (2) a dispersion of ultra-long perovskite nanowires (length 200 μm) in n-hexane solvent, with a surface tension of 18.4 mN / m;

[0115] (3) Using the nanowire orientation device provided in Equipment Example 1, supply liquid (the dispersion prepared in step 2) to the orientation component, and output the nanowire dispersion at a speed of 2.5 μL / s; then adjust the position of the orientation component and the substrate to be patterned, and control the distance between the orientation component and the substrate to be patterned, so that the length of the main orientation area is 8 mm; at this time, the distance between the conical flexible component and the substrate in the main orientation area is 0, and the angle is less than 2°; the angle between the auxiliary orientation area and the substrate to be patterned is greater than 2°; in the main orientation area, the length of the liquid bridge area is 8 mm, and the width is 54-64 μm;

[0116] (4) along the D2 direction, the alignment component and the substrate to be patterned are moved relative to each other at a relative movement speed of 6 mm / s; D2 is perpendicular to D3, and D2 is perpendicular to D1; and an aligned ultra-long perovskite nanowire layer is obtained.

[0117] The half-peak width of the oriented ultra-long perovskite nanowire layer was measured by using the plug-in OrientationJ of ImageJ (image processing software) to calculate the direction information of the characteristic pixels; the measurement result was 3.16°.

[0118] (5) The sample obtained in step (4) was placed on the chuck of a coating machine, the rotation speed was set to 3000 rpm, 60 μL of ZnO solution was added, and the film was rotated for 45 seconds. Then, the prepared film was placed on a hot plate at 80°C (front side facing up), and thermally annealed for 20 minutes to obtain a ZnO film. A patterned mask was attached to the obtained ZnO film, and a silver electrode (thickness 100 nm) was evaporated to obtain a linearly polarized light-emitting diode, and the electroluminescence polarization degree could reach 0.6.

[0119] Example 9

[0120] A method for preparing a transparent conductive film:

[0121] (1) The glass substrate / PET substrate was sequentially placed in a washing solution, deionized water, ethanol, acetone, and isopropanol for 15 minutes each, and then dried for later use;

[0122] (2) a dispersion of silver nanowires (length 10 μm) in isopropanol solvent, with a surface tension of 21.7 mN / m;

[0123] (3) Using the nanowire orientation device provided in Equipment Example 2, supply liquid (the dispersion prepared in step 2) to the orientation component, and output the nanowire dispersion at a speed of 4 μL / s; then adjust the position of the orientation component and the substrate, and control the distance between the orientation component and the substrate so that the length of the main orientation area is 5 mm; at this time, the distance between the conical flexible component and the substrate in the main orientation area is 0, and the angle is less than 2°; the angle between the auxiliary orientation area and the substrate is greater than 2°; in the main orientation area, the length of the liquid bridge area is 5 mm, and the width is 96-104 μm;

[0124] (4) along the direction D2, the alignment component and the substrate are moved relative to each other at a relative movement speed of 10 mm / s; D2 is perpendicular to D3, and D2 is perpendicular to D1; and an aligned silver nanowire layer is obtained.

[0125] The half-peak width of the oriented ultra-long silver nanowire layer was measured by using the plug-in OrientationJ of ImageJ (image processing software) to calculate the direction information of the characteristic pixels; the measurement result was 14°.

[0126] (5) A PEDOT:PSS layer was prepared by spin coating on top of the obtained ultra-long silver nanowire layer to obtain a flexible transparent electrode.

[0127] Example 10

[0128] A polarized light detector is prepared by the following method:

[0129] (1) The glass substrate was sequentially placed in a cleaning solution, deionized water, ethanol, acetone, and isopropanol for 15 minutes each, and then dried for later use;

[0130] (2) a dispersion of ultra-long perovskite nanowires (length 300 μm) in n-hexane solvent, with a surface tension of 18.4 mN / m;

[0131] (3) Using the nanowire orientation device provided in Equipment Example 1, supply liquid (the dispersion prepared in step 2) to the orientation component, and output the nanowire dispersion at a speed of 3 μL / s; then adjust the position of the orientation component and the substrate, and control the distance between the orientation component and the substrate so that the length of the main orientation area is 8 mm; at this time, the distance between the conical flexible component and the substrate in the main orientation area is 0, and the angle is less than 2°; the angle between the auxiliary orientation area and the substrate is greater than 2°; in the main orientation area, the length of the liquid bridge area is 8 mm, and the width is 55-67 μm;

[0132] (4) along the direction of D2, the alignment component and the substrate are moved relative to each other at a relative movement speed of 10 mm / s; D2 is perpendicular to D3, and D2 is perpendicular to D1; and an aligned ultra-long perovskite nanowire layer is obtained.

[0133] The half-peak width of the oriented ultra-long perovskite nanowire layer was measured by using the plug-in OrientationJ of ImageJ (image processing software) to calculate the direction information of the characteristic pixels; the half-peak width was measured to be 3.4°.

[0134] (5) A patterned mask is attached to the obtained array of ultra-long perovskite nanowire layers; then, chromium / gold electrodes are sequentially evaporated (the thickness of the chromium electrode and the gold electrode are 10 nm and 100 nm, respectively), thereby obtaining a photoconductive polarization photodetector.

[0135] Comparative Example 1

[0136] A polarized light detector, which differs from Example 1 only in that the comparative device example 1 is used to replace the device example 1, the position of the orientation component and the substrate is adjusted, and the distance between the orientation component and the substrate is controlled so that the orientation component moves as close to the substrate as possible. The half-peak width of the oriented ultra-long perovskite nanowire layer is measured, and the half-peak width is 22.54°. The results show that the prepared nanowire layer has problems such as aggregation distribution and poor orientation (such as Figure 3 As shown, Figure 3 Fluorescence microscope optical image and half-peak width statistical results of the ultra-long perovskite nanowire layer provided for Comparative Example 1).

[0137] Finally, it should be noted that the above embodiments are only used to illustrate the technical solutions of the present invention, rather than to limit it. Although the present invention has been described in detail with reference to the aforementioned embodiments, those skilled in the art should understand that they can still modify the technical solutions described in the aforementioned embodiments, or replace some or all of the technical features therein with equivalents. However, these modifications or replacements do not cause the essence of the corresponding technical solutions to deviate from the scope of the technical solutions of the embodiments of the present invention.

Claims

1. A method for aligning nanowires, characterized in that: The nanowire alignment method comprises the following steps: (1) providing an orientation component and a substrate, wherein the orientation component comprises at least one orientation unit, wherein the orientation unit comprises a fixing member and at least two conical flexible members fixed on the fixing member and arranged side by side, wherein along the length direction D1 of the conical flexible member, the conical bottom of the conical flexible member is fixed on the fixing member, the conical tip is a free end, and the axes of the conical flexible members are arranged parallel to each other in a natural state; The conical flexible member is divided into a main orientation area, an auxiliary orientation area and a liquid supply area from the root to the tip; (2) The alignment component stores the nanowire dispersion to be aligned and outputs the nanowire dispersion; (3) causing the orientation component to move relative to the substrate in a relative movement direction of D2, causing the conical flexible member to deform, wherein an angle α between the outer surface of the portion of the conical flexible member in the main orientation region and the surface of the substrate is α, α≤2°; an angle β between the outer surface of the portion of the conical flexible member in the auxiliary orientation region and the surface of the substrate is β, and β>α; During the relative movement, the angle between the conical flexible component part in the main orientation area and the substrate surface is maintained at ≤α; the arrangement direction of the conical flexible components of the same orientation unit is a first arrangement direction D3, the first arrangement direction D3 is perpendicular to the relative movement direction D2, and the first arrangement direction D3 is parallel to the substrate surface.

2. The nanowire alignment method according to claim 1, characterized in that: The speed of the relative motion in step (3) is 2 mm / s to 15 mm / s; Preferably, the output speed of the nanowire dispersion is 0.5 to 100 μL / s.

3. The nanowire alignment method according to claim 1 or 2, characterized in that: In the main orientation region, the distance between the tapered flexible member and the substrate is 0; The area between adjacent tapered flexible members is defined as the liquid bridge area; The length of the liquid bridge area along the length direction of the tapered flexible member is 1.5 mm to 12 mm, preferably 3 to 8 mm; The width of the liquid bridge region is 2 μm to 500 μm, preferably 2 μm to 120 μm.

4. The method for aligning nanowires according to any one of claims 1 to 3, characterized in that: The orientation component comprises at least two orientation units, and the roots of the orientation units are staggered along the direction of the relative movement direction D2; In the liquid supply region, a liquid storage space is formed between the tapered flexible members of the orientation component for storing the nanowire solution to be oriented; In the auxiliary orientation area, an orientation transition space is formed between the tapered flexible components of the orientation unit. Along the relative movement direction D2, the width of the orientation transition space gradually decreases to the width of the liquid bridge area, and the offset tapered flexible components of adjacent orientation units gradually tend to be coplanar.

5. The method for aligning nanowires according to any one of claims 1 to 4, characterized in that: The number of tapered flexible components of different orientation units is the same or different, preferably the number of tapered flexible components of different orientation units is the same; Preferably, the number of the orientation units in the orientation component is 1 to 20; Preferably, the number of the tapered flexible components of the orientation unit is 2 to 200,000.

6. The method for aligning nanowires according to any one of claims 1 to 5, characterized in that: The length of the nanowire is 5 μm to 300 μm, preferably 30 μm to 300 μm, preferably 100 μm to 300 μm; Preferably, the nanowires to be oriented include any one of perovskite nanowires, silver nanowires, copper nanowires, silicon nanowires, and oxide nanowires, or a combination of at least two thereof; Preferably, the surface tension of the nanowire solution to be oriented is 15 mN / m to 30 mN / m; Preferably, the solvent of the nano-solution to be oriented includes any one of n-octane, n-hexane, toluene, isopropanol, and ethanol, or a combination of at least two thereof.

7. A film prepared by the nanowire orientation method according to any one of claims 1 to 6, characterized in that: The film comprises a substrate and an oriented one-dimensional nanomaterial attached to the surface of the substrate; Preferably, the orientation statistical half-peak width of the one-dimensional nanomaterial is 3.16° to 16°; Preferably, the length of the one-dimensional nanomaterial is 5 μm to 300 μm, preferably 30 μm to 300 μm, preferably 50 μm to 300 μm; Preferably, the substrate is any one of a glass substrate, a silicon substrate, polydimethylsiloxane, polyethylene terephthalate, and polyurethane, or a combination of at least two thereof.

8. Use of the film according to claim 7, characterized in that: The film is used for making polarized photoelectric devices, preferably used as a functional layer of polarized photoelectric devices, and further preferably used as a light-emitting layer of a light-emitting diode or a photosensitive layer of a light detector.

9. A polarized light emitting diode, characterized in that: The light emitting diode comprises the thin film as claimed in claim 7, wherein a hole transport layer, a hole injection layer and an anode layer are sequentially arranged on one side of the thin film from near to far, and an electron transport layer and a cathode layer are sequentially arranged on the other side of the thin film from near to far.

10. A polarized light detector, characterized in that: The photodetector comprises the film as claimed in claim 7, and conductive electrodes are respectively arranged at two ends along the extension direction of the one-dimensional nanomaterial in the film.

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