Preparation method, product and application of multi-element doped symbiotic tetrapod-like zinc oxide whisker

Abstract

The invention discloses a preparation method, a product and application of a multi-element doped symbiotic tetrapod-like zinc oxide whisker, and relates to the technical field of micro and nano materials. The invention relates to a preparation method of a multi-element doped symbiotic tetrapod-like zinc oxide whisker, which comprises the following steps: stirring and dissolving polyethylene glycol in water to form gel, putting zinc particles into the gel, and adding oxides of doped elements at the same time, so that the oxides of the doped elements are attached to the zinc particles; filtering to remove the gel to obtain zinc particles attached with doped element oxides; and drying the zinc particles attached with the doped element oxide, carrying out heating reaction symbiosis, and cooling to room temperature to obtain the doped tetrapod-like zinc oxide whisker. Compared with the prior art, the tetrapod-like zinc oxide whisker has the advantages that crystal growth is promoted and combined by zinc particle reaction symbiosis of sol attached doping elements, formed zinc oxide does not need to be used as an intrinsic material for doping, the doping elements can be selected according to performance requirements, and the tetrapod-like zinc oxide whisker can meet various different photoelectric performance requirements.

Description

Technical Field

[0001] The present application relates to the field of micro- and nanomaterial technology, and in particular to a preparation method, product, and application of multi-element doped symbiotic tetrapod-shaped zinc oxide whiskers. Background Art

[0002] Tetrapod-like zinc oxide whiskers (T-ZnOw) are a novel, self-activated, direct wide bandgap semiconductor material with a direct bandgap of 3.3 eV. (T-ZnOw) exhibits a three-dimensional, four-needle structure grown as a single crystal. Due to the highly ordered atomic structure during crystallization, the diameter of (T-ZnOw) is too small to accommodate the defects found in larger crystals. This unique, three-dimensional, four-needle structure allows for easy uniform distribution within the matrix, thereby isotropically improving the material's physical properties while imparting a variety of unique functional properties unmatched by ordinary zinc oxide. These properties include antistatic, wear-resistant enhancement, vibration reduction, noise reduction, wave absorption, anti-aging, and antibacterial properties. T-ZnOw is widely used in semiconductor targets, short-wavelength luminescence, field emission, and laser devices, playing an important role in electronics, chemical engineering, light industry, transportation, and other fields. Doping is a highly effective method for improving the optoelectronic properties of semiconductors. Doped T-ZnOw exhibits two conductive mechanisms: the presence of intrinsic donors or the introduction of extrinsic donors, both of which contribute to conductivity, resulting in T-ZnOw semiconductor materials with excellent optoelectronic properties. Currently available doping techniques include metal-organic chemical vapor deposition, ion beam implantation, and pulsed laser deposition. These all utilize preformed tetrapod-shaped zinc oxide as the intrinsic material for doping. These processes are complex, require high equipment requirements, and are very limited in the types of doping elements that can be used. Summary of the Invention

[0003] The main purpose of this application is to provide a preparation method, product and application of multi-element doped symbiotic tetrapod-shaped zinc oxide whiskers, aiming to solve the technical problems of the existing tetrapod-shaped zinc oxide whiskers with limited doping element types and complex process conditions.

[0004] To achieve the above objectives, the present application proposes a method for preparing multi-element doped symbiotic tetrapod-shaped zinc oxide whiskers, comprising the following steps:

[0005] Stirring and dissolving polyethylene glycol in water to form a gel, placing zinc particles in the gel, and simultaneously adding an oxide of a doping element so that the oxide of the doping element adheres to the zinc particles;

[0006] filtering again to remove the gel and obtain zinc particles attached with doping element oxides;

[0007] The zinc particles with the doping element oxide attached thereto are dried, heated for reaction and then cooled to room temperature to obtain doped four-needle zinc oxide whiskers.

[0008] Optionally, the doping elements include beryllium, boron, carbon, silicon, phosphorus, sulfur, calcium, magnesium, scandium, titanium, vanadium, chromium, manganese, iron, cobalt, nickel, copper, zinc, gallium, germanium, arsenic, selenium, bromine, strontium, yttrium, zirconium, niobium, molybdenum, technetium, ruthenium, rhodium, palladium, silver, cadmium, indium, tin, antimony, tellurium, iodine, barium, lanthanum, , cerium, praseodymium, neodymium, promethium, samarium, europium, gadolinium, terbium, dysprosium, holmium, erbium, thulium, ytterbium, lutetium, hafnium, tantalum, tungsten, rhenium, osmium, iridium, platinum, gold, mercury, thallium, lead, bismuth, polonium, astatine, francium, radium, actinium, protactinium, uranium, neptunium, plutonium, americium, curium, berkelium, californium, einsteinium, fermium, mendelevium, nobelium, lawrencium, ruthenium, Copper, niobium, feldspar, molybdenum, lead, and At least one of .

[0009] Optionally, in the zinc particles attached with the doping element oxide, the molar ratio of zinc to the doping element is (50-99): (1-49).

[0010] Optionally, the purity of the zinc particles is 99%.

[0011] Optionally, the step of stirring and dissolving polyethylene glycol in water to form a gel comprises:

[0012] The polyethylene glycol is placed in a constant temperature water bath at 20° C.-30° C. and stirred to dissolve for 1 h-2 h, so that the polyethylene glycol swells and forms a gel.

[0013] Optionally, in the step of stirring and dissolving polyethylene glycol in water, the mass ratio of the polyethylene glycol to water is (15-25):100.

[0014] Optionally, the step of drying the zinc particles attached with the doping element oxide comprises:

[0015] The zinc particles attached with the doping element oxide are dried at 75° C.-85° C. for 30 min-180 min.

[0016] Optionally, the step of performing heating reaction symbiosis includes:

[0017] The dried zinc particles with the doping element oxide attached thereto are placed in a box-type resistance furnace, and then heated to 500°C-1200°C and reacted for 10 minutes-25 minutes.

[0018] The present application also proposes a multi-element doped symbiotic tetrapod-shaped zinc oxide whisker product, which is obtained by using the above-mentioned preparation method of the multi-element doped symbiotic tetrapod-shaped zinc oxide whisker.

[0019] This application also proposes the application of a multi-element doped symbiotic tetrapod-shaped zinc oxide whisker product, and applies the multi-element doped symbiotic tetrapod-shaped zinc oxide whisker product to the fields of transparent conductivity, field emission and electroluminescence.

[0020] The present application forms a gel through polyethylene glycol, so that the oxide of the doping element is attached to the zinc particles through the gel. After filtering and removing the gel, zinc particles with the oxide of the doping element attached are obtained. Then, by heating, the zinc element and the doping element are combined to form four-needle zinc oxide whiskers. The four-needle zinc oxide whiskers are in a single crystal state with a micron structure and a three-dimensional four-needle structure at a microscopic level. The whiskers have a core and four needle-like crystals extending radially from the core. Each needle-like body is a single crystal microfiber, and the overall morphology is four-needle, which can be used as an ideal material for making transparent conductive targets and field emission cathodes. The present application uses the reaction symbiosis of zinc particles attached to the sol and doping elements to promote crystal growth and combination. The process is simple, the production cost is low, and it is easy to implement. There is no need to use the formed four-needle zinc oxide as the intrinsic material to complete the doping, thereby avoiding the problem that the conventional doping method has high requirements for process conditions and equipment and is limited in the types of doping elements. In addition, the photoelectric physical properties of the zinc oxide nanomaterial can be further improved by doping. The doping elements can be selected according to the performance requirements, so that the four-needle zinc oxide whiskers can meet a variety of different optoelectronic performance requirements, forming a four-needle zinc oxide whisker semiconductor material with excellent photoelectric properties. BRIEF DESCRIPTION OF THE DRAWINGS

[0021] In order to more clearly illustrate the embodiments of the present application or the technical solutions in the prior art, the following briefly introduces the drawings required for use in the embodiments or the description of the prior art. Obviously, the drawings described below are only some embodiments of the present application. For ordinary technicians in this field, other drawings can be obtained based on the structures shown in these drawings without paying any creative work.

[0022] Figure 1 This is the XRD diffraction pattern of the four-needle zinc oxide whisker described in Example 1 of the present application;

[0023] Figure 2 This is a scanning electron microscope image of the four-needle zinc oxide whisker described in Example 1 of the present application;

[0024] Figure 3 This is a scanning electron microscope image of the four-needle zinc oxide whisker described in Example 2 of the present application;

[0025] Figure 4 This is a scanning electron microscope image of the four-needle zinc oxide whisker described in Example 3 of the present application;

[0026] Figure 5This is a scanning electron microscope image of the four-needle zinc oxide whisker described in Example 4 of the present application;

[0027] Figure 6 This is a scanning electron microscope image of the four-needle zinc oxide whisker described in Example 5 of the present application;

[0028] Figure 7 This is a scanning electron microscope image of the four-needle zinc oxide whisker described in Example 6 of the present application;

[0029] Figure 8 This is a scanning electron microscope image of the four-needle zinc oxide whisker described in Example 7 of the present application.

[0030] The realization of the objectives, functional features and advantages of this application will be further explained in conjunction with embodiments and with reference to the accompanying drawings. DETAILED DESCRIPTION

[0031] The following will be combined with the drawings in the embodiments of this application to clearly and completely describe the technical solutions in the embodiments of this application. Obviously, the embodiments described are only part of the embodiments of this application, not all of the embodiments. Based on the embodiments of this application, all other embodiments obtained by ordinary technicians in this field without making creative efforts are within the scope of protection of this application.

[0032] In order to solve the technical problems existing in the prior art, the embodiments of the present application provide a method for preparing multi-element doped symbiotic tetrapod-shaped zinc oxide whiskers, comprising the following steps:

[0033] Stirring and dissolving polyethylene glycol in water to form a gel, placing zinc particles in the gel, and simultaneously adding an oxide of a doping element so that the oxide of the doping element adheres to the zinc particles;

[0034] filtering again to remove the gel and obtain zinc particles attached with doping element oxides;

[0035] The zinc particles with the doping element oxide attached thereto are dried, heated for reaction and then cooled to room temperature to obtain doped four-needle zinc oxide whiskers.

[0036] The present application forms a gel through polyethylene glycol, so that the oxide of the doping element is attached to the zinc particles through the gel. After filtering and removing the gel, zinc particles with the oxide of the doping element attached are obtained. Then, by heating, the zinc element and the doping element are combined to form four-needle zinc oxide whiskers. The four-needle zinc oxide whiskers are in a single crystal state with a micron structure and a three-dimensional four-needle structure at a microscopic level. The whiskers have a core and four needle-like crystals extending radially from the core. Each needle-like body is a single crystal microfiber, and the overall morphology is four-needle, which can be used as an ideal material for making transparent conductive targets and field emission cathodes. The present application uses the reaction symbiosis of zinc particles attached to the sol and doping elements to promote crystal growth and combination. The process is simple, the production cost is low, and it is easy to implement. There is no need to use the formed four-needle zinc oxide as the intrinsic material to complete the doping, thereby avoiding the problem that the conventional doping method has high requirements for process conditions and equipment and is limited in the types of doping elements. In addition, the photoelectric physical properties of the zinc oxide nanomaterial can be further improved by doping. The doping elements can be selected according to the performance requirements, so that the four-needle zinc oxide whiskers can meet a variety of different optoelectronic performance requirements, forming a four-needle zinc oxide whisker semiconductor material with excellent photoelectric properties.

[0037] As an embodiment of the present invention, the doping elements include beryllium, boron, carbon, silicon, phosphorus, sulfur, calcium, magnesium, scandium, titanium, vanadium, chromium, manganese, iron, cobalt, nickel, copper, zinc, gallium, germanium, arsenic, selenium, bromine, strontium, yttrium, zirconium, niobium, molybdenum, technetium, ruthenium, rhodium, palladium, silver, cadmium, indium, tin, antimony, tellurium, Iodine, barium, lanthanum, cerium, praseodymium, neodymium, promethium, samarium, europium, gadolinium, terbium, dysprosium, holmium, erbium, thulium, ytterbium, lutetium, hafnium, tantalum, tungsten, rhenium, osmium, iridium, platinum, gold, mercury, thallium, lead, bismuth, polonium, astatine, francium, radium, actinium, protactinium, uranium, neptunium, plutonium, americium, curium, berkelium, californium, einsteinium, fermium, mendelevium, nobelium, lawrencium, ruthenium, Copper, niobium, feldspar, molybdenum, lead, and At least one of .

[0038] In this embodiment, according to the performance requirements of the four-needle zinc oxide whiskers, the doping elements can be beryllium (Be), boron (B), carbon (C), silicon (Si), phosphorus (P), sulfur (S), calcium (Ca), magnesium (Mg), scandium (Sc), titanium (Ti), vanadium (V), chromium (Cr), manganese (Mn), iron (Fe), cobalt (Co), nickel (Ni), copper (Cu), zinc (Zn), gallium (Ga), germanium (Ge), arsenic (As), selenium (Se), bromine (Br), strontium (Br), yttrium (Y), zirconium (Zr), niobium (Nb), molybdenum (Mo), technetium (Tc), ruthenium (Ru), rhodium (Rh), palladium (Pd), silver (Ag), cadmium (Cd), indium (In), tin (Sn), antimony (Sb), tellurium (Te), iodine (I), barium (Ba), lanthanum (La), cerium ( Ce), praseodymium (Pr), neodymium (Nd), promethium (Pm), samarium (Sm), europium (Eu), gadolinium (Gd), terbium (Tb), dysprosium (Dy), holmium (Ho), erbium (Er), thulium (Tm), ytterbium (Yb), lutetium (Lu), hafnium (Hf), tantalum (Ta), tungsten (W), rhenium (Re), osmium (Os), iridium (Ir), platinum (Pt), gold (Au), mercury (Hg), thallium (Tl), lead (Pb), bismuth (Bi), polonium (Po), astatine (At), francium (Fr), radium (Ra), actinium (Ac), thorium (Th), protactinium (Pa), uranium (U), neptunium (Np), plutonium (Pu), americium (Am), curium (Cm), berkelium (Bk), californium (Cf), einsteinium (Es), fermium (Fm), mendelevium (Md), nobelium (No), lawrencium (Lr), ruthenium (Rf), (Db), (Sg), (Bh), (Hs), (Mt), (Ds), (Rg), cobalt (Cn), niobium (Nh), ferrum (Fl), magnesium (Mc), liverwood (Lv), and One or more of the above compounds (Ts) are selected to dope zinc oxide. The doping elements enter the four-needle lattice structure as doping ions to replace Zn. The doping elements and zinc co-generate four needles without changing the crystal structure of the four needles. The doping process is a symbiotic doping of the doping elements and zinc, thereby effectively improving the performance of the four-needle zinc oxide whiskers as semiconductor nanodevices.

[0039] Specifically, when the four-needle zinc oxide whiskers are doped with aluminum and gallium as doping elements, the obtained aluminum- and gallium-doped symbiotic four-needle zinc oxide whiskers have lower resistivity than undoped four-needle zinc oxide whiskers, and can be used in the field of transparent conductivity; when the four-needle zinc oxide whiskers are doped with magnesium as a doping element, the obtained magnesium-doped symbiotic four-needle zinc oxide whiskers have better electron field emission stability than undoped four-needle zinc oxide whiskers, and can be used in the field of field emission.

[0040] As an implementation method of the present application, in the zinc particles attached with the doping element oxide, the molar ratio of zinc to the doping element is (50-99): (1-49).

[0041] In the specific implementation process, different doping elements are selected according to the performance requirements of the four-needle zinc oxide whiskers in optoelectronics as nanomaterials, and the mass ratio of zinc particles to the oxide of the doping element is determined according to the different doping elements, thereby completing the doping of the four-needle zinc oxide whiskers.

[0042] As an implementation method of the present application, the purity of the zinc particles is 99%.

[0043] As an embodiment of the present application, the step of stirring and dissolving polyethylene glycol in water to form a gel includes:

[0044] The polyethylene glycol is placed in a constant temperature water bath at 20° C.-30° C. and stirred to dissolve for 1 h-2 h, so that the polyethylene glycol swells and forms a gel.

[0045] Specifically, polyethylene glycol is a common water-soluble polymer. The hydrogel produced from it is non-toxic and has good biocompatibility. In addition, there are functional groups - hydroxyl groups at both ends of the polyethylene glycol molecular chain, which are easy to undergo chemical reactions. The preparation of a structurally uniform gel by polyethylene glycol is conducive to the attachment of the oxide of the doped element to the zinc particles through the gel.

[0046] As an embodiment of the present application, in the step of stirring and dissolving polyethylene glycol in water, the mass ratio of the polyethylene glycol to water is (15-25):100.

[0047] Preferably, when the mass ratio of polyethylene glycol to water is 20:100, polyethylene glycol can be uniformly dispersed in water, thereby preparing a gel with uniform structure.

[0048] As an embodiment of the present application, the step of drying the zinc particles attached with the doping element oxide includes:

[0049] The zinc particles attached with the doping element oxide are dried at 75° C.-85° C. for 30 min-180 min.

[0050] Specifically, after the gel is removed by filtration, a large amount of water molecules remain on the zinc particles attached with the doped element oxide. In order to avoid the negative impact of the residual water molecules in the subsequent symbiotic reaction, the zinc particles attached with the doped element oxide are first dried. Preferably, the drying temperature is 80° C. and the drying time is 100 min.

[0051] As an embodiment of the present application, the step of performing heating reaction symbiosis includes:

[0052] The dried zinc particles with the doping element oxide attached thereto are placed in a box-type resistance furnace, and then heated to 500°C-1200°C and reacted for 10 minutes-25 minutes.

[0053] In the specific implementation process, by heating the zinc particles attached with the doping element oxide in a box-type resistance furnace for symbiotic reaction, the crystal growth can be promoted. During the reaction process, the dopant and zinc co-generate four needles, and the doping element enters the lattice structure of the four needles and exists in the form of replacing zinc, thus forming a symbiotic doping of the doping element and zinc.

[0054] The embodiments of the present application also provide a multi-element doped symbiotic tetrapod-shaped zinc oxide whisker product, which is obtained by the above-mentioned method for preparing the multi-element doped symbiotic tetrapod-shaped zinc oxide whisker.

[0055] The embodiments of the present application also provide applications of multi-element doped symbiotic tetrapod-shaped zinc oxide whisker products, which are applied to the fields of transparent conduction, field emission, and electroluminescence.

[0056] The four-needle zinc oxide whiskers prepared in the present application have the appearance of a white loose powder, and a three-dimensional four-needle structure at a microscopic level. The whiskers have a core, and four needle-like crystals extend radially from the core. Each needle-like body is a single crystal microfiber, and the overall morphology is four-needle. The physical properties of the four-needle zinc oxide whiskers as a nanomaterial in optoelectronics are further improved by doping. Different doping elements are selected according to the performance requirements of the four-needle zinc oxide whiskers to obtain four-needle zinc oxide whiskers with multi-element doping symbiosis, which are suitable for the fields of transparent conduction, field emission and electroluminescence.

[0057] The above technical solutions of the present application are described in detail below with reference to specific embodiments.

[0058] Example 1

[0059] The preparation method of multi-element doped symbiotic tetrapod-shaped zinc oxide whiskers comprises the following steps:

[0060] Placing polyethylene glycol in a constant temperature water bath at 25° C. and stirring and dissolving for 1.5 hours to allow the polyethylene glycol to swell and form a gel, wherein the mass ratio of polyethylene glycol to water is 20:100, then placing 99% pure zinc particles in the gel, and simultaneously adding oxides doped with elemental aluminum and gallium (aluminum oxide and gallium oxide) to adhere the aluminum oxide and gallium oxide to the zinc particles, wherein the molar ratio of zinc to aluminum and gallium is 97:1:2;

[0061] Filter again to remove the gel and obtain zinc particles attached with aluminum oxide and gallium oxide;

[0062] The zinc particles attached with aluminum oxide and gallium oxide were dried at 80°C for 100 minutes, and then placed in a box-type resistance furnace, heated to 850°C, reacted for 17 minutes, and cooled to room temperature to obtain aluminum- and gallium-doped symbiotic four-needle zinc oxide whiskers, the electron microscope scanning image of which at 10 μm is as follows: Figure 2 As shown, it is in a single crystal state with a micron structure.

[0063] The aluminum and gallium doped tetrapod-shaped zinc oxide whiskers prepared in this application were subjected to X-ray diffraction, and the results were as follows: Figure 1 As shown in the figure, (100), (002), (101), (102), (110), (103), (200), (112), and (201) are all diffraction peaks of different crystal planes of zinc oxide. The position and relative intensity of the diffraction peaks are basically consistent with the diffraction data of JCPDS card NO.36-1451, which is a wurtzite structure and no second phase is found. If there is single Al or Ga, different diffraction peaks will be shown. Therefore, it is shown that a complete symbiotic doping of Al, Ga and Zn is formed during the doping process. Al and Ga enter the lattice structure of the four-needle as doping ions to replace Zn. After the four-needle is co-generated, the crystal structure of the four-needle is not changed. Among them, the diffraction peak position of the (002) crystal plane (34.450°) is not deviated from the standard peak position (34.450°). It can be seen that the prepared symbiotic doped four-needle zinc oxide whiskers are a preferentially oriented lead zinc mineral ZnO structure with a C-axis preferential orientation.

[0064] The resistivity of the aluminum and gallium doped tetrapod-shaped zinc oxide whiskers prepared in this application was tested, and the results showed that the resistivity was 1.2×10 -1 Ω·cm, indicating that the four-needle zinc oxide whisker has a low resistivity and can be used in the field of transparent conductivity.

[0065] Example 2

[0066] The preparation method of multi-element doped symbiotic tetrapod-shaped zinc oxide whiskers comprises the following steps:

[0067] Placing polyethylene glycol in a constant temperature water bath at 25° C. and stirring and dissolving for 1.5 hours to allow the polyethylene glycol to swell and form a gel, wherein the mass ratio of polyethylene glycol to water is 20:100, then placing zinc particles with a purity of 99% in the gel, and simultaneously adding an oxide doped with elemental magnesium (magnesium oxide) to allow the magnesium oxide to adhere to the zinc particles, wherein the molar ratio of zinc to magnesium is 97.5:2.5;

[0068] Filter again to remove the gel and obtain zinc particles attached with magnesium oxide;

[0069] The zinc particles attached with magnesium oxide were dried at 80°C for 100 minutes, and then placed in a box-type resistance furnace, heated to 850°C, reacted for 17 minutes, and cooled to room temperature to obtain magnesium-doped co-grown four-needle zinc oxide whiskers. The electron microscope scanning image at 20 μm is as follows: Figure 3 As shown in FIG. 1 (where Pa R represents different whisker groups, Pa represents the microscopic diameter of each whisker group, and Pb represents the angle between each whisker group), it is in a single crystal state with a micron structure.

[0070] The magnesium-doped symbiotic tetrapod-shaped zinc oxide whiskers obtained in this application were tested for electron field emission. The results showed that the turn-on voltage was 3 V / μm, and the electric field required to obtain an emission current of 1 mA / cm-2 mA / cm was only 5.7 V / μm. The sample showed good electron field emission stability and could be used for field emission.

[0071] Example 3

[0072] The preparation method of multi-element doped symbiotic tetrapod-shaped zinc oxide whiskers comprises the following steps:

[0073] Placing polyethylene glycol in a constant temperature water bath at 25° C. and stirring and dissolving for 1.5 hours to allow the polyethylene glycol to swell and form a gel, wherein the mass ratio of polyethylene glycol to water is 15:100, then placing zinc particles with a purity of 99% in the gel, and simultaneously adding oxides of doped barium and cadmium elements (barium oxide and cadmium oxide) to adhere the barium oxide and cadmium oxide to the zinc particles, wherein the molar ratio of zinc to barium to cadmium is 98:1:1;

[0074] Filter again to remove the gel and obtain zinc particles attached with barium oxide and cadmium oxide;

[0075] The zinc particles attached with barium oxide and cadmium oxide were dried at 75°C for 180 minutes, and then placed in a box-type resistance furnace, heated to 500°C, reacted for 25 minutes, and cooled to room temperature to obtain four-needle zinc oxide whiskers doped with barium and cadmium. The electron microscope scanning image at 20 μm is as follows: Figure 4 As shown, it is in a single crystal state with a micron structure.

[0076] Example 4

[0077] The preparation method of multi-element doped symbiotic tetrapod-shaped zinc oxide whiskers comprises the following steps:

[0078] Placing polyethylene glycol in a constant temperature water bath at 20° C. and stirring to dissolve for 2 hours to allow the polyethylene glycol to swell and form a gel, wherein the mass ratio of polyethylene glycol to water is 15:100. Then, zinc particles with a purity of 99% are placed in the gel, and an oxide doped with the element lanthanum (lanthanum oxide) is added to adhere the lanthanum oxide to the zinc particles, wherein the molar ratio of zinc to lanthanum is 96.5:3.5.

[0079] Filter again to remove the gel and obtain zinc particles attached with lanthanum oxide;

[0080] The zinc particles attached with lanthanum oxide were dried at 85°C for 30 minutes, and then placed in a box-type resistance furnace, heated to 1200°C, and reacted for 10 minutes. After cooling to room temperature, lanthanum-doped symbiotic tetrapod-shaped zinc oxide whiskers were obtained, and the electron microscope scanning image thereof at 20 μm was as follows: Figure 5 As shown, it is in a single crystal state with a micron structure.

[0081] Example 5

[0082] The preparation method of multi-element doped symbiotic tetrapod-shaped zinc oxide whiskers comprises the following steps:

[0083] Placing polyethylene glycol in a constant temperature water bath at 25°C and stirring to dissolve for 2 hours to allow the polyethylene glycol to swell and form a gel, wherein the mass ratio of polyethylene glycol to water is 23:100. Then, zinc particles with a purity of 99% are placed in the gel, and an oxide doped with elemental lead (lead oxide) is added to adhere the lead oxide to the zinc particles, wherein the molar ratio of zinc to lead is 98.5:1.5.

[0084] Filter again to remove the gel and obtain zinc particles with lead oxide attached;

[0085] The zinc particles with lead oxide attached were dried at 78°C for 60 minutes, and then placed in a box-type resistance furnace, heated to 800°C, reacted for 12 minutes, and cooled to room temperature to obtain lead-doped co-grown four-needle zinc oxide whiskers. The electron microscope scanning image at 10 μm is as follows: Figure 6 As shown, it is in a single crystal state with a micron structure.

[0086] Example 6

[0087] The preparation method of multi-element doped symbiotic tetrapod-shaped zinc oxide whiskers comprises the following steps:

[0088] Placing polyethylene glycol in a constant temperature water bath at 25° C. and stirring and dissolving for 1 hour to allow the polyethylene glycol to swell and form a gel, wherein the mass ratio of polyethylene glycol to water is 22:100, then placing zinc particles with a purity of 99% in the gel, and simultaneously adding oxides of doped nickel and copper (nickel oxide and copper oxide) to adhere the nickel oxide and copper oxide to the zinc particles, wherein the molar ratio of zinc to nickel and copper is 95:1.5:3.5;

[0089] Filter again to remove the gel and obtain zinc particles attached with nickel oxide and copper oxide;

[0090] The zinc particles attached with nickel oxide and copper oxide were dried at 83°C for 80 minutes, and then placed in a box-type resistance furnace, heated to 800°C, reacted for 15 minutes, and cooled to room temperature to obtain nickel- and copper-doped four-needle zinc oxide whiskers. The electron microscope scanning image at 20 μm is as follows: Figure 7 As shown, it is in a single crystal state with a micron structure.

[0091] Example 7

[0092] The preparation method of multi-element doped symbiotic tetrapod-shaped zinc oxide whiskers comprises the following steps:

[0093] Placing polyethylene glycol in a constant temperature water bath at 20° C. and stirring and dissolving for 2 hours to allow the polyethylene glycol to swell and form a gel, wherein the mass ratio of polyethylene glycol to water is 18:100, then placing zinc particles with a purity of 99% in the gel, and simultaneously adding oxides of doping elements of gallium, lanthanum, and cerium (gallium oxide, lanthanum oxide, and cerium oxide) to adhere the gallium oxide, lanthanum oxide, and cerium oxide to the zinc particles, wherein the molar ratio of zinc to gallium, lanthanum, and cerium is 93:2:2:3;

[0094] Filtering again to remove the gel, obtaining zinc particles attached with gallium oxide, lanthanum oxide and cerium oxide;

[0095] The zinc particles attached with gallium oxide, lanthanum oxide and cerium oxide were dried at 84°C for 40 minutes, and then placed in a box-type resistance furnace, heated to 600°C, reacted for 25 minutes, and cooled to room temperature to obtain gallium, lanthanum and cerium doped four-needle zinc oxide whiskers, the electron microscope scanning image of which at 10 μm is as follows: Figure 8 As shown, it is in a single crystal state with a micron structure.

[0096] The above description is merely an optional embodiment of the present application and does not limit the patent scope of the present application. All equivalent structural transformations made using the contents of the present application specification and drawings under the inventive concept of the present application, or direct / indirect application in other related technical fields are included in the patent protection scope of the present application.

Claims

1. A method for preparing multi-element doped symbiotic tetrapod-shaped zinc oxide whiskers, characterized in that: The following steps are involved: Stirring and dissolving polyethylene glycol in water to form a gel, placing zinc particles in the gel, and simultaneously adding an oxide of a doping element so that the oxide of the doping element adheres to the zinc particles; filtering again to remove the gel and obtain zinc particles attached with doping element oxides; The zinc particles with the doping element oxide attached thereto are dried, heated for reaction and then cooled to room temperature to obtain doped four-needle zinc oxide whiskers.

2. The method for preparing multi-element doped symbiotic tetrapod-shaped zinc oxide whiskers according to claim 1, wherein: The doping elements include beryllium, boron, carbon, silicon, phosphorus, sulfur, calcium, magnesium, scandium, titanium, vanadium, chromium, manganese, iron, cobalt, nickel, copper, zinc, gallium, germanium, arsenic, selenium, bromine, strontium, yttrium, zirconium, niobium, molybdenum, technetium, ruthenium, rhodium, palladium, silver, cadmium, indium, tin, antimony, tellurium, iodine, barium, lanthanum, cerium, etc. , praseodymium, neodymium, promethium, samarium, europium, gadolinium, terbium, dysprosium, holmium, erbium, thulium, ytterbium, lutetium, hafnium, tantalum, tungsten, rhenium, osmium, iridium, platinum, gold, mercury, thallium, lead, bismuth, polonium, astatine, francium, radium, actinium, protactinium, uranium, neptunium, plutonium, americium, curium, berkelium, californium, einsteinium, fermium, mendelevium, nobelium, lawrencium, ruthenium, Copper, niobium, feldspar, molybdenum, lead, and At least one of .

3. The method for preparing multi-element doped symbiotic tetrapod-shaped zinc oxide whiskers according to claim 1, wherein: In the zinc particles attached with the doping element oxide, the molar ratio of zinc to the doping element is (50-99): (1-49).

4. The method for preparing multi-element doped symbiotic tetrapod-shaped zinc oxide whiskers according to claim 1, wherein: The purity of the zinc particles is 99%.

5. The method for preparing multi-element doped symbiotic tetrapod-shaped zinc oxide whiskers according to claim 1, wherein: The step of stirring and dissolving polyethylene glycol in water to form a gel comprises: The polyethylene glycol is placed in a constant temperature water bath at 20° C.-30° C. and stirred to dissolve for 1 h-2 h, so that the polyethylene glycol swells and forms a gel.

6. The method for preparing multi-element doped symbiotic tetrapod-shaped zinc oxide whiskers according to claim 1, characterized in that: In the step of stirring and dissolving polyethylene glycol in water, the mass ratio of the polyethylene glycol to water is (15-25):

100.

7. The method for preparing multi-element doped symbiotic tetrapod-shaped zinc oxide whiskers according to claim 1, wherein: The step of drying the zinc particles attached with the doping element oxide comprises: The zinc particles attached with the doping element oxide are dried at 75° C.-85° C. for 30 min-180 min.

8. The method for preparing multi-element doped symbiotic tetrapod-shaped zinc oxide whiskers according to claim 1, characterized in that: The step of performing heating reaction symbiosis comprises: The dried zinc particles with the doping element oxide attached thereto are placed in a box-type resistance furnace, and then heated to 500°C-1200°C and reacted for 10 minutes-25 minutes.

9. Multi-element doped symbiotic tetrapod-shaped zinc oxide whisker product, characterized in that: The whiskers are obtained by the preparation method of multi-element doped symbiotic tetrapod-shaped zinc oxide whiskers as described in any one of claims 1 to 9.

10. Application of multi-element doped symbiotic tetrapod-shaped zinc oxide whisker products, characterized in that: The multi-element doped symbiotic tetrapod-shaped zinc oxide whisker product as claimed in claim 9 is applied to the fields of transparent conduction, field emission and electroluminescence.

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