CN113881918B - Metal phthalocyanine nanowire array and preparation method and application thereof - Google Patents
Metal phthalocyanine nanowire array and preparation method and application thereof Download PDFInfo
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- 239000002070 nanowire Substances 0.000 title claims abstract description 183
- IEQIEDJGQAUEQZ-UHFFFAOYSA-N phthalocyanine Chemical compound N1C(N=C2C3=CC=CC=C3C(N=C3C4=CC=CC=C4C(=N4)N3)=N2)=C(C=CC=C2)C2=C1N=C1C2=CC=CC=C2C4=N1 IEQIEDJGQAUEQZ-UHFFFAOYSA-N 0.000 title claims abstract description 158
- 239000002184 metal Substances 0.000 title claims abstract description 146
- 229910052751 metal Inorganic materials 0.000 title claims abstract description 146
- 238000002360 preparation method Methods 0.000 title claims abstract description 31
- 239000000758 substrate Substances 0.000 claims abstract description 155
- 229910052594 sapphire Inorganic materials 0.000 claims abstract description 149
- 239000010980 sapphire Substances 0.000 claims abstract description 149
- 230000002209 hydrophobic effect Effects 0.000 claims abstract description 81
- 238000000034 method Methods 0.000 claims abstract description 70
- 238000005240 physical vapour deposition Methods 0.000 claims abstract description 24
- 239000010437 gem Substances 0.000 claims abstract description 4
- 229910001751 gemstone Inorganic materials 0.000 claims abstract description 4
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 99
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 88
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 80
- 229910052757 nitrogen Inorganic materials 0.000 claims description 49
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 claims description 27
- 238000004140 cleaning Methods 0.000 claims description 25
- RBTKNAXYKSUFRK-UHFFFAOYSA-N heliogen blue Chemical compound [Cu].[N-]1C2=C(C=CC=C3)C3=C1N=C([N-]1)C3=CC=CC=C3C1=NC([N-]1)=C(C=CC=C3)C3=C1N=C([N-]1)C3=CC=CC=C3C1=N2 RBTKNAXYKSUFRK-UHFFFAOYSA-N 0.000 claims description 23
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- MIINHRNQLVVCEW-UHFFFAOYSA-N 132-16-1 Chemical compound [Fe+2].C12=CC=CC=C2C(N=C2[N-]C(C3=CC=CC=C32)=N2)=NC1=NC([C]1C=CC=CC1=1)=NC=1N=C1[C]3C=CC=CC3=C2[N-]1 MIINHRNQLVVCEW-UHFFFAOYSA-N 0.000 claims description 12
- MPMSMUBQXQALQI-UHFFFAOYSA-N cobalt phthalocyanine Chemical compound [Co+2].C12=CC=CC=C2C(N=C2[N-]C(C3=CC=CC=C32)=N2)=NC1=NC([C]1C=CC=CC1=1)=NC=1N=C1[C]3C=CC=CC3=C2[N-]1 MPMSMUBQXQALQI-UHFFFAOYSA-N 0.000 claims description 12
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 claims description 11
- WDEQGLDWZMIMJM-UHFFFAOYSA-N benzyl 4-hydroxy-2-(hydroxymethyl)pyrrolidine-1-carboxylate Chemical compound OCC1CC(O)CN1C(=O)OCC1=CC=CC=C1 WDEQGLDWZMIMJM-UHFFFAOYSA-N 0.000 claims description 11
- 239000003153 chemical reaction reagent Substances 0.000 claims description 11
- 239000012299 nitrogen atmosphere Substances 0.000 claims description 11
- 229910052725 zinc Inorganic materials 0.000 claims description 11
- 239000011701 zinc Substances 0.000 claims description 11
- 238000000137 annealing Methods 0.000 claims description 9
- 238000000151 deposition Methods 0.000 claims description 9
- 230000005693 optoelectronics Effects 0.000 claims description 8
- 230000008021 deposition Effects 0.000 claims description 7
- -1 perfluoro copper phthalocyanine Chemical compound 0.000 claims description 6
- 239000012298 atmosphere Substances 0.000 claims description 4
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- 125000001165 hydrophobic group Chemical group 0.000 description 4
- VVOPUZNLRVJDJQ-UHFFFAOYSA-N phthalocyanine copper Chemical class [Cu].C12=CC=CC=C2C(N=C2NC(C3=CC=CC=C32)=N2)=NC1=NC([C]1C=CC=CC1=1)=NC=1N=C1[C]3C=CC=CC3=C2N1 VVOPUZNLRVJDJQ-UHFFFAOYSA-N 0.000 description 4
- 230000009286 beneficial effect Effects 0.000 description 3
- 229910052802 copper Inorganic materials 0.000 description 3
- 239000010949 copper Substances 0.000 description 3
- XCJYREBRNVKWGJ-UHFFFAOYSA-N copper(II) phthalocyanine Chemical compound [Cu+2].C12=CC=CC=C2C(N=C2[N-]C(C3=CC=CC=C32)=N2)=NC1=NC([C]1C=CC=CC1=1)=NC=1N=C1[C]3C=CC=CC3=C2[N-]1 XCJYREBRNVKWGJ-UHFFFAOYSA-N 0.000 description 3
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- PYJJCSYBSYXGQQ-UHFFFAOYSA-N trichloro(octadecyl)silane Chemical compound CCCCCCCCCCCCCCCCCC[Si](Cl)(Cl)Cl PYJJCSYBSYXGQQ-UHFFFAOYSA-N 0.000 description 3
- 239000011248 coating agent Substances 0.000 description 2
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- 229910018072 Al 2 O 3 Inorganic materials 0.000 description 1
- 102100028292 Aladin Human genes 0.000 description 1
- 101710065039 Aladin Proteins 0.000 description 1
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 1
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- 238000002207 thermal evaporation Methods 0.000 description 1
- 231100000701 toxic element Toxicity 0.000 description 1
- 239000003440 toxic substance Substances 0.000 description 1
- 238000007740 vapor deposition Methods 0.000 description 1
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- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C14/00—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material
- C23C14/06—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material characterised by the coating material
- C23C14/12—Organic material
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B82—NANOTECHNOLOGY
- B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
- B82Y30/00—Nanotechnology for materials or surface science, e.g. nanocomposites
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B82—NANOTECHNOLOGY
- B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
- B82Y40/00—Manufacture or treatment of nanostructures
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- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C14/00—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material
- C23C14/02—Pretreatment of the material to be coated
- C23C14/024—Deposition of sublayers, e.g. to promote adhesion of the coating
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- H—ELECTRICITY
- H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
- H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
- H10K71/00—Manufacture or treatment specially adapted for the organic devices covered by this subclass
- H10K71/10—Deposition of organic active material
- H10K71/16—Deposition of organic active material using physical vapour deposition [PVD], e.g. vacuum deposition or sputtering
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- Organic Chemistry (AREA)
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- Physics & Mathematics (AREA)
- Condensed Matter Physics & Semiconductors (AREA)
- General Physics & Mathematics (AREA)
- Manufacturing & Machinery (AREA)
- Crystallography & Structural Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Composite Materials (AREA)
- Crystals, And After-Treatments Of Crystals (AREA)
Abstract
The invention discloses a metal phthalocyanine nanowire array and a preparation method and application thereof, wherein the preparation method of the metal phthalocyanine nanowire array comprises the following steps: s1, taking a precious stone with a channel array on the surface as a substrate, and performing hydrophobic treatment on the channel array; s2, taking metal phthalocyanine, and forming a plurality of metal phthalocyanine nanowires on the surface of the substrate treated in the step S1 through physical vapor deposition to obtain a metal phthalocyanine nanowire array. According to the preparation method disclosed by the invention, the sapphire substrate with the channel array on the surface is subjected to surface hydrophobic treatment, and then the metal phthalocyanine nanowire array is grown by combining the traditional PVD (physical vapor deposition) growth method, so that the prepared metal phthalocyanine nanowire array is ordered in level, straight in orientation, few in defects, simple in preparation flow and low in cost, can be used for large-scale production, and provides an ideal material platform for developing various micro-nano photoelectric devices based on batch construction of the metal phthalocyanine nanowire.
Description
Technical Field
The invention relates to the technical field of nano materials, in particular to a metal phthalocyanine nanowire array and a preparation method and application thereof.
Background
The highly ordered nanowire array is a precondition for realizing the large-scale manufacture, batch test and efficient research and development of nanowire functional devices (field effect transistors, photovoltaic cells, sensors and the like). Compared with inorganic semiconductor nanowires, the semiconductor nanowires formed by organic molecules have better flexibility and scalability, unique pi-pi conjugated bonds and charge carrier transmission established according to molecular stacking orientation, so the organic semiconductor nanowires are ideal material systems for developing flexible devices with excellent performance, and particularly for flexible wearable electronic equipment, the inorganic semiconductor nanowires contain sulfur, lead and other toxic elements, are not suitable for manufacturing the wearable electronic equipment, and the organic semiconductor nanowires basically do not contain toxic substances, so the manufactured wearable electronic equipment does not have any harm to human bodies. Most of the organic semiconductor nanowires reported in the literature are randomly oriented, however, it is highly desirable to assemble organic molecules into highly ordered nanowire arrays for performance applications that enhance the functioning of the organic nanowire device.
The metal phthalocyanine system is a branch of pi conjugated molecule family, is an organic semiconductor molecule which has been widely studied, wherein zinc phthalocyanine (ZnPc), copper phthalocyanine (CuPc), cobalt phthalocyanine (CoPc), nickel phthalocyanine (NiPc), ferrous phthalocyanine (FePc) and the like are p-type semiconductors, and perfluoro copper phthalocyanine (F) 16 CuPc) is an n-type semiconductor. The metal phthalocyanine system has wide application prospect in photoelectric, thermoelectric, photovoltaic and other aspects, and is an active element of various photon devices, organic Field Effect Transistors (OFETs), photoelectric transistors and solar cells. In addition, the metal phthalocyanine system can be applied to organic-inorganic hybrid devices such as: hybrid p-n junction diode and hybrid photoelectric detectionA device, etc.
Nowadays, there are various methods for preparing metal phthalocyanine organic nanowire in-plane arrays, wherein the two-step preparation method is one of the more commonly used methods, and specifically may be: the first step is to form metal phthalocyanine nanowires in a dual temperature zone tube furnace without carrier gas by adopting a traditional Physical Vapor Deposition (PVD) method; and secondly, arranging the prepared metal phthalocyanine nanowires into nanowire in-plane arrays by a Langmuir-Blodgett (LB) method. Nanowires arranged by the LB method are bent to a certain extent, the disorder degree of the nanowire array is high, and the surface defects of the nanowires are more.
Disclosure of Invention
The present invention aims to solve at least one of the technical problems existing in the prior art. Therefore, the invention provides a preparation method of a metal phthalocyanine nanowire array, and the metal phthalocyanine nanowire array prepared by the method has the characteristics of ordered height level, straight orientation and few defects.
The invention also provides a metal phthalocyanine nanowire array prepared by the method.
The invention also provides application of the metal phthalocyanine nanowire array.
In a first aspect of the present invention, a method for preparing a metal phthalocyanine nanowire array is provided, including the following steps:
s1, taking a precious stone with a channel array on the surface as a substrate, and performing hydrophobic treatment on the channel array;
s2, taking metal phthalocyanine, and forming a plurality of metal phthalocyanine nanowires on the surface of the substrate treated in the step S1 through physical vapor deposition to obtain a metal phthalocyanine nanowire array.
The preparation method of the metal phthalocyanine nanowire array provided by the embodiment of the invention has at least the following beneficial effects: in the Physical Vapor Deposition (PVD) growth process, metal phthalocyanine vapor molecules preferentially form nuclei along the channel direction of the sapphire substrate channel array, hydrophobic treatment leads hydrophobic groups introduced on the surface of the substrate to strengthen the hydrophobicity of the substrate, so that the substrate can absorb nonpolar molecules more easily, and the absorption and the extension of the metal phthalocyanine vapor molecules on the sapphire substrate are more facilitated. The finally prepared metal phthalocyanine nanowire in-plane array is orderly and horizontally oriented, uniform in diameter, high in density, few in defects, low in array disorder degree, few in surface defects and high in repeatability, and the length of the finally prepared metal phthalocyanine nanowire can reach between tens of micrometers and hundreds of micrometers. The preparation process is simple, the growth and ordered arrangement of the metal phthalocyanine nanowires can be synchronously realized by the simple process, the preparation process of the nanowire array is greatly simplified on the premise of greatly reducing the cost, and the crystallization quality, the uniformity of the wire diameter and the order degree of the nanowires are improved. Meanwhile, in the preparation process of the metal phthalocyanine nanowire array, a subsequent nanowire alignment step is not needed, the damage to the nanowire in the alignment process is avoided, and the surface defect of the nanowire is less, so that the optimal performance of the nanowire is ensured.
The invention can realize large-scale preparation of the high-quality metal phthalocyanine nanowire array by enlarging the size of the growth substrate, has simple flow and low cost, can be used for large-scale production, has high repeatability, can build micro-nano photoelectric devices in batches by means of a commercial micro-nano processing technology, is hopeful to improve the performance surface of the devices, and provides an ideal material platform for developing various micro-nano photoelectric devices based on the mass construction of the metal phthalocyanine nanowire. Meanwhile, the metal phthalocyanine nanowire array prepared by the method can be an ideal material of a flexible device, and particularly can be applied to flexible wearable electronic equipment, and has wide application range and good application prospect.
In some embodiments of the invention, the gemstone comprises sapphire.
In some preferred embodiments of the invention, the sapphire is M-plane sapphire.
In some preferred embodiments of the invention, the sapphire surface has an array of horizontal channels.
In some preferred embodiments of the invention, the sapphire surface has an array of micro-nano channels.
In some preferred embodiments of the invention, the sapphire surface has an array of micro-nano horizontal channels.
In some embodiments of the invention, the metal phthalocyanine comprises at least one of zinc phthalocyanine, cobalt phthalocyanine, copper phthalocyanine, perfluoro copper phthalocyanine, ferrous phthalocyanine, or nickel phthalocyanine.
In some embodiments of the invention, the metal phthalocyanine is a metal phthalocyanine powder.
In some embodiments of the present invention, in step S1, M-plane sapphire is annealed to obtain sapphire having an array of channels on the surface.
By the above embodiment, the M-plane sapphire (i.e., α -Al 2 O 3 Orientation of crystal planes) After annealing the single crystal wafer, the surface of the annealed M-plane sapphire substrate has been provided with an array of channels (in the direction +.>A horizontal channel array structure with the interval between adjacent channels of 50-150nm and the included angle between the adjacent channel forming surfaces of 100-140 degrees), and the channel array plays a role in guiding in the growth process of the nano wires. The M-plane sapphire after annealing treatment is subjected to hydrophobic treatment, metal phthalocyanine gas-phase molecules can preferentially nucleate and grow along the channel direction in the Physical Vapor Deposition (PVD) growth process, hydrophobic groups introduced on the surface of the substrate are enhanced by the hydrophobic treatment, the sapphire substrate is enabled to absorb nonpolar molecules more easily, and the adsorption and the extension of the metal phthalocyanine gas-phase molecules on the sapphire substrate are facilitated. The finally prepared metal phthalocyanine nanowire in-plane array is orderly and horizontally oriented, uniform in diameter, high in density, few in defects, low in array disorder degree, few in surface defects and high in repeatability, and the length of the finally prepared metal phthalocyanine nanowire can reach between tens of micrometers and hundreds of micrometers.
According to the invention, the surface of the annealed M-plane sapphire substrate is subjected to hydrophobic treatment, and then the metal phthalocyanine nanowire array is formed by combining with a PVD (physical vapor deposition) growth method, so that the preparation flow is simple, the subsequent nanowire alignment step is not needed, the damage to the nanowire in the alignment process is avoided, the surface defect of the nanowire is less, and the optimal performance of the nanowire is ensured.
The invention can realize large-scale preparation of the high-quality metal phthalocyanine nanowire array by enlarging the size of the growth substrate, has simple flow and low cost, can be used for large-scale production, has high repeatability, can build micro-nano photoelectric devices in batches by means of a commercial micro-nano processing technology, is hopeful to improve the performance surface of the devices, and provides an ideal material platform for developing various micro-nano photoelectric devices based on the mass construction of the metal phthalocyanine nanowire.
In some embodiments of the present invention, in step S1, after the M-plane sapphire is pre-cleaned, an annealing treatment is performed.
In some preferred embodiments of the present invention, in step S1, after the M-plane sapphire is pre-cleaned, a high temperature annealing treatment is performed.
In some more preferred embodiments of the present invention, in step S1, the sapphire pre-cleaning includes: the sapphire was ultrasonically cleaned with acetone.
Through the implementation mode, acetone is used for ultrasonic cleaning, oil stains on the surface of the sapphire are removed, the surface is dried by dry nitrogen, and residual organic solvent is removed.
In some more preferred embodiments of the present invention, in step S1, the sapphire pre-cleaning includes: and (3) ultrasonically cleaning the sapphire with acetone, and drying with nitrogen.
In some preferred embodiments of the present invention, in step S1, the high temperature annealing process includes: raising the temperature to 1550-1650 ℃ at the speed of 8-12 ℃/min, keeping the temperature for 9-11h, and cooling to room temperature.
In some preferred embodiments of the present invention, in step S1, the high temperature annealing process includes: and (3) placing the M-plane sapphire into a high-temperature box type furnace, heating to 1550-1650 ℃ at the speed of 8-12 ℃/min, keeping the temperature for 9-11h, and cooling to room temperature.
In some preferred embodiments of the present invention, in step S1, the high temperature annealing process includes: and (3) placing the M-plane sapphire into a high-temperature box furnace, raising the temperature to about 1600 ℃ at the speed of about 10 ℃/min, keeping the temperature for about 10 hours, and cooling to the room temperature.
In some embodiments of the present invention, in step S1, the annealed sapphire is subjected to a hydrophobic treatment after being first washed.
In some preferred embodiments of the present invention, in step S1, the first cleaning step of the sapphire is: sequentially ultrasonically cleaning the sapphire with ethanol, acetone, ethanol, water and ethanol.
In some preferred embodiments of the present invention, in step S1, the first cleaning step of the sapphire is: sequentially ultrasonically cleaning the sapphire with ethanol, acetone, ethanol, water and ethanol, and drying with nitrogen.
Through the above embodiment, the surface oil dirt and impurities are removed by ultrasonic cleaning, and nitrogen blow-drying is performed by adopting a nitrogen gun.
In some more preferred embodiments of the present invention, in the first cleaning step of the sapphire in step S1, the sapphire is sequentially ultrasonically cleaned with ethanol, acetone, ethanol, water, and ethanol, respectively, for 5-15min.
In some more preferred embodiments of the present invention, in the first cleaning step of the sapphire in step S1, the sapphire is sequentially ultrasonically cleaned with ethanol, acetone, ethanol, water, and ethanol, respectively, for 10 minutes.
In some embodiments of the invention, the M-plane sapphire is an M-plane sapphire single crystal wafer.
In some preferred embodiments of the invention, the annealed sapphire wafer surface has a surface orientationAnd the interval between adjacent channels is 50-150nm, and the included angle between the adjacent channel forming surfaces is 100-140 degrees.
In some preferred embodiments of the present invention, the annealed sapphire wafer is cut to a size of 1cm×1cm for use as a substrate.
In some embodiments of the present invention, in step S1, the substrate is subjected to a hydrophobic treatment using a hydrophobic reagent.
In some preferred embodiments of the present invention, the hydrophobic treatment time is 1 to 3 hours in step S1.
In some preferred embodiments of the present invention, the hydrophobic treatment time is 1 to 2 hours in step S1.
In some preferred embodiments of the present invention, the hydrophobic treatment time is about 2 hours in step S1.
In some preferred embodiments of the present invention, in step S1, the hydrophobic reagent comprises a silylating reagent.
In some more preferred embodiments of the present invention, in step S1, the hydrophobic agent comprises OTS.
Wherein OTS is n-octadecyl trichlorosilane.
In some more preferred embodiments of the present invention, in step S1, the hydrophobic reagent comprises a mixture of OTS and n-hexane.
In some preferred embodiments of the present invention, in step S1, the substrate is immersed in a hydrophobic agent to be subjected to a hydrophobic treatment.
In some more preferred embodiments of the present invention, in step S1, the substrate is immersed in a mixed solution of OTS and n-hexane to be subjected to a hydrophobic treatment.
Through the embodiment, the OTS solution is used for carrying out the hydrophobic treatment on the sapphire substrate, so that the contact angle between the surface of the sapphire substrate and water can be increased, and meanwhile, the horizontal channel on the sapphire substrate is used as a micro-nano structure, so that the hydrophobicity of the surface can be amplified. The enhanced hydrophobicity of the sapphire substrate makes the sapphire substrate easier to adsorb nonpolar molecules, and is favorable for the adsorption and extension of metal phthalocyanine gaseous molecules on the sapphire substrate. And the surface energy at the channel is higher, and the transported gaseous molecules are easier to deposit at the channel, so that the metal phthalocyanine gaseous molecules preferentially nucleate and grow along the channel direction to form a nanowire array for guiding growth.
In some more preferred embodiments of the present invention, in step S1, the hydrophobic agent is a mixed solution of OTS and n-hexane.
In some more preferred embodiments of the present invention, in step S1, the ratio of OTS to n-hexane is about 1:1000 by volume.
In some embodiments of the present invention, in step S1, the substrate is subjected to a hydrophobic treatment under anhydrous conditions.
In some embodiments of the invention, in step S1, the hydrophobic agent is isolated from air during the hydrophobic treatment.
With the above embodiment, the container (e.g., beaker) containing the hydrophobic agent can be sealed during the hydrophobic treatment process to prevent the moisture in the air from reacting with the hydrophobic agent.
In some embodiments of the present invention, in step S1, after the hydrophobic treatment, the substrate is subjected to a second cleaning and nitrogen blow-drying.
In some preferred embodiments of the present invention, in step S1, the second cleaning comprises rinsing the substrate with acetone.
With the above embodiment, the sapphire substrate after the hydrophobic treatment is washed with acetone in order to prevent the residual solution of the sapphire substrate from reacting with moisture in the air to contaminate the substrate.
In some more preferred embodiments of the present invention, in step S1, the second cleaning includes rinsing the substrate with acetone, ethanol, and water, respectively.
In some more preferred embodiments of the present invention, in step S1, the second cleaning includes rinsing the substrate with acetone, ethanol, and water sequentially.
Through the embodiment, the substrate after the hydrophobic treatment is taken out of the hydrophobic reagent (such as OTS solution), is quickly washed by acetone, ethanol and water in sequence, and is then dried by a nitrogen gun.
In some embodiments of the present invention, in step S2, the physical vapor deposition specifically includes: firstly gasifying metal phthalocyanine in a source temperature region, and then depositing a plurality of metal phthalocyanine nanowires on the surface of a substrate in a growth temperature region, wherein the temperature of the growth temperature region is lower than that of the source temperature region.
In some preferred embodiments of the present invention, in step S2, the source temperature zone temperature is 420-480 ℃ and the growth temperature zone temperature is 220-280 ℃.
In some more preferred embodiments of the present invention, in step S2, the source temperature zone temperature is 440-450 ℃ and the growth temperature zone temperature is 240-270 ℃.
In some more preferred embodiments of the present invention, in step S2, the source temperature zone temperature is 440-450 ℃ and the growth temperature zone temperature is 240-260 ℃.
In some more preferred embodiments of the present invention, in step S2, the source temperature zone temperature is about 450 ℃, and the growth temperature zone temperature is about 250 ℃.
In some embodiments of the invention, in step S2, the deposition time is 60-180min.
In some preferred embodiments of the present invention, the time of the deposition is 90 to 150 minutes in step S2.
In some more preferred embodiments of the present invention, the time of deposition in step S2 is about 150 minutes.
In some more preferred embodiments of the present invention, in step S2, the source temperature zone temperature is about 450 ℃, the growth temperature zone temperature is about 250 ℃, and the physical vapor deposition time is about 150 minutes.
In some preferred embodiments of the present invention, in step S2, the metal phthalocyanine and the hydrophobically treated substrate are placed in a source temperature zone and a growth temperature zone, respectively.
In some more preferred embodiments of the present invention, in step S2, the distance of the metal phthalocyanine from the substrate is 12.5 to 19cm.
In some more preferred embodiments of the present invention, in step S2, the metal phthalocyanine is spaced from the substrate by a distance of 12.5 to 14cm.
In some more preferred embodiments of the present invention, in step S2, the distance of the metal phthalocyanine from the substrate is 17-19cm.
In some more preferred embodiments of the present invention, in step S2, the metal phthalocyanine is spaced from the substrate by about 18cm.
In some more preferred embodiments of the present invention, in step S2, the metal phthalocyanine and the substrate are located in the source temperature region and the growth temperature region, respectively, and the metal phthalocyanine is located at a distance of about 18cm from the substrate.
In some more preferred embodiments of the present invention, in step S2, the mass of the metal phthalocyanine is 10-15mg, the metal phthalocyanine and the substrate are located in the source temperature zone and the growth temperature zone, respectively, and the metal phthalocyanine is located at a distance of 12.5-19cm from the substrate.
In some preferred embodiments of the present invention, in step S2, the metal phthalocyanine nanowire is formed under a protective gas atmosphere.
In some more preferred embodiments of the present invention, in step S2, the shielding gas is nitrogen or an inert gas.
In some more preferred embodiments of the present invention, the flow rate of nitrogen gas in step S2 is 50-200sccm.
In some more preferred embodiments of the invention, the gas pressure of the protective gas atmosphere is between 10 and 20mbar.
In some more preferred embodiments of the invention, the flow rate of nitrogen is about 50sccm and the pressure of the nitrogen atmosphere is about 10mbar.
In some more preferred embodiments of the invention, in step S2, the flow rate of nitrogen is 50-200sccm and the pressure of the nitrogen atmosphere is 10-20mbar.
In some more preferred embodiments of the invention, in step S2, the flow rate of nitrogen is 45-55sccm and the pressure of the nitrogen atmosphere is 9-11mbar.
In some more preferred embodiments of the invention, in step S2, the flow rate of nitrogen is about 50sccm and the pressure of the nitrogen atmosphere is about 10mbar.
In some embodiments of the present invention, in step S2, using the sapphire obtained in step S1 as a substrate, forming metal phthalocyanine nanowires in a dual-temperature-zone device by using a physical vapor deposition method, thereby obtaining a metal phthalocyanine nanowire array.
In some preferred embodiments of the present invention, in step S2, the dual temperature zone device is a sliding rail dual temperature zone tube furnace.
In some preferred embodiments of the present invention, in step S2, the metal phthalocyanine is placed in a quartz boat, and then, the substrate after the hydrophobic treatment is placed in a source temperature zone and a growth temperature zone in the dual temperature zone apparatus, respectively.
In some preferred embodiments of the invention, in step S2, nitrogen is fed into the double temperature zone device at a flow rate of 50-200sccm, the gas pressure in the double temperature zone device being controlled at 10-20mbar.
In some more preferred embodiments of the invention, in step S2, nitrogen is fed into the double temperature zone device at a flow rate of 45-55sccm, the gas pressure in the double temperature zone device being controlled at 9-11mbar.
In some more preferred embodiments of the invention, in step S2, the double temperature zone device is purged with nitrogen at a flow rate of about 50sccm, the gas pressure within the double temperature zone device being controlled at about 10mbar.
In a second aspect of the present invention, a metal phthalocyanine nanowire array prepared by the above preparation method is provided.
According to the embodiment of the invention, the metal phthalocyanine nanowire array has at least the following beneficial effects: the metal phthalocyanine nanowire array is prepared by combining the sapphire substrate surface modification treatment and the channel-assisted PVD method, the channel on the surface of the sapphire substrate plays a role in guiding in the nanowire growth process, and the hydrophobic groups introduced on the surface of the substrate in the hydrophobic treatment play a role in promoting nanowire extension. The invention uses simple equipment, and can synchronously realize the growth and ordered arrangement of the metal phthalocyanine nanowires only through a simple process. On the premise of greatly reducing the cost, the preparation flow of the nanowire array is greatly simplified, the crystallization quality, the uniformity and the order degree of the wire diameter of the nanowires are improved, and an ideal material platform is provided for developing various micro-nano photoelectric devices based on the batch construction of the metal phthalocyanine nanowires.
In a third aspect of the present invention, an application of the above metal phthalocyanine nanowire array in an optoelectronic device is provided.
In some embodiments of the present invention, the use of the above-described metal phthalocyanine nanowire arrays in micro-nano optoelectronic devices is presented.
In some embodiments of the invention, the application of the metal phthalocyanine nanowire array in field effect transistors, photovoltaic cells and sensors is provided.
In some embodiments of the invention, the application of the metal phthalocyanine nanowire array in field effect transistors, photovoltaic cells and photoelectric sensors is provided.
In a fourth aspect of the present invention, an optoelectronic device is provided, which includes the above-described metal phthalocyanine nanowire array.
Drawings
The invention is further described with reference to the accompanying drawings and examples, in which:
FIG. 1 is a flow chart of a process for preparing metal phthalocyanine nanowires in an embodiment of the invention;
FIG. 2 is a schematic view of a dual temperature zone tube furnace with a slide rail according to an embodiment of the present invention;
fig. 3 is a microstructure of a scanning electron microscope of the surface of a sapphire substrate subjected to high-temperature annealing in example 1 of the present invention.
FIG. 4 is a microscopic structural diagram of a scanning electron microscope of an in-plane array of zinc phthalocyanine nanowires prepared on a sapphire substrate in accordance with example 1 of the present invention;
FIG. 5 is a scanning electron microscope microstructure of an in-plane array of cobalt phthalocyanine nanowires fabricated on a sapphire substrate in accordance with example 2 of the present invention;
FIG. 6 is a microscopic structural diagram of a scanning electron microscope of an in-plane array of copper perfluorinated phthalocyanine nanowires prepared on a sapphire substrate in example 4 of the present invention;
FIG. 7 is a scanning electron microscope microstructure of an in-plane array of ferrous phthalocyanine nanowires fabricated on a sapphire substrate in accordance with example 5 of the present invention;
FIG. 8 is a scanning electron microscope microstructure of an in-plane array of nickel phthalocyanine nanowires fabricated on a sapphire substrate in accordance with example 6 of the present invention;
FIG. 9 is an optical microscope image of various metal phthalocyanine nanowires prepared on an annealed M-plane sapphire substrate without a hydrophobic treatment of comparative examples 1-6;
fig. 10 is an optical microscope image of the copper phthalocyanine nanowire prepared in example 3, examples 7 to 8 of the present invention, wherein fig. 10 (a) is an optical microscope image of the copper phthalocyanine nanowire prepared in example 7, fig. 10 (b) is an optical microscope image of the copper phthalocyanine nanowire prepared in example 3, and fig. 10 (c) is an optical microscope image of the copper phthalocyanine nanowire prepared in example 8;
fig. 11 is an optical microscope image of the copper phthalocyanine nanowire prepared in examples 9 to 11 in the present invention, wherein fig. 11 (a) is an optical microscope image of the copper phthalocyanine nanowire prepared in example 9, fig. 11 (b) is an optical microscope image of the copper phthalocyanine nanowire prepared in example 10, fig. 11 (c) is an optical microscope image of the copper phthalocyanine nanowire prepared in example 11, and fig. 11 (d) is an optical microscope image of the copper phthalocyanine nanowire prepared in example 3;
FIG. 12 is an optical microscope image of an optoelectronic device made in example 12 of the present invention;
fig. 13 is an I-V characteristic curve of the photovoltaic device prepared in example 12 of the present invention.
Detailed Description
Embodiments of the present invention are described in detail below, examples of which are illustrated in the accompanying drawings, wherein like or similar reference numerals refer to like or similar elements or elements having like or similar functions throughout. The embodiments described below by referring to the drawings are illustrative only and are not to be construed as limiting the invention.
In the description of the present invention, it should be understood that references to orientation descriptions such as upper, lower, front, rear, left, right, etc. are based on the orientation or positional relationship shown in the drawings, are merely for convenience of description of the present invention and to simplify the description, and do not indicate or imply that the apparatus or elements referred to must have a particular orientation, be constructed and operated in a particular orientation, and thus should not be construed as limiting the present invention.
In the description of the present invention, the meaning of a number is one or more, the meaning of a number is two or more, and greater than, less than, exceeding, etc. are understood to exclude the present number, and the meaning of a number is understood to include the present number. The description of the first and second is for the purpose of distinguishing between technical features only and should not be construed 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, unless explicitly defined otherwise, terms such as arrangement, installation, connection, etc. should be construed broadly and the specific meaning of the terms in the present invention can be reasonably determined by a person skilled in the art in combination with the specific contents of the technical scheme.
In the description of the present invention, the descriptions of the terms "one embodiment," "some embodiments," "illustrative embodiments," "examples," "specific examples," or "some examples," etc., mean 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, schematic representations of the above terms do not necessarily refer to the same embodiments or examples. Furthermore, the particular features, structures, materials, or characteristics described may be combined in any suitable manner in any one or more embodiments or examples.
The details of the chemical reagents used in the examples of the present invention are as follows:
zinc phthalocyanine: alfa Aesar, CAS:14320-04-8;
cobalt phthalocyanine: alfa Aesar, CAS:3317-67-7;
copper phthalocyanine: alfa Aesar, CAS:147-14-8;
copper perfluoro phthalocyanine: sigma-Aldrich, CAS: 1496-87-1;
Ferrous phthalocyanine: alfa Aesar, CAS:132-16-1;
nickel phthalocyanine: alfa Aesar, CAS:14055-02-8;
OTS: n-octadecyl trichlorosilane: alfa Aesar, CAS:112-04-9;
n-hexane: aladin, CAS:110-54-3;
ultrasonic cleaner: the manufacturer: shanghai Bilang instruments Co., ltd., model: BILON6-180;
slide rail double temperature zone tube furnace: the manufacturer: shanghai micro-industry Co., ltd., model: TF1200-60II-SL.
Example 1
A preparation method of a metal phthalocyanine nanowire array comprises the following steps:
and (I) taking the M-surface sapphire single crystal wafer as a raw material, putting the raw material into acetone, and cleaning the raw material for 10 minutes by an ultrasonic cleaner to remove oil stains on the surface. And taking out the cleaned sapphire wafer from the acetone, drying the surface by using dry nitrogen, and removing residual organic solvent. Then placing the mixture into a high-temperature box type furnace, heating to 1600 ℃ at the speed of 10 ℃/min, keeping the temperature for 10 hours, and finally cooling to about 25 ℃ along with the furnace and taking out for standby. The surface of the processed wafer is provided with a horizontal channel along the direction, the wafer is cut into the size of 1cm multiplied by 1cm by using a diamond pen, then ethanol, acetone, ethanol, distilled water and ethanol are sequentially used for ultrasonic cleaning for 10min respectively, and a nitrogen gun is used for blow-drying for standby, so that the sapphire substrate (I) is obtained.
(II) 10mL of n-hexane and 10. Mu.L of OTS were measured separately by a pipette, and mixed in a beaker and stirred uniformly to obtain an OTS solution. And (3) placing the sapphire substrate (I) obtained in the step (I) into OTS solution for hydrophobic treatment for 2 hours, and sealing a beaker containing a hydrophobic agent so as to prevent the OTS solution from being deteriorated by moisture in the air. And (3) taking the sapphire substrate subjected to the hydrophobic treatment out of the OTS solution, quickly and sequentially flushing the sapphire substrate three times by using a bottle respectively filled with acetone, ethanol and distilled water, and then drying the sapphire substrate by using a nitrogen gun to obtain the sapphire substrate (II).
And (III) weighing 10mg of zinc phthalocyanine powder, putting the zinc phthalocyanine powder and the sapphire substrate (II) obtained in the step (II) into a quartz tube of a sliding rail double-temperature-zone tube furnace, wherein the distance between the zinc phthalocyanine powder and the sapphire substrate (II) is 18cm, ensuring that the zinc phthalocyanine powder and the sapphire substrate (II) are positioned in different temperature zones, and marking the zinc phthalocyanine powder and the sapphire substrate (II) so as to facilitate the positioning of the tube furnace.
And (IV) flushing the quartz tube with nitrogen, regulating the flow rate of the nitrogen in the quartz tube to 50sccm, simultaneously opening an air pump to control the air pressure in the tube to 10mbar, heating the temperature of a tube furnace source temperature region to 450 ℃, heating the temperature of a growth temperature region to 250 ℃, pushing the tube furnace to a marked position after the temperature is stable, growing for 150min, cooling the tube furnace to room temperature along with the furnace in a nitrogen atmosphere, taking out the sapphire substrate, and finally preparing the zinc phthalocyanine nanowire array in the substrate surface.
Example 2
A preparation method of a metal phthalocyanine nanowire array comprises the following steps:
and (I) taking the M-surface sapphire single crystal wafer as a raw material, putting the raw material into acetone, and cleaning the raw material for 10 minutes by an ultrasonic cleaner to remove oil stains on the surface. And taking out the cleaned sapphire wafer from the acetone, drying the surface by using dry nitrogen, and removing residual organic solvent. Then placing the mixture into a high-temperature box type furnace, heating to 1600 ℃ at the speed of 10 ℃/min, keeping the temperature for 10 hours, and finally cooling to about 25 ℃ along with the furnace and taking out for standby. The surface of the processed wafer is provided with a horizontal channel along the direction, the wafer is cut into the size of 1cm multiplied by 1cm by using a diamond pen, then ethanol, acetone, ethanol, distilled water and ethanol are sequentially used for ultrasonic cleaning for 10min respectively, and a nitrogen gun is used for blow-drying for standby, so that the sapphire substrate (I) is obtained.
(II) 10mL of n-hexane and 10. Mu.L of OTS were measured separately by a pipette, and mixed in a beaker and stirred uniformly to obtain an OTS solution. And (3) placing the sapphire substrate (I) obtained in the step (I) into OTS solution for hydrophobic treatment for 2 hours, and sealing a beaker containing a hydrophobic agent so as to prevent the OTS solution from being deteriorated by moisture in the air. And (3) taking the sapphire substrate subjected to the hydrophobic treatment out of the OTS solution, quickly and sequentially flushing the sapphire substrate three times by using a bottle respectively filled with acetone, ethanol and distilled water, and then drying the sapphire substrate by using a nitrogen gun to obtain the sapphire substrate (II).
And (III) weighing 10mg of cobalt phthalocyanine powder, and placing the cobalt phthalocyanine powder and the sapphire substrate (II) obtained in the step (II) into a quartz tube of a sliding rail double-temperature-zone tube furnace, wherein the distance between the cobalt phthalocyanine powder and the sapphire substrate (II) is 18cm, so that the cobalt phthalocyanine powder and the sapphire substrate (II) are ensured to be positioned in different temperature zones, marks are made, and the tube furnace is conveniently positioned.
And (IV) flushing the quartz tube with nitrogen, regulating the flow rate of the nitrogen in the quartz tube to 50sccm, simultaneously opening an air pump to control the air pressure in the tube to 10mbar, heating the temperature of a tube furnace source temperature region to 450 ℃, heating the temperature of a growth temperature region to 240 ℃, pushing the tube furnace to a marked position after the temperature is stable, growing for 150min, cooling the tube furnace to room temperature along with the furnace in a nitrogen atmosphere, taking out the sapphire substrate, and finally preparing the cobalt phthalocyanine nanowire array in the substrate surface.
Example 3
A preparation method of a metal phthalocyanine nanowire array comprises the following steps:
and (I) taking the M-surface sapphire single crystal wafer as a raw material, putting the raw material into acetone, and cleaning the raw material for 10 minutes by an ultrasonic cleaner to remove oil stains on the surface. And taking out the cleaned sapphire wafer from the acetone, drying the surface by using dry nitrogen, and removing residual organic solvent. Then placing the mixture into a high-temperature box type furnace, heating to 1600 ℃ at the speed of 10 ℃/min, keeping the temperature for 10 hours, and finally cooling to about 25 ℃ along with the furnace and taking out for standby. The surface of the processed wafer is provided with a horizontal channel along the direction, the wafer is cut into the size of 1cm multiplied by 1cm by using a diamond pen, then ethanol, acetone, ethanol, distilled water and ethanol are sequentially used for ultrasonic cleaning for 10min respectively, and a nitrogen gun is used for blow-drying for standby, so that the sapphire substrate (I) is obtained.
(II) 10mL of n-hexane and 10. Mu.L of OTS were measured separately by a pipette, and mixed in a beaker and stirred uniformly to obtain an OTS solution. And (3) placing the sapphire substrate (I) obtained in the step (I) into OTS solution for hydrophobic treatment for 2 hours, and sealing a beaker containing a hydrophobic agent so as to prevent the OTS solution from being deteriorated by moisture in the air. And (3) taking the sapphire substrate subjected to the hydrophobic treatment out of the OTS solution, quickly and sequentially flushing the sapphire substrate three times by using a bottle respectively filled with acetone, ethanol and distilled water, and then drying the sapphire substrate by using a nitrogen gun to obtain the sapphire substrate (II).
And (III) weighing 10mg of copper phthalocyanine powder, and placing the copper phthalocyanine powder and the sapphire substrate (II) obtained in the step (II) into a quartz tube of a sliding rail double-temperature-zone tube furnace, wherein the distance between the copper phthalocyanine powder and the sapphire substrate (II) is 18cm, so that the copper phthalocyanine powder and the sapphire substrate (II) are ensured to be positioned in different temperature zones, marks are made, and the tube furnace is conveniently positioned.
And (IV) flushing the quartz tube with nitrogen, regulating the flow rate of the nitrogen in the quartz tube to 50sccm, simultaneously opening an air pump to control the air pressure in the tube to 10mbar, heating the temperature of a tube furnace source temperature region to 440 ℃, heating the temperature of a growth temperature region to 240 ℃, pushing the tube furnace to a marked position after the temperature is stable, growing for 150min, cooling to room temperature along with the furnace in a nitrogen atmosphere, taking out the sapphire substrate, and finally preparing the copper phthalocyanine nanowire array in the substrate surface.
Example 4
A preparation method of a metal phthalocyanine nanowire array comprises the following steps:
and (I) taking the M-surface sapphire single crystal wafer as a raw material, putting the raw material into acetone, and cleaning the raw material for 10 minutes by an ultrasonic cleaner to remove oil stains on the surface. And taking out the cleaned sapphire wafer from the acetone, drying the surface by using dry nitrogen, and removing residual organic solvent. Then placing the mixture into a high-temperature box type furnace, heating to 1600 ℃ at the speed of 10 ℃/min, keeping the temperature for 10 hours, and finally cooling to about 25 ℃ along with the furnace and taking out for standby. The surface of the processed wafer is provided with a horizontal channel along the direction, the wafer is cut into the size of 1cm multiplied by 1cm by using a diamond pen, then ethanol, acetone, ethanol, distilled water and ethanol are sequentially used for ultrasonic cleaning for 10min respectively, and a nitrogen gun is used for blow-drying for standby, so that the sapphire substrate (I) is obtained.
(II) 10mL of n-hexane and 10. Mu.L of OTS were measured separately by a pipette, and mixed in a beaker and stirred uniformly to obtain an OTS solution. And (3) placing the sapphire substrate (I) obtained in the step (I) into OTS solution for hydrophobic treatment for 2 hours, and sealing a beaker containing a hydrophobic agent so as to prevent the OTS solution from being deteriorated by moisture in the air. And (3) taking the sapphire substrate subjected to the hydrophobic treatment out of the OTS solution, quickly and sequentially flushing the sapphire substrate three times by using a bottle respectively filled with acetone, ethanol and distilled water, and then drying the sapphire substrate by using a nitrogen gun to obtain the sapphire substrate (II).
And (III) weighing 15mg of perfluorinated phthalocyanine copper powder, and placing the perfluorinated phthalocyanine copper powder and the sapphire substrate (II) obtained in the step (II) into a quartz tube of a sliding rail double-temperature-zone tube furnace, wherein the distance between the perfluorinated phthalocyanine copper powder and the sapphire substrate (II) is 12.5cm, so that the perfluorinated phthalocyanine copper powder and the sapphire substrate (II) are ensured to be positioned in different temperature zones, and marks are made, thereby being convenient for positioning the tube furnace.
And (IV) flushing the quartz tube with nitrogen, regulating the flow rate of the nitrogen in the quartz tube to 200sccm, simultaneously opening an air pump to control the air pressure in the tube to 20mbar, heating the temperature of a tube furnace source temperature region to 450 ℃, heating the temperature of a growth temperature region to 250 ℃, pushing the tube furnace to a marked position after the temperature is stable, growing for 90min, cooling to room temperature along with the furnace in a nitrogen atmosphere, taking out the sapphire substrate, and finally preparing the copper perfluorinated phthalocyanine nanowire array in the substrate surface.
Example 5
A preparation method of a metal phthalocyanine nanowire array comprises the following steps:
and (I) taking the M-surface sapphire single crystal wafer as a raw material, putting the raw material into acetone, and cleaning the raw material for 10 minutes by an ultrasonic cleaner to remove oil stains on the surface. And taking out the cleaned sapphire wafer from the acetone, drying the surface by using dry nitrogen, and removing residual organic solvent. Then placing the mixture into a high-temperature box type furnace, heating to 1600 ℃ at the speed of 10 ℃/min, keeping the temperature for 10 hours, and finally cooling to about 25 ℃ along with the furnace and taking out for standby. The surface of the processed wafer is provided with a horizontal channel along the direction, the wafer is cut into the size of 1cm multiplied by 1cm by using a diamond pen, then ethanol, acetone, ethanol, distilled water and ethanol are sequentially used for ultrasonic cleaning for 10min respectively, and a nitrogen gun is used for blow-drying for standby, so that the sapphire substrate (I) is obtained.
(II) 10mL of n-hexane and 10. Mu.L of OTS were measured separately by a pipette, and mixed in a beaker and stirred uniformly to obtain an OTS solution. And (3) placing the sapphire substrate (I) obtained in the step (I) into OTS solution for hydrophobic treatment for 2 hours, and sealing a beaker containing a hydrophobic agent so as to prevent the OTS solution from being deteriorated by moisture in the air. And (3) taking the sapphire substrate subjected to the hydrophobic treatment out of the OTS solution, quickly and sequentially flushing the sapphire substrate three times by using a bottle respectively filled with acetone, ethanol and distilled water, and then drying the sapphire substrate by using a nitrogen gun to obtain the sapphire substrate (II).
And (III) weighing 10mg of ferrous phthalocyanine powder, and placing the ferrous phthalocyanine powder and the sapphire substrate (II) obtained in the step (II) into a quartz tube of a sliding rail double-temperature-zone tube furnace together, wherein the distance between the ferrous phthalocyanine powder and the sapphire substrate (II) is 18cm, so that the ferrous phthalocyanine powder and the sapphire substrate (II) are ensured to be positioned in different temperature zones, marks are made, and the tube furnace is convenient to position.
And (IV) flushing the quartz tube with nitrogen, regulating the flow rate of the nitrogen in the quartz tube to 50sccm, simultaneously opening an air pump to control the air pressure in the tube to 10mbar, heating the temperature of a tube furnace source temperature region to 450 ℃, heating the temperature of a growth temperature region to 250 ℃, pushing the tube furnace to a marked position after the temperature is stable, growing for 150min, cooling the tube furnace to room temperature along with the furnace in a nitrogen atmosphere, taking out the sapphire substrate, and finally preparing the ferrous phthalocyanine nanowire array in the substrate surface.
Example 6
A preparation method of a metal phthalocyanine nanowire array comprises the following steps:
and (I) taking the M-surface sapphire single crystal wafer as a raw material, putting the raw material into acetone, and cleaning the raw material for 10 minutes by an ultrasonic cleaner to remove oil stains on the surface. And taking out the cleaned sapphire wafer from the acetone, drying the surface by using dry nitrogen, and removing residual organic solvent. Then placing the mixture into a high-temperature box type furnace, heating to 1600 ℃ at the speed of 10 ℃/min, keeping the temperature for 10 hours, and finally cooling to about 25 ℃ along with the furnace and taking out for standby. The surface of the processed wafer is provided with a horizontal channel along the direction, the wafer is cut into the size of 1cm multiplied by 1cm by using a diamond pen, then ethanol, acetone, ethanol, distilled water and ethanol are sequentially used for ultrasonic cleaning for 10min respectively, and a nitrogen gun is used for blow-drying for standby, so that the sapphire substrate (I) is obtained.
(II) 10mL of n-hexane and 10. Mu.L of OTS were measured separately by a pipette, and mixed in a beaker and stirred uniformly to obtain an OTS solution. And (3) placing the sapphire substrate (I) obtained in the step (I) into OTS solution for hydrophobic treatment for 2 hours, and sealing a beaker containing a hydrophobic agent so as to prevent the OTS solution from being deteriorated by moisture in the air. And (3) taking the sapphire substrate subjected to the hydrophobic treatment out of the OTS solution, quickly and sequentially flushing the sapphire substrate three times by using a bottle respectively filled with acetone, ethanol and distilled water, and then drying the sapphire substrate by using a nitrogen gun to obtain the sapphire substrate (II).
And (III) weighing 10mg of nickel phthalocyanine powder, and placing the nickel phthalocyanine powder and the sapphire substrate (II) obtained in the step (II) into a quartz tube of a sliding rail double-temperature-zone tube furnace, wherein the distance between the nickel phthalocyanine powder and the sapphire substrate (II) is 18cm, so that the nickel phthalocyanine powder and the sapphire substrate (II) are ensured to be positioned in different temperature zones, marks are made, and the tube furnace is convenient to position.
And (IV) flushing the quartz tube with nitrogen, regulating the flow rate of the nitrogen in the quartz tube to 50sccm, simultaneously opening an air pump to control the air pressure in the tube to 10mbar, heating the temperature of a tube furnace source temperature region to 450 ℃, heating the temperature of a growth temperature region to 250 ℃, pushing the tube furnace to a marked position after the temperature is stable, growing for 150min, cooling the tube furnace to room temperature along with the furnace in a nitrogen atmosphere, taking out the sapphire substrate, and finally preparing the nickel phthalocyanine nanowire array in the substrate surface.
Comparative example 1
A method for preparing a metal phthalocyanine nanowire array, which is different from example 1 in that a sapphire substrate is not subjected to a hydrophobic treatment.
Comparative example 2
A method for preparing a metal phthalocyanine nanowire array, which is different from example 2 in that the sapphire substrate is not subjected to hydrophobic treatment.
Comparative example 3
A method for preparing a metal phthalocyanine nanowire array, which is different from example 3 in that the sapphire substrate is not subjected to hydrophobic treatment.
Comparative example 4
A method for preparing a metal phthalocyanine nanowire array, which is different from example 4 in that the sapphire substrate is not subjected to hydrophobic treatment.
Comparative example 5
A method for preparing a metal phthalocyanine nanowire array, which is different from example 5 in that the sapphire substrate is not subjected to hydrophobic treatment.
Comparative example 6
A method for preparing a metal phthalocyanine nanowire array, which is different from example 6 in that the sapphire substrate is not subjected to hydrophobic treatment.
Example 7
A method for preparing a metal phthalocyanine nanowire array, which is different from example 3 in that the source liner distance is 17cm.
Example 8
A method for preparing a metal phthalocyanine nanowire array, which is different from example 3 in that the source liner distance is 19cm.
Example 9
A method for preparing a metal phthalocyanine nanowire array, which is different from example 3 in that the growth time is 30min.
Example 10
A method for preparing a metal phthalocyanine nanowire array, which is different from example 3 in that the growth time is 60min.
Example 11
A method for preparing a metal phthalocyanine nanowire array, which is different from example 3 in that the growth time is 120min.
Example 12
An optoelectronic device comprising an in-plane array of copper phthalocyanine nanowires, the method of making the optoelectronic device comprising:
and (I) preparing the copper phthalocyanine nanowire in-plane array, wherein the preparation method is the same as that of the copper phthalocyanine nanowire in-plane array in example 3.
(II) on the copper phthalocyanine nanowire in-plane array prepared in the step (I), a thermal evaporation coating apparatus is used for coatingThe line width of the vapor deposition is 150 mu m, the length is 300 mu m, the distance is 10 mu m, and the thickness is 120nm, so that the photoelectric device is obtained.
Test examples
This test example tested the annealed sapphire substrate, the metal phthalocyanine nanowire arrays prepared in examples 1 to 11 and comparative examples 1 to 6, and the photovoltaic device prepared in example 12: the annealed sapphire substrate in the embodiment and the prepared metal phthalocyanine nanowire array microstructure are tested by adopting a scanning electron microscope, and the test results are shown in figures 3-8; the microstructure of the metal phthalocyanine nanowire array prepared in the comparative example and the example is tested by adopting an optical microscope, and the test results are shown in fig. 9-11. In addition, the photoelectric device prepared in example 12 was also placed on a probe station, and tested using a universal source meter of model g Shi Li 2400, and the I-V characteristic curves were measured in dark (under dark conditions) and bright (under ordinary white light), and the test results are shown in fig. 13, where the current of the device under light conditions was significantly higher than the current under dark conditions, demonstrating that the photoelectric device had a strong light response.
As shown by test results, the annealed M-surface sapphire single crystal wafer is taken as a substrate, and the direction of the in-plane array of the PVD-grown metal phthalocyanine nanowire is provided alongThe horizontal channel array structure with the interval between adjacent channels being 50-150nm and the included angle between the adjacent channel forming surfaces being 100-140 degrees is combined with OTS solution to carry out hydrophobic treatment, so that sublimated metal phthalocyanine gaseous molecules preferentially form nuclei and grow along the channel direction in the PVD process, and finally the prepared metal phthalocyanine nanowire in-plane array is orderly and horizontally oriented, straight, uniform in diameter, high in density, few in defects, and high in repeatability, the length can reach between tens of micrometers and hundreds of micrometers, and the array disorder degree is low, the surface defects are few.
By comparing the metal phthalocyanine nanowire array growing on the annealed M-surface sapphire substrate with or without the hydrophobic treatment, the length of the nanowire growing after the hydrophobic treatment is increased by hundreds of times compared with that of the nanowire obtained without the hydrophobic treatment, the channel plays a role in guiding in the growth process of the nanowire, and hydrophobic groups introduced on the surface of the substrate by the hydrophobic treatment play a role in promoting the extension of the nanowire. The surface channel and the surface hydrophobic treatment of the substrate are two necessary conditions for growing the ordered metal phthalocyanine nanowire nano-array, which is indispensable. The preparation method combining the surface channel and the surface hydrophobic treatment of the substrate is more beneficial to constructing the photoelectric device integrated array based on the metal phthalocyanine nanowire in-plane array.
The preparation process is simple, the growth and ordered arrangement of the metal phthalocyanine nanowires can be synchronously realized by using simple tubular furnace equipment only through the simple process, the preparation process of the nanowire array is greatly simplified, and the crystallization quality, the uniformity of the wire diameter and the order degree of the nanowires are improved. Meanwhile, the large-scale preparation of the high-quality metal phthalocyanine nanowire array can be realized by enlarging the size of the growth substrate, the cost is low, the repeatability is high, the micro-nano photoelectric devices can be constructed in batches by means of a commercial micro-nano processing technology, the performance surface of the devices is expected to be improved, and an ideal material platform is provided for the research and development of various micro-nano photoelectric devices based on the metal phthalocyanine nanowire in batches.
The length, the position and the density of the nanowire array can be regulated and controlled by changing the growth parameters of the PVD process. The PVD preferred growth parameters for various metal phthalocyanine nanowires are shown in table 1 below:
table 1 growth parameters table for various metal phthalocyanine nanowire PVD processes
Where m= Co, fe, zn, cu, ni.
Wherein, the source lining distance is: during PVD growth of nanowires, the distance between the metal phthalocyanine and the substrate (linear distance). Powder mass: the mass of the metal phthalocyanine powder.
As can be seen from the above Table 1, the growth parameters of the various metal phthalocyanine nanowires prepared by the method are basically the same, which proves the universality of the in-plane array of the metal phthalocyanine nanowires prepared by the method, and the length and the density of the nanowires can be regulated and controlled by changing the growth parameters within a certain range, and the method specifically comprises the following steps: within a suitable range, increasing the source liner distance will decrease the nanowire density, and the test results for the related comparative example are shown in fig. 10; the length of the nanowire is proportional to the growth time in a certain growth time, and the test results of the related comparative example are shown in fig. 11; the source temperature is positively correlated with the nanowire density, the higher the source temperature is, the higher the nanowire density is, and the higher the source temperature can increase the nanowire density because the source temperature is increased to increase the evaporation amount; the growth temperature is inversely related to the density of the nano wire, the lower the growth temperature is, the higher the density of the nano wire is, the growth temperature controls the deposition amount of the metal phthalocyanine molecule, the temperature is increased, the deposition amount is reduced, and the density of the nano wire is reduced. In addition, the gas pressure is increased, the density of the nano wires is reduced, the gas pressure can control the evaporation capacity, the evaporation capacity is reduced when the gas pressure is increased, and the density of the nano wires is reduced.
The terms "about" and "left and right" used herein refer to an error of 2%.
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 one of ordinary skill in the art without departing from the spirit of the present invention. Furthermore, embodiments of the invention and features of the embodiments may be combined with each other without conflict.
Claims (30)
1. The preparation method of the metal phthalocyanine nanowire array is characterized by comprising the following steps of:
s1, taking a precious stone with a channel array on the surface as a substrate, and performing hydrophobic treatment on the channel array;
s2, taking metal phthalocyanine and forming a plurality of metal phthalocyanine nanowires on the surface of the substrate treated in the step S1 through physical vapor deposition to obtain a metal phthalocyanine nanowire array;
the sapphire comprises sapphire, and the sapphire is M-plane sapphire;
in the step S1, annealing the M-plane sapphire to obtain the sapphire with the surface provided with the channel array;
in step S1, a substrate is subjected to a hydrophobic treatment using a hydrophobic reagent; the hydrophobic reagent comprises a silylating reagent;
In step S2, the physical vapor deposition specifically includes: firstly gasifying metal phthalocyanine in a source temperature zone, and then depositing a plurality of metal phthalocyanine nanowires on the surface of a substrate in a growth temperature zone, wherein the temperature of the growth temperature zone is lower than that of the source temperature zone; the temperature of the source temperature region is 440-450 ℃, and the temperature of the growth temperature region is 240-260 ℃; the deposition time is 60-180 min; the metal phthalocyanine is at a distance of 12.5-19. 19 cm from the substrate.
2. The method for preparing a metal phthalocyanine nanowire array according to claim 1, wherein the metal phthalocyanine comprises at least one of zinc phthalocyanine, cobalt phthalocyanine, copper phthalocyanine, ferrous phthalocyanine or nickel phthalocyanine.
3. The method of preparing a metal phthalocyanine nanowire array according to claim 2, wherein the copper phthalocyanine comprises perfluoro copper phthalocyanine.
4. The method of preparing a metal phthalocyanine nanowire array according to claim 1, wherein in step S1, the annealed sapphire is first washed and then subjected to a hydrophobic treatment.
5. The method for preparing a metal phthalocyanine nanowire array according to claim 4, wherein in the step S1, the first cleaning step of the sapphire is: sequentially ultrasonically cleaning the sapphire with ethanol, acetone, ethanol, water and ethanol.
6. The method of claim 1, wherein the hydrophobic agent comprises OTS.
7. The method for preparing a metal phthalocyanine nanowire array according to claim 1, wherein the hydrophobic reagent comprises a mixed solution of OTS and n-hexane.
8. The method for preparing a metal phthalocyanine nanowire array according to claim 1, wherein the hydrophobic treatment time is 1-2 h.
9. The method for preparing a metal phthalocyanine nanowire array according to claim 1, wherein the hydrophobic treatment time is 2 h.
10. The method for preparing a metal phthalocyanine nanowire array according to claim 1, wherein in step S1, the substrate is immersed in a hydrophobic reagent to perform a hydrophobic treatment.
11. The method for preparing a metal phthalocyanine nanowire array according to claim 10, wherein in step S1, the substrate is immersed in a mixed solution of OTS and n-hexane for hydrophobic treatment.
12. The method of preparing a metal phthalocyanine nanowire array according to claim 1, wherein in step S1, the substrate is subjected to a hydrophobic treatment under anhydrous conditions.
13. The method of claim 1, wherein the hydrophobic agent is isolated from air during the hydrophobic treatment.
14. The method for preparing a metal phthalocyanine nanowire array according to claim 1, wherein the substrate is subjected to a second cleaning after the hydrophobic treatment, and is dried by nitrogen.
15. The method of claim 14, wherein the second cleaning comprises rinsing the substrate with acetone.
16. The method of claim 14, wherein the second cleaning comprises rinsing the substrate with acetone, ethanol, or water, respectively.
17. The method of claim 14, wherein the second cleaning comprises sequentially washing the substrate with acetone, ethanol, and water.
18. The method for preparing a metal phthalocyanine nanowire array according to claim 1, wherein the deposition time is 90-150 min.
19. The method for preparing a metal phthalocyanine nanowire array according to claim 1, wherein the source temperature is 450 ℃, the growth temperature is 250 ℃, and the physical vapor deposition time is 150 min.
20. The method for preparing a metal phthalocyanine nanowire array according to claim 1, wherein the metal phthalocyanine is spaced from the substrate by a distance of 12.5-14 cm.
21. The method for preparing a metal phthalocyanine nanowire array according to claim 1, wherein the metal phthalocyanine is spaced from the substrate by a distance of 17-19 cm.
22. The method of claim 1, wherein the metal phthalocyanine nanowire array is 18 cm a from the substrate.
23. The method for preparing a metal phthalocyanine nanowire array according to claim 1, wherein in step S2, the metal phthalocyanine nanowires are formed under a protective gas atmosphere.
24. The method for preparing a metal phthalocyanine nanowire array according to claim 23, wherein the shielding gas is nitrogen or inert gas.
25. The method for preparing a metal phthalocyanine nanowire array according to claim 24, wherein the flow rate of nitrogen is 50-200 sccm.
26. The method for preparing a metal phthalocyanine nanowire array according to claim 23, wherein the gas pressure of the protective gas atmosphere is 10-20 mbar.
27. The method for preparing a metal phthalocyanine nanowire array according to claim 24, wherein the flow rate of nitrogen is 50 sccm and the gas pressure of the nitrogen atmosphere is 10 mbar.
28. A metal phthalocyanine nanowire array prepared by the preparation method of any one of claims 1-27.
29. Use of the metal phthalocyanine nanowire array of claim 28 in an optoelectronic device.
30. An optoelectronic device comprising the metal phthalocyanine nanowire array of claim 28.
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