阅读说明：本技术 一种Alq3纳米线水平阵列的制备方法及其应用 (Alq3Preparation method and application of nanowire horizontal array ) 是由 许金友 廖记辉 王兴宇 周国富 于 2021-07-30 设计创作，主要内容包括：本发明公开了一种Alq-(3)纳米线水平阵列的制备方法及其应用。这种Alq-(3)纳米线水平阵列的制备方法包括以下步骤：S1.将M面蓝宝石于1600℃,恒温10h进行退火处理；S2.以PDMS(聚二甲基硅氧烷)对步骤S1所得M面蓝宝石进行表面处理；S3.利用PVD设备,以Alq-(3)粉末为原料在步骤S2所得M面蓝宝石表面进行物理气相沉积。本发明提出的制备方法能够直接制备Alq-(3)纳米线水平阵列,这种纳米线阵列在有序度、均匀性、密度以及结晶性等方面均具有显著优势。(The invention discloses an Alq 3 A method for preparing a horizontal array of nanowires and applications thereof. Such Alq 3 The preparation method of the nanowire horizontal array comprises the following steps: s1, annealing M-surface sapphire at 1600 ℃ for 10h at constant temperature; s2, performing surface treatment on the M-surface sapphire obtained in the step S1 by using PDMS (polydimethylsiloxane); s3, utilizing PVD equipment to perform Alq 3 The powder is used as a raw material, and physical vapor deposition is carried out on the surface of the M-surface sapphire obtained in the step S2. The preparation method provided by the invention can be used for directly preparing Alq 3 The nanowire array has remarkable advantages in the aspects of order degree, uniformity, density, crystallinity and the like.)

1. Alq₃The preparation method of the nanowire horizontal array is characterized by comprising the following steps of:

s1, annealing the M-surface sapphire at 1400-1600 ℃;

s2, carrying out surface treatment on the M-surface sapphire obtained in the step S1 by using organic silicon;

s3, using Alq to₃The powder is used as a raw material, and physical vapor deposition is carried out on the surface of the M-surface sapphire obtained in the step S2.

2. The method according to claim 1, wherein in step S1, the M-plane sapphire has a crystal plane index of

3. The method according to claim 1, wherein the annealing is performed for 5 to 15 hours in step S1.

4. The method according to claim 1, wherein in step S2, the silicone is at least one of PDMS and a silane coupling agent; preferably, the surface treatment is carried out by attaching the gel formed by the organic silicon to the M-plane sapphire obtained in step S1; preferably, the attaching is left for 24-96 hours.

5. The method according to claim 1, wherein the physical vapor deposition in step S3 includes the steps of:

s3a. mixing Alq₃Powder is placed at the upstream of a quartz tube of the double-temperature-zone tube furnace; placing the M-surface sapphire obtained in the step S2 at the downstream of the quartz tube;

s3b, setting Alq₃The temperature of the powder is 330-360 ℃, and the temperature of the M-surface sapphire is 180-220 ℃; removing carrier gas from said Alq₃And (3) flowing powder to the direction of the M-surface sapphire, and performing the physical vapor deposition.

6. The method according to claim 5, wherein in step S3a, the Alq is₃The distance between the powder and the M-surface sapphire is 18-25 cm.

7. The method according to claim 5, wherein in step S3b, the carrier gas is selected from the group consisting of an inert gas and N₂At least one of; preferably, the flow rate of the carrier gas is 150-300sccm, and preferably, the pressure of the carrier gas is 300-500 mbar.

8. The method according to claim 5, wherein in step S3b, the PVD is performed for 0.5-2 hours.

9. A process as claimed in any one of claims 1 to 8Alq prepared by the preparation method₃The application of the nanowire horizontal array in the field of semiconductors.

10. The use according to claim 9, wherein the semiconductor field comprises at least one of a photodetector, an Organic Field Effect Transistor (OFET), an organic photovoltaic cell (OSC) and an Organic Light Emitting Diode (OLED).

Technical Field

The invention belongs to the technical field of micro-nano material preparation, and particularly relates to Alq₃Preparation method and application of nanowire horizontal array。

Background

Since the discovery of conductive high molecular polymers by Shirakawa et al in 1977, organic semiconductors composed of pi-pi conjugated bonds have rapidly become one of the research hotspots in the basic scientific field. Compared with conventional inorganic semiconductors, the electronic layout of organic semiconductors is significantly different. For example: functional modulation can generally be achieved by altering the molecular structure in organic semiconductors. At present, researchers have synthesized a large number of organic semiconductors with diverse properties in succession and successfully applied them to different fields, such as: organic semiconductor field effect transistors, organic solar cells, organic light emitting diodes, organic photodetectors, and the like. Alq₃(8-Hydroxyquinoline aluminum, tris (8-Hydroxyquinoline) aluminum) is a typical representative of organic semiconductors, and has been successfully applied to organic light emitting diodes with stable commercial performance.

The nanowire, as a one-dimensional structure, has been a hot point of research for nearly two decades due to its excellent material quality and excellent electrical, optical and optoelectronic properties. If the nano-wire has the aligned growth direction, the performance of the nano-wire device can be qualitatively leap compared with that of the nano-wire which is randomly distributed, the processing technology of the nano-wire device can be greatly simplified, and the large-scale device integration can be realized.

The conventional top-down method for preparing organic semiconductor nanowires mainly includes Template-Assisted Chemical Vapor Deposition (TA-CVD), evaporation-Induced Self-Assembly (evaporative-Induced Self-Assembly), and physical Vapor transport (pvd) method for modifying the surface of a substrate with a silane coupling agent. The Template-assisted Chemical Vapor Deposition method is most commonly used, and comprises four processes of Template (usually, Anodic Aluminum Oxide, AAO, the preparation method is a two-step Anodic oxidation method) preparation, Chemical Vapor Deposition growth (CVD), Ion-Beam Etching (Ion-Beam Etching) and polished Template Etching (polished Template Etching), wherein the process of the method is complicated and the production cost is high; in addition, since the pore size and pore spacing of the template (often alumina) are limited by a number of factors, the nanowire parameters are limited by the templateThe plate aperture is determined, so that the quality fluctuation of the prepared nanowire array is large, and the obtained vertical nanowire array is incompatible with the current commercial micro-nano processing technology of the semiconductor device, so that the batch manufacturing and on-chip integration of the micro-nano device are difficult to realize by utilizing the vertical nanowire array. The evaporation-induced self-assembly is a method for realizing the preparation and alignment of nanowires in one step on a solid substrate or a liquid-liquid interface, is commonly used for preparing large-area nanowires, has poor controllability (including the controllability of impurities), and is difficult to predict the shape and the periodic interval of a pattern, and in addition, toxic solvents are required to influence the physical health of operators. The silane coupling agent adopted in physical vapor transport for modifying the surface of a substrate through the silane coupling agent is normally Octadecyltrichlorosilane (OTS), the OTS solution is unstable and has a harsh storage environment, so that the performance of the generated nanowire can be influenced, the OTS solution can also adopt a toxic organic solvent, the health of an operator can be influenced, and the method is complicated because the procedures such as photoetching and the like are required to be carried out if the limited-area growth is realized. However, organic semiconductors are generally incompatible with traditional micro-nano processing techniques, and it is difficult for the existing preparation method to obtain aligned Alq₃Nanowires, which resulted in the inability to produce aligned Alq via a "top-down" strategy₃Nanowires hinder the scale fabrication and on-chip integration of organic semiconductor nanowires.

Disclosure of Invention

The present invention is directed to solving at least one of the problems of the prior art described above. Therefore, the invention provides an Alq₃The preparation method of the nanowire horizontal array prepares the Alq with excellent degree of order, uniformity, density, crystallinity and the like through the synergistic effect of the steps₃A horizontal array of nanowires.

The invention also provides Alq obtained by the preparation method₃The application of the nanowire horizontal array in the field of semiconductors.

According to one aspect of the invention, an Alq is provided₃The preparation method of the nanowire horizontal array comprises the following steps:

s1, annealing the M-surface sapphire at 1400-1600 ℃;

s2, carrying out surface treatment on the M-surface sapphire obtained in the step S1 by using organic silicon;

s3, using Alq to₃The powder is used as a raw material, and physical vapor deposition is carried out on the surface of the M-surface sapphire obtained in the step S2.

According to a preferred embodiment of the present invention, at least the following advantages are provided:

(1) compared with a template-assisted chemical vapor deposition method, the preparation method provided by the invention has the advantages that an extra growth template is not required to be prepared, and Alq is directly grown on the M-plane sapphire₃A horizontal array of nanowires; in addition, the complex technologies such as mechanical polishing, ion beam etching and the like are avoided, the production cost and the production period are greatly reduced, and Alq is facilitated₃Large-scale and batch preparation of the nanowire horizontal array; and can generate horizontal arrays;

(2) compared with the evaporation-induced self-assembly method, the preparation method provided by the invention has the advantages that the sapphire is processed in the step S1, so that the in-plane Alq with high orderliness and good controllability can be obtained₃The nanowire horizontal array avoids introducing other impurities in the growth process;

(3) the preparation method provided by the invention comprises the step of annealing treatment in the step S1, and forming V-shaped parallel channels on the surface of the M-surface sapphire substrate for subsequent Alq₃Growth of the horizontal array of nanowires provides a pattern while reducing the defect density and greasy impurities on the M-plane sapphire surface, thus resulting Alq₃The nanowire horizontal array is superior to the three methods in the aspects of order degree, uniformity, density, crystallinity and the like;

(4) according to the preparation method provided by the invention, the Si-O-Al bond can be formed on the surface of the M-surface sapphire substrate by the surface treatment in the step S2, so that the Si-O-Al bond and Alq are improved₃Alq in nanowire horizontal arrays₃Affinity of the nanowires; meanwhile, the bottom of the nano channel of the M-surface sapphire is lower than the top of the channel, and Alq is lower than the top of the channel₃The molecules are preferentially nucleated at the channel position on the surface of the M-plane sapphire and grow along the channel; is Alq₃The molecule preferentially nucleates at the channelAnd ultimately ordered growth along the channel direction provides a key basis.

(5) The preparation method provided by the invention belongs to a physical vapor deposition method, but the annealing treatment of the M-surface sapphire in the step S1 and the surface treatment in the step S2 ensure that the oriented growth Alq is obtained₃Action of nanowires, resulting Alq₃The nanowires can form lines (graph epitaxial growth) along the pattern direction of the M-surface sapphire surface, orderly arranged ordered micro-nano structures can be formed without a post-manufacturing process, and the method is a growth method capable of preparing high-quality ordered nanowire arrays through a simple process. Therefore, although the method also belongs to a physical vapor deposition method, the method has great potential in the aspect of solving the technical problems of scale integration of the organic semiconductor nanowire device and the like, and can scientifically research the process and the general rule of oriented growth of the organic semiconductor.

(6) In conclusion, the invention can synchronously realize the growth of the nanowires and the horizontal ordered arrangement and assembly, and provides an in-plane nanowire array growth technology which is safe in operation, simple in process, economical and practical; the nanowire in-plane array grown by the preparation method provided by the invention has the advantages of high length uniformity, good distribution uniformity, good orientation, high stability, high crystal quality and the like, and the in-plane nanowire array grown by the graphoepitaxy method is compatible with the existing micro-nano processing technology, thereby being beneficial to the large-scale production and on-chip integration of semiconductor micro-nano devices, simplifying the process parameters and reducing the preparation cost.

In some embodiments of the invention, in step S3, the resulting Alq is₃Alq in nanowire horizontal arrays₃The distribution range of the length of the nanowires is 200-400 μm.

In some embodiments of the invention, the Alq is₃The height distribution of the nanowires ranges between 1 and 1.5 μm.

The height is defined as the height of the substrate in the Alq range₃Vertical height of nanowire, about equal to said Alq₃The diameter of the nanowire.

In some embodiments of the invention, in step S3, the physical vapor depositionDeposition of Alq₃The length-diameter ratio of the nanowire is within the range of 100-400.

In some embodiments of the invention, in step S3, the physical vapor deposition deposits Alq₃The nano wires are high-density and uniformly distributed collimation nano wires.

In some embodiments of the invention, the Alq is₃The density of the nanowire horizontal array can reach 50000-100000 roots/cm²。

The density is the distribution density, i.e. the Alq grows in unit area₃The number of nanowires.

In some embodiments of the invention, in step S1, the M-plane sapphire has a crystal plane index of。

When the M-plane sapphire is replaced by other materials such as silicon wafer and C-plane sapphire, the grown non-oriented and curved Alq is obtained₃Nanowires, can not grow to obtain aligned, oriented Alq₃A horizontal array of nanowires.

In some embodiments of the present invention, in step S1, the annealing time is 5-15 h.

In some preferred embodiments of the present invention, in step S1, the annealing process is performed for 10 hours.

In some embodiments of the present invention, the annealing process is performed in a box furnace in step S1.

In some embodiments of the present invention, in step S1, after the annealing treatment, the temperature is naturally reduced (without any intervention of cooling means, only the heating procedure is stopped) to room temperature and then the substrate is taken out.

In some embodiments of the present invention, in step S1, the resulting M-plane sapphire has a surface with "V" shaped parallel horizontal channels.

Said horizontal channel, i.e. corresponding to said Alq₃The pattern (confinement) of nanowire array growth can improve the obtained Alq₃Degree of order of horizontal array of nanowiresUniformity and density.

In some embodiments of the present invention, the method further comprises cleaning the M-plane sapphire obtained in step S1 before step S2.

In some embodiments of the invention, the cleaning is performed by: sequentially carrying out ultrasonic cleaning by using acetone, 95% ethanol and deionized water, and then drying.

In some embodiments of the present invention, the ultrasonic cleaning is performed at an ultrasonic power of 120-.

In some preferred embodiments of the present invention, the ultrasonic cleaning is performed at about 135W.

In some embodiments of the invention, the ultrasonic cleaning is performed for 10-20min each time.

In some preferred embodiments of the present invention, the ultrasonic cleaning is performed for about 10min each time.

In some embodiments of the invention, the drying is by nitrogen purge to remove residual moisture and stains.

In some embodiments of the present invention, in step S2, the silicone is at least one of PDMS (silicone oil, CAS: 63148-62-9) and a silane coupling agent.

In some preferred embodiments of the present invention, in step S2, the silicone is PDMS.

In some embodiments of the present invention, in step S2, the surface treatment is performed by attaching the gel formed by the silicone to the M-plane sapphire obtained in step S1.

In some embodiments of the invention, the attaching is performed for a period of 24 to 96 hours.

In some preferred embodiments of the present invention, the attaching is performed for a period of 30 to 50 hours.

In some preferred embodiments of the invention, the attachment is left for a period of 48 hours.

In step S2, the surface treatment may be performed by using M-plane sapphire (mainly containing Al)₂O₃) Al in the PDMS and silicon-oxygen bonds in the PDMS to generate Si-O-Al bonds, so that the M-surface sapphire and the subsequently formed Alq are improved₃Affinity of the nanowires; in the second aspect, the formation energy of the bottom of the M-plane sapphire nano channel can be reduced, so that Alq is enabled₃Nucleating at the bottom of the nano channel and growing along the channel; in a third aspect, the hydrophobicity of the obtained M-surface sapphire can be improved, so that the M-surface sapphire is more suitable for Alq₃And (4) depositing the nanowire.

In some embodiments of the present invention, in step S3, the physical vapor deposition comprises the steps of:

s3a. mixing Alq₃Powder is placed at the upstream of a quartz tube of the double-temperature-zone tube furnace; placing the M-surface sapphire obtained in the step S2 at the downstream of the quartz tube;

s3b, setting Alq₃The temperature of the powder is 330-360 ℃, and the temperature of the M-surface sapphire is 180-220 ℃; removing carrier gas from said Alq₃And (3) flowing powder to the direction of the M-surface sapphire, and performing the physical vapor deposition.

In some embodiments of the invention, in step S3a, the Alq is₃Powder with a mass of 10-20 mg.

In some preferred embodiments of the present invention, in step S3a, the Alq is₃Powder, mass about 20 mg.

In some embodiments of the invention, in step S3a, the Alq is₃The distance (L) between the powder and the M-plane sapphire is 18-25 cm.

In some preferred embodiments of the present invention, in step S3a, the Alq is₃The distance (L) of the powder from the M-plane sapphire is about 25 cm.

In some embodiments of the present invention, in step S3a, the specific placement method of the M-plane sapphire is: the M-surface sapphire is placed on a groove plate with the height of 8mm, and the M-surface sapphire and the groove plate are placed in a quartz boat with the inner diameter of 29 mm.

The size of the quartz boat is feasible as long as it matches the size of the quartz tube of the tube furnace used, and is therefore not strictly limited to 29 mm.

In the inventionIn some preferred embodiments of (1), in step S3b, the Alq is₃The temperature at the powder was about 350 deg.c.

In some preferred embodiments of the present invention, in step S3b, the temperature of the M-plane sapphire is 200 ℃.

In some embodiments of the invention, in step S3b, the carrier gas is selected from the group consisting of an inert gas and N₂At least one of (1).

In some embodiments of the present invention, in step S3b, the carrier gas has a flow rate of 150sccm and 300 sccm.

In some preferred embodiments of the present invention, in step S3b, the carrier gas has a flow rate of about 150 sccm.

In some embodiments of the present invention, in step S3b, the carrier gas has a pressure of 300-.

In some preferred embodiments of the present invention, in step S3b, the carrier gas has a pressure of about 500 mbar.

In some embodiments of the present invention, in step S3b, the physical vapor deposition is performed for 0.5 to 2 hours.

In some preferred embodiments of the present invention, in step S3b, the time period for physical vapor deposition is about 1 h.

In some embodiments of the present invention, in step S3b, the physical vapor deposition can be performed on Alq by controlling the deposition conditions (i.e., substrate temperature, growth time, and carrier gas volume flow rate)₃And regulating and controlling the length, height and density of the nanowire.

According to still another aspect of the present invention, Alq prepared by the above preparation method is provided₃The application of the nanowire horizontal array in the field of semiconductors.

The application according to a preferred embodiment of the invention has at least the following advantageous effects:

(1) alq obtained by the invention₃The nanowire horizontal array is an array formed by directional assembly in a plane, so that the nanowire horizontal array is compatible with the existing semiconductor micro-nano processing technology, and the difficulty of subsequent semiconductor processing is reduced; meanwhile, Alq therein₃The nano-wire has a collimated growth direction, and the comprehensive performance of the obtained semiconductor can be improved.

In some embodiments of the invention, the semiconductor comprises at least one of a photodetector, an Organic Field Effect Transistor (OFET), an organic photovoltaic cell (OSC), and an Organic Light Emitting Diode (OLED).

The photoelectric detector is a semiconductor device for detecting the existence of photons, an optical signal can be converted into an electric signal, the photoconductive type photoelectric detector is one of the photoelectric detectors, when light irradiates the surface of a semiconductor, and excess carriers are generated in the semiconductor, the conductivity of the material is increased, namely, the photoelectric signal is generated, the photoconductive type photoelectric detector has a simple structure and is easy to prepare, and the large-scale production and integration of the nanowire-oriented photoelectric detector are favorably realized₃Preferred application areas for horizontal arrays of nanowires.

Drawings

The invention is further described with reference to the following figures and examples, in which:

FIG. 1 is a schematic flow chart of example 1 of the present invention and the positions of raw materials during physical vapor deposition;

FIG. 2 is an SEM photograph of an M-plane sapphire material used in example 1 of the present invention;

FIG. 3 is an SEM photograph of M-plane sapphire obtained in step D1 of example 1;

FIG. 4 shows Alq obtained in example 1 of the present invention₃SEM images of horizontal arrays of nanowires;

FIG. 5 shows Alq obtained in example 2 of the present invention₃SEM images of horizontal arrays of nanowires;

FIG. 6 shows Alq obtained in example 3 of the present invention₃SEM images of horizontal arrays of nanowires;

FIG. 7 shows Alq in comparative example 1 of the present invention₃SEM images of horizontal arrays of nanowires;

FIG. 8 shows Alq in comparative example 2 of the present invention₃SEM images of horizontal arrays of nanowires;

FIG. 9 is an AFM of M-plane sapphire from step D1 of example 1;

FIG. 10 is an AFM of M-plane sapphire from step D5 of example 1;

FIG. 11 is a graph showing the contact angles of M-plane sapphire obtained in step D3 and step D4 according to example 1 of the present invention;

FIG. 12 shows Alq used in example 1 of the present invention₃Powder and Alq obtained₃Alq in nanowire horizontal arrays₃XRD pattern of the nanowires.

Detailed Description

The concept and technical effects of the present invention will be clearly and completely described below in conjunction with the embodiments to fully understand the objects, features and effects of the present invention. It is obvious that the described embodiments are only a part of the embodiments of the present invention, and not all embodiments, and those skilled in the art can obtain other embodiments without inventive effort based on the embodiments of the present invention, and all embodiments are within the protection scope of the present invention.

If the first and second are described for the purpose of distinguishing technical features, they are not to be understood as indicating or implying relative importance or implicitly indicating the number of technical features indicated or implicitly indicating the precedence of the technical features indicated. In the description of the present invention, reference to the description of the terms "one embodiment," "some embodiments," "an illustrative embodiment," "an example," "a specific example," or "some examples," etc., means that a particular feature, structure, material, or characteristic described in connection with the embodiment or example is included in at least one embodiment or example of the present invention. In this specification, the schematic representations of the terms used above do not necessarily refer to the same embodiment or example. Furthermore, the particular features, structures, materials, or characteristics described may be combined in any suitable manner in any one or more embodiments or examples.

Unless otherwise specified, in the detailed description, the information of the instruments and materials used is as follows:

tube furnace for physical vapor deposition: TF1200-60 type tubular furnace of Shanghai micro-industry Co., Ltd;

quartz tube for physical vapor deposition method: the outer diameter, the inner diameter and the length of the quartz tube are respectively 35mm, 29mm and 1500 mm;

in the physical vapor deposition method, a flow meter for controlling the flow rate of the carrier gas: D08-4E type flow display instrument and D07-19B type mass flow controller of Beijing seven-star Huachuang flow meter, Inc.;

weighing scales for raw materials: electronic balance model ME103E/02 of the Metler-Tollido instruments (Shanghai) YouLimit company;

an ultrasonic cleaning machine: BILON6-180 model ultrasonic cleaning machine of Shanghai Bilang instruments manufacturing company;

PDMS gel: chip storage cases from paradise electronics;

Alq₃powder: tris (8-hydroxyquinoline) aluminum available from Alfa Aesar having a purity of 99%.

Example 1

This example prepares an Alq₃The horizontal array of the nano-wire comprises the following specific processes:

D1. putting two-inch (diameter) M-surface sapphire into a box furnace, heating to 1600 ℃, and carrying out annealing treatment after heat preservation for 10 hours; after the cooling, the mixture is naturally cooled to room temperature and taken out;

D2. cutting the annealed M-plane sapphire into pieces with maximum surface area of 1 × 1cm²Square shape of the substrate to facilitate subsequent Physical Vapor Deposition (PVD) growth of Alq₃A horizontal array of nanowires;

D3. putting the cut M-surface sapphire into a beaker, and sequentially carrying out ultrasonic cleaning by using acetone, 95% ethanol and deionized water, wherein the cleaning time is 10min each time, and the ultrasonic power is 135W, so as to remove impurities attached to oil stains on the surface of the M-surface sapphire;

D4. attaching PDMS and the M-plane sapphire obtained in the step D3 for 24 h;

D5. with Alq₃Depositing Alq on the M-surface sapphire obtained in the step D4 by using a physical vapor deposition method in a tube furnace by using the powder as a raw material₃A horizontal array of nanowires; the method comprises the following specific steps:

d5a. weighing 20mg Alq₃Powder is placed at the upstream of a quartz tube of the double-temperature-zone tube furnace; d4, placing the M-surface sapphire obtained in the step D4 at the downstream of the quartz tube; alq₃The distance between the powder and the M-surface sapphire is 25 cm;

the specific placement method of the M-surface sapphire comprises the following steps: the M-surface sapphire is placed on a groove plate with the height of 8mm, and the M-surface sapphire and the groove plate are placed in a quartz boat with the inner diameter of 29 mm;

d5b. setting temperature to Alq₃The temperature of the powder is 350 ℃, and the temperature of the M-surface sapphire is 200 ℃; with N₂From Alq as carrier gas₃Powder to M-plane sapphire direction transport; the carrier gas flow was 150sccm, the pressure was 500mbar, and the growth time was 1 h.

The flow chart of the embodiment is shown in fig. 1;

in step D5 of this embodiment, the placement positions of the devices are as shown in fig. 1.

Example 2

This example prepares an Alq₃The difference between the specific process of the horizontal array of nanowires and the example 1 is as follows:

(1) in step D4, the patch was left for 48 h.

Example 3

This example prepares an Alq₃The difference between the specific process of the horizontal array of nanowires and the example 1 is as follows:

(1) in step D4, the patch was left for 96 h.

Comparative example 1

This comparative example prepared an Alq₃The difference between the specific process of the horizontal array of nanowires and the example 1 is as follows:

(1) step D4 is not performed.

Comparative example 2

This comparative example prepared an Alq₃The difference between the specific process of the horizontal array of nanowires and the example 1 is as follows:

(1) step D1 is not performed.

Test examples

First aspect of the present test example M-plane sapphire as a raw material and obtained after the step S1 treatment in example 1, and Alq as obtained in examples 1 to 3 and comparative examples 1 to 2 were tested₃The shape of the nanowire horizontal array is tested by the following method: scanning by ZEISS Gemini500 field emissionThe electron microscope was measured at an accelerating voltage of 2.00 kV. The test results are shown in FIGS. 2 to 8.

The comparison of the results of FIG. 2 and FIG. 3 shows that after the annealing treatment of step D1, a single-orientation V-shaped channel is spontaneously formed on the surface of the M-plane sapphire, and the crystal plane index of the channel isThis is the subsequent Alq₃The directional growth of the horizontal array of nanowires provides a patterned template.

FIGS. 4-6 show that Alq prepared within the parameters provided by the present invention₃The density (namely the number of the guide nanowires and the collimation nanowires on the substrate with the same specification), the distribution uniformity, the length uniformity and the guidance quality of the collimation nanowires are greatly improved; and the longer the surface modification treatment time (longest in example 3, corresponding to FIG. 6), the longer Alq₃The better the horizontal array growth of nanowires.

As is clear from comparison of FIGS. 4 to 6 with FIGS. 7 to 8, when the surface modification treatment is not performed or the heat treatment in step D1 is not performed when M-plane sapphire is used as the substrate, Alq is obtained₃Although the nanowires are also arranged in a one-dimensional linear mode, the nanowires are scattered and disordered in distribution, and the batch manufacturing and on-chip integration of the micro-nano devices are not met.

Second aspect of this test example M-plane sapphire obtained in step D1 of example 1 and Alq obtained in example 1 were tested₃The AFM images of the nanowire horizontal array are shown in FIGS. 9-10, and the test results of FIG. 9 correspond to the SEM images of FIGS. 2-3, which further proves that the heat treatment of step D1 can form a single-orientation V-shaped channel on the surface of the M-plane sapphire; the results of fig. 10 correspond to fig. 4, illustrating that the cross-sectional diameter of the resulting nanowire is about 1 μm.

In the third aspect of this experimental example, before and after step D4 in example 1, the hydrophobic property pattern of M-plane sapphire was measured, and the test results are shown in fig. 11, where: after surface modification treatment, the contact angle between the M-surface sapphire and water drops is obviously increased, and the hydrophobicity is enhanced.

Fourth aspect of this Experimental example Alq used in example 1 was tested₃Powder and Alq obtained₃The XRD spectrum of the nanowire horizontal array is tested by the following method: measured by a BRPUKER D8ADVANCE X-ray polycrystal diffractometer at an acceleration voltage of 40kV, and the test results are shown in FIG. 12.

FIG. 12 shows the results of the tests, in which Alq prepared by the present invention₃The nanowire horizontal array has high crystallinity and high crystal quality.

In conclusion, the above results show that Alq prepared by the invention₃The density, distribution uniformity, length uniformity, guiding property and crystallinity of the nanowire horizontal array are all excellent, and the application requirements in the fields of photoelectric detectors, Organic Field Effect Transistors (OFETs), organic photovoltaic cells (OSCs), Organic Light Emitting Diodes (OLEDs) and the like are met.

The embodiments of the present invention have been described in detail with reference to the accompanying drawings, but the present invention is not limited to the above embodiments, and various changes can be made within the knowledge of those skilled in the art without departing from the gist of the present invention. Furthermore, the embodiments of the present invention and the features of the embodiments may be combined with each other without conflict.