CN113479928A - InGaZnO4Preparation method of single-phase nano powder - Google Patents
InGaZnO4Preparation method of single-phase nano powder Download PDFInfo
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Abstract
InGaZnO4The preparation method of the single-phase nano powder comprises the following steps: the molar ratio is 1:1:1, putting the metal indium particles, the metal gallium particles and the metal zinc particles into a container, and adding a nitric acid solution with the mass concentration of 50-60% into the container in batches to obtain a metal ion solution with the ion concentration of 0.1-0.6 mol/L; dropwise adding a precipitator into the metal ion solution, and controlling the stirring speed to be 400-450 rpm when the pH of the solution is less than 4; stopping dripping the precipitator when the pH value of the solution is between 4 and 4.5, and keeping the reaction for 0.5 to 1 hour; stopping dripping the precipitator when the pH value of the solution is between 5.5 and 6, and keeping the reaction for 0.5 to 1 hour; when the pH value is more than 6, the stirring speed is controlled to be 450-500 rpm; stopping dripping the precipitator when the pH is more than 7.5-8.8, continuously stirring for 1-2 h, and then aging for 18-24 h at room temperature; washing and drying to obtain a powder precursor; calcining the powder precursor twice to obtain InGaZnO4Single-phase nano powder.
Description
Technical Field
The application belongs to the technical field of oxide powder materials, and particularly relates to InGaZnO4Single phase nano-meterA method for preparing powder.
Background
As Transparent Amorphous Oxide Semiconductor (TAOSs) materials for fabricating channel layers of high performance Thin Film Transistors (TFTs), oxide semiconductor thin films have good low temperature growth, simple fabrication process, and high mobility and light transmittance, and become the most promising next-generation display technology driver devices, and are increasingly valued and developed. Common TAOS-TFT channel layer material systems are In-Ga-Zn-O, In-Zn-O, Sn-Zn-O and Al-Zn-Sn-O. In particular, IGZO has a large band gap and controllability of carrier concentration, which makes it very promising in transparent TFT applications.
The IGZO band gap is about 3.5eV, the electron mobility is 1-2 orders of magnitude higher than that of amorphous silicon, and the amorphous silicon/having a band gap of about 3.5eV and 1-amorphous silicon/still has a maximum characteristic. Because the influence of crystal boundary is avoided, the amorphous structure material has better uniformity than a polycrystalline material, and has great advantage for large-area preparation. And the IGZO-TFT has more excellent indexes such as field effect mobility, switching current ratio, threshold voltage stability and the like, and the IGZO-TFT has four advantages of high mobility, amorphous channel structure, full transparency and low-temperature preparation, so that the IGZO as a TFT channel material is more consistent with the future development trend of large size, high definition, flexibility and low energy consumption of a display than polysilicon and amorphous silicon, and is widely applied to the fields of AMOLED, LCD, flexible display and electronic paper.
The density and microstructure of the oxygen ceramic target have a large effect on the quality of the sputtered film. In order to obtain a high-quality film, a corresponding high-quality target is needed, and the high-quality IGZO powder is a key basis for the performance and application of the target and the film. Typically, the indium gallium zinc oxide is In composition2O3、Ga2O3And ZnO is sintered according to a specific proportion, wherein the commercial ratio is mainly 1:1:1, and the target material phase after complete reaction sintering is InGaZnO4How to obtain InGaZnO4The single-phase powder is a technical problem which needs to be solved urgently.
Disclosure of Invention
In view of this, some embodiments discloseInGaZnO4The preparation method of the single-phase nano powder comprises the following steps:
the molar ratio is 1:1:1, putting the metal indium particles, the metal gallium particles and the metal zinc particles into a container, adding a nitric acid solution with the mass concentration of 50-60% into the container in a grading manner, and dissolving the metal indium, the metal gallium and the metal zinc to obtain a metal ion solution with the ion concentration of 0.1-0.6 mol/L;
dropwise adding a precipitator into the metal ion solution, stirring, and monitoring the pH value of the solution, wherein when the pH value of the solution is less than 4, the stirring speed is controlled to be 400-450 rpm; stopping dripping the precipitator when the pH value of the solution is between 4 and 4.5, and keeping the reaction for 0.5 to 1 hour; then continuously dropwise adding a precipitator, stopping dropwise adding the precipitator when the pH value of the solution is between 5.5 and 6, and keeping the reaction for 0.5 to 1 hour; when the pH value is more than 6, the stirring speed is controlled to be 450-500 rpm; stopping dripping the precipitator when the pH is more than 7.5-8.8, continuously stirring for 1-2 h, and then aging for 18-24 h at room temperature;
washing the product aged at room temperature, and drying the washed product to obtain a powder precursor;
placing the powder precursor in a corundum crucible, heating to 700-800 ℃ at a heating rate of 2-3 ℃/min, calcining, preserving heat for 20-40 min, heating to 1000-1150 ℃ at the same heating rate, calcining again, preserving heat for 1-4 h, cooling to 200 ℃ at a cooling rate of 3-5 ℃/min, and naturally cooling to room temperature to obtain the InGaZnO4Single-phase nano powder.
Further, some embodiments disclose InGaZnO4The preparation method of the single-phase nano powder comprises the following steps of: firstly, controlling the temperature of the solution to be 20-30 ℃ to dissolve metal zinc; then controlling the temperature of the solution to be 55-70 ℃, stirring the solution at a rotating speed of 200-350 rpm, and dissolving the metal indium; and then raising the temperature of the solution to 75-90 ℃, stirring the solution at the rotating speed of 250-300 rpm, and dissolving the metal gallium.
Some examples disclose InGaZnO4The preparation method of the single-phase nano powder comprises the following steps of: centrifugally washing twice with pure water at 2500rpm for each centrifugal treatmentThe time is 5 min; centrifuging and washing twice by pure water at the rotating speed of 3500rpm, wherein the centrifuging time is 5min each time; centrifuging and washing twice by pure water at the rotating speed of 4000rpm, wherein the centrifuging time is 5min each time; the mixture is centrifugally washed twice by absolute ethyl alcohol at the rotating speed of 4000rpm, and the centrifugal treatment time is 5min each time.
Some examples disclose InGaZnO4According to the preparation method of the single-phase nano powder, in the drying process of a washing product, the drying temperature is set to be 85-115 ℃, and the heat preservation time is 18-24 hours.
Some examples disclose InGaZnO4The preparation method of the single-phase nano powder adopts ammonia water or sodium hydroxide solution as a precipitator.
Some examples disclose InGaZnO4The preparation method of the single-phase nano powder comprises the step of adding nitric acid solution into a container for at least three times.
Some examples disclose InGaZnO4The preparation method of the single-phase nano powder comprises the steps of adding a nitric acid solution with the same chemical equivalent as that of metal zinc in the process of dissolving metal zinc, adding a nitric acid solution with the same chemical equivalent as that of metal indium in the process of dissolving metal indium, and adding a nitric acid solution with the same chemical equivalent as that of metal gallium in the process of dissolving metal gallium.
Some examples disclose InGaZnO4The preparation method of the single-phase nano powder comprises the steps of adding a nitric acid solution with the same chemical equivalent as that of the metal zinc for multiple times in the process of dissolving the metal zinc, adding a nitric acid solution with the same chemical equivalent as that of the metal indium for multiple times in the process of dissolving the metal indium, and adding a nitric acid solution with the same chemical equivalent as that of the metal gallium for multiple times in the process of dissolving the metal gallium.
The embodiment of the application discloses InGaZnO4The preparation method of the single-phase nano powder comprises the following steps of: 1:1, dissolving indium, gallium and zinc in a nitric acid solution to form a metal ion solution with three metal ions uniformly distributed, performing fractional precipitation on the three metal ions at different pH values to obtain IGZO co-precipitated starch, and calcining to obtain the InGaZnO with small initial grain size, narrow particle size distribution range and high purity4The single-phase nano powder has simple preparation method and process,low cost, easily controlled preparation conditions, short process period, and wide application range in InGaZnO4Has important application value in the preparation of single-phase nano powder.
Drawings
FIG. 1 example 1 InGaZnO4SEM image of single-phase nano powder
FIG. 2 example 1 InGaZnO4Single-phase nano powder TEM image
FIG. 3 example 1 InGaZnO4Single-phase nano powder XRD pattern
Detailed Description
The word "embodiment" as used herein, is not necessarily to be construed as preferred or advantageous over other embodiments, including any embodiment illustrated as "exemplary". Performance index tests in the examples of this application, unless otherwise indicated, were performed using routine experimentation in the art. It is to be understood that the terminology used herein is for the purpose of describing particular embodiments only and is not intended to be limiting of the disclosure.
Unless defined otherwise, technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this application belongs; other test methods and techniques not specifically mentioned in the present application are those commonly employed by those of ordinary skill in the art.
The terms "substantially" and "about" are used herein to describe small fluctuations. For example, they may mean less than or equal to ± 5%, such as less than or equal to ± 2%, such as less than or equal to ± 1%, such as less than or equal to ± 0.5%, such as less than or equal to ± 0.2%, such as less than or equal to ± 0.1%, such as less than or equal to ± 0.05%. Numerical data represented or presented herein in a range format is used merely for convenience and brevity and thus should be interpreted flexibly to include not only the numerical values explicitly recited as the limits of the range, but also to include all the individual numerical values or sub-ranges encompassed within that range as if each numerical value and sub-range is explicitly recited. For example, a numerical range of "1 to 5%" should be interpreted to include not only the explicitly recited values of 1% to 5%, but also include individual values and sub-ranges within the indicated range. Thus, included in this numerical range are individual values, such as 2%, 3.5%, and 4%, and sub-ranges, such as 1% to 3%, 2% to 4%, and 3% to 5%, etc. This principle applies equally to ranges reciting only one numerical value. Moreover, such an interpretation applies regardless of the breadth of the range or the characteristics being described.
In this document, including the claims, conjunctions such as "comprising," including, "" carrying, "" having, "" containing, "" involving, "" containing, "and the like are understood to be open-ended, i.e., to mean" including but not limited to. Only the conjunctions "consisting of … …" and "consisting of … …" are closed conjunctions.
In the following detailed description, numerous specific details are set forth in order to provide a better understanding of the present disclosure. It will be understood by those skilled in the art that the present application may be practiced without some of these specific details. In the examples, some methods, means, instruments, apparatuses, etc. known to those skilled in the art are not described in detail in order to highlight the subject matter of the present application.
On the premise of no conflict, the technical features disclosed in the embodiments of the present application may be combined arbitrarily, and the obtained technical solution belongs to the content disclosed in the embodiments of the present application.
In some embodiments, InGaZnO4The preparation method of the single-phase nano powder comprises the following steps:
the molar ratio is 1:1:1, putting the metal indium particles, the metal gallium particles and the metal zinc particles into a container, adding a nitric acid solution with the mass concentration of 50-60% into the container in a grading manner, and dissolving the metal indium, the metal gallium and the metal zinc to obtain a metal ion solution with the ion concentration of 0.1-0.6 mol/L; specifically, a certain amount of indium particles, gallium particles and zinc particles are weighed and placed in a beaker, nitric acid with the mass concentration of 50% -60% is selected, and the nitric acid is added in several times due to different reaction intensity degrees of different metals, so that the metal dissolution process is controlled, the metal zinc can be dissolved firstly, the metal indium and the metal gallium can be dissolved secondly, and the whole dissolution process is carried out on a constant-temperature magnetic stirrer; for example, the temperature of the nitric acid solution is controlled to be 20-30 ℃ to dissolve zinc, the rotating speed of a magnetic stirrer is not required to be adjusted, then the temperature of the nitric acid solution is controlled to be 55-70 ℃ to dissolve metal indium, the rotating speed is controlled to be 200-250 rpm, after 20-30 min, the temperature of the nitric acid solution is increased to 75-90 ℃, metal gallium is dissolved, the rotating speed is adjusted within the range of 250-300 rpm, the dissolving process is controlled, and the reaction is ensured to be carried out stably; after complete dissolution, performing constant volume by using a volumetric flask, firstly, folding filter paper into a flower shape, putting the flower shape into a funnel, then pouring the solution to filter impurities in the solution, and finally, adding pure water to the scale mark of the volumetric flask to obtain a metal ion solution with the metal ion concentration of 0.1-0.6 mol/L; wherein the metal ion concentration refers to the sum of metal indium ions, gallium ions and zinc ions;
in the general oxidation-reduction reaction process of nitric acid and metal, if all nitric acid is added into metal particles at one time, the reaction speed is too high, the reaction is violent, a large amount of heat and gas are generated instantly, the reaction is not uniform easily, if a small amount of nitric acid is added for multiple times, the dissolving process of the metal can be controlled to be performed slowly and uniformly, if the characteristics of three metals are further combined, the adding amount of the nitric acid is controlled while the dissolving temperature is controlled, the uniform and complete dissolution of the three metals can be further promoted, and finally, a uniform multi-metal ion solution with accurate component proportion is obtained;
as an alternative embodiment, a nitric acid solution with the same chemical equivalent as that of the metal zinc is added in the process of dissolving the zinc, the partial nitric acid solution and the metal zinc can completely react, and the metal zinc is completely dissolved; adding a nitric acid solution with the same chemical equivalent as the metal indium in the process of dissolving the metal indium, wherein the part of nitric acid solution can completely react with the metal indium, and the metal indium is completely dissolved; adding nitric acid with the same chemical equivalent as the metal gallium in the process of dissolving the metal gallium, wherein the part of nitric acid solution can completely react with the metal gallium, the metal gallium is completely dissolved, and finally, three kinds of metal particles are completely dissolved to form uniform multi-metal ion solution;
further as an optional embodiment, in the process of dissolving zinc, adding a nitric acid solution with the same chemical equivalent as that of the metallic zinc for multiple times, for example, for 2 to 3 times, to control the dissolving speed of the metallic zinc;
further as an optional embodiment, in the indium dissolving process, the nitric acid solution with the same chemical equivalent as the metal indium is further added for multiple times, for example, 2 to 3 times, so as to control the metal indium dissolving speed;
further as an optional embodiment, in the process of dissolving gallium, adding a nitric acid solution with the same chemical equivalent as that of gallium metal for multiple times, for example, for 2 to 3 times, to control the dissolving speed of gallium metal;
dropwise adding a precipitator into the metal ion solution, stirring, and monitoring the pH value of the solution, wherein when the pH value of the solution is less than 4, the stirring speed is controlled to be 400-450 rpm; stopping dripping the precipitator when the pH value of the solution is between 4 and 4.5, and keeping the reaction for 0.5 to 1 hour; then continuously dropwise adding a precipitator, stopping dropwise adding the precipitator when the pH value of the solution is between 5.5 and 6, and keeping the reaction for 0.5 to 1 hour; when the pH value of the solution is within the range of 4-6, the precipitation is continuously increased and aggregated along with the dropwise addition of the precipitator, the solution is pasty, the viscosity is increased, and a glass rod is required to be used for manual stirring; when the pH value is more than 6, the stirring speed is controlled to be 450-500 rpm; stopping dripping the precipitator when the pH is more than 7.5-8.8, continuously stirring for 1-2 h, then aging for 18-24 h at room temperature, and inoculating crystal grains; in the aging process, the precipitate stands in the mother liquor, small particles gradually dissolve and disappear, and large particles gradually grow up to form particles with the same appearance and narrow particle size distribution range; meanwhile, the stability of the crystal phase structure of the precipitate is poor due to the fluctuation of the early precipitation reaction process, and the crystal phase structure of the precipitate can be more stable in the final aging process;
as an alternative embodiment, the precipitant is ammonia water or sodium hydroxide solution;
washing the product aged at room temperature, and drying the washed product to obtain a powder precursor; specifically, for example, the supernatant in the aged product is poured off, the residual product is uniformly stirred by a glass rod, the aged product is averagely transferred to two centrifuge bottles, then a proper amount of pure water is added into the centrifuge bottles, the mixture is weighed by a balance special for a centrifuge, the mass of the two centrifuge bottles is basically consistent, the error is controlled to be about 1g, the mixture is placed into the centrifuge after shaking up, the first centrifugation speed is set to be 2500rpm, the time is 5min, the supernatant is poured off after finishing, the pure water is added again, the mixture is uniformly stirred for centrifugation, the step is repeated for 6 times, and the centrifugation speed is gradually increased from 2500rpm to 4000rpm, 5min each time; then washing with anhydrous ethanol for 2 times, and centrifuging at 4000rpm for 5min each time; transferring the powder obtained after the last centrifugation to a beaker, placing the beaker in a numerical control electric heating oven for drying, setting the drying temperature to be 85-115 ℃, and preserving the heat for 18-24 hours to obtain a powder precursor;
placing the powder precursor in a corundum crucible, heating to 700-800 ℃ at a heating rate of 2-3 ℃/min, sintering, preserving heat for 20-40 min, heating to 1000-1150 ℃ at the same heating rate, sintering again, preserving heat for 1-4 h, cooling to 200 ℃ at a cooling rate of 3-5 ℃/min, and naturally cooling to room temperature to obtain the InGaZnO4Single-phase nano powder.
The technical details are further illustrated in the following examples.
Example 1
EXAMPLE 1 preparation of InGaZnO4The method for preparing the single-phase nano powder comprises the following steps:
according to a molar ratio of 1:1:1 weighing a certain amount of indium particles, gallium particles and zinc particles, putting the indium particles, the gallium particles and the zinc particles into a beaker, selecting a 55% nitric acid solution, adding nitric acid in several times, controlling the dissolution of metal, dissolving metal zinc firstly, and then dissolving metal indium and metal gallium, wherein the whole dissolving process is carried out on a constant-temperature magnetic stirrer; specifically, a nitric acid solution for dissolving metal zinc is added in two times, the zinc is dissolved when the temperature of the nitric acid solution is 25 ℃, and the rotating speed of a magnetic stirrer does not need to be adjusted; adding a nitric acid solution for dissolving metal indium twice after metal zinc is dissolved, then adjusting the temperature to 65 ℃ to dissolve the metal indium, controlling the rotating speed at 230rpm, adding a nitric acid solution for dissolving metal gallium twice after the metal indium is dissolved, raising the temperature of the nitric acid solution to 80 ℃, and dissolving the metal gallium at 280 rpm; after complete dissolution, performing constant volume by using a volumetric flask, firstly, folding filter paper into a flower shape, putting the flower shape into a funnel, then pouring the solution to filter impurities in the solution, and finally, adding pure water to the scale mark of the volumetric flask to obtain 0.15mol/L metal ion solution;
pouring the prepared metal ion solution into a beaker, placing the beaker on a constant-temperature magnetic stirrer, slowly dropwise adding an ammonia water solution into the solution by using a dropping funnel, slowly generating white precipitate, measuring the pH value of the solution by using a pH meter, controlling the precipitation process by using the pH, controlling the rotating speed of the stirrer to be 450rpm when the pH is less than 4, stopping dropwise adding when the pH reaches 4.3, keeping the precipitation reaction for 45min, continuously adding the ammonia water along with the dropwise addition of the precipitate when the pH is within the range of 4.3-6 to form paste, increasing the viscosity, manually stirring by using a glass rod until the pH reaches 6, stopping dropwise adding at the moment, continuously keeping the reaction for 1h, controlling the rotating speed of the stirrer to be 480rpm when the pH is more than 6, stopping dropwise adding after the pH value is 8.3, stopping stirring after stirring for 1.5h, aging for 20h at room temperature, and inoculating crystal grains;
pouring out the supernatant, uniformly stirring by using a glass rod, averagely transferring to two 1L centrifuge bottles, then adding a proper amount of pure water into the centrifuge bottles, weighing by using a balance special for a centrifuge, ensuring that the masses of the two centrifuge bottles are basically consistent, controlling the error to be about 1g, uniformly shaking, then putting into the centrifuge, setting the first centrifugation speed to be 2500rpm for 5min, pouring out the supernatant after finishing, adding the pure water again, uniformly stirring, centrifuging, repeating the step for 6 times, setting the centrifugation speed to be 2500rpm for the first two times, increasing the middle two times to 3500rpm, and finally increasing the centrifugation speed to 4000rpm for 5min each time; then washing with anhydrous ethanol for 2 times, and centrifuging at 4000rpm for 5min each time;
transferring the powder obtained after the last centrifugation to a beaker, and drying in a numerical control electric heating oven, wherein the drying temperature is set to 100 ℃, and the drying heat preservation time is set to 20 hours, so as to obtain a powder precursor;
placing the dried powder precursor into a corundum crucible, heating the temperature of a resistance furnace to 750 ℃ at a heating rate of 2.5 ℃/min, preserving the heat for 30min, then heating to 1050 ℃ at the same heating rate, preserving the heat for 2h, cooling the resistance furnace to 200 ℃ at a cooling rate of 4 ℃/min after the heat preservation is finished, cooling to room temperature, and taking out to obtain the InGaZnO4Single-phase nano powder.
For the InGaZnO prepared in example 14The single-phase nano powder is tested, and figure 1 shows InGaZnO4SEM of single-phase nano powder, FIG. 2 is InGaZnO4TEM image of single-phase nano-powder transmission electron microscope, known to those skilled in the art, InGaZnO4Single-phase nano powder particleThe particle size distribution range is narrow, and the particle size is uniform; FIG. 3 is InGaZnO4The XRD pattern of the single-phase nano powder corresponds to the diffraction peak of the standard card PDF #38-1104, which shows that the obtained InGaZnO4The single-phase nano powder product is InGaZnO with hexagonal crystal form4The powder has high purity and good crystallization performance.
Example 2
Example 2 preparation of InGaZnO4The method for preparing the single-phase nano powder comprises the following steps:
according to a molar ratio of 1:1:1, weighing a certain amount of indium particles, gallium particles and zinc particles, putting the indium particles, the gallium particles and the zinc particles into a beaker, selecting a 50% nitric acid solution, adding nitric acid in several times, controlling the dissolution of metal, dissolving metal zinc firstly, and then dissolving metal indium and metal gallium, wherein the whole dissolving process is carried out on a constant-temperature magnetic stirrer; specifically, a nitric acid solution for dissolving metal zinc is added, the zinc is dissolved when the temperature of the nitric acid solution is 20 ℃, and the rotating speed of a magnetic stirrer does not need to be adjusted; adding a nitric acid solution for dissolving metal indium after dissolving metal zinc, then adjusting the temperature to 55 ℃ to dissolve metal indium, controlling the rotating speed at 200rpm, adding a nitric acid solution for dissolving metal gallium after dissolving metal indium, raising the temperature of the nitric acid solution to 75 ℃, and dissolving metal gallium at the rotating speed of 250 rpm; after complete dissolution, performing constant volume by using a volumetric flask, firstly, folding filter paper into a flower shape, putting the flower shape into a funnel, then pouring the solution to filter impurities in the solution, and finally, adding pure water to the scale mark of the volumetric flask to obtain 0.9mol/L metal ion solution;
pouring the prepared metal ion solution into a beaker, placing the beaker on a constant-temperature magnetic stirrer, slowly dropwise adding a sodium hydroxide solution into the solution by using a dropping funnel, slowly generating white precipitate, simultaneously measuring the pH value of the solution by using a pH meter, controlling the precipitation process by using the pH, controlling the rotating speed of the stirrer to be 400rpm when the pH is less than 4, stopping dropwise adding when the pH reaches 4, keeping the precipitation reaction for 30min, continuously adding the sodium hydroxide solution with the dropwise addition of the precipitate when the pH is within the range of 4-6 to form paste, increasing the viscosity, manually stirring by using a glass rod until the pH reaches 6.0, stopping dropwise adding at the moment, continuously keeping the reaction for 1h, controlling the rotating speed of the stirrer to be 450rpm when the pH is more than 6.0, stopping dropwise adding after the pH value is 7.8, stopping stirring after 1h, aging at room temperature for 18h, and inoculating crystal grains;
pouring out the supernatant, uniformly stirring by using a glass rod, averagely transferring to two 1L centrifuge bottles, then adding a proper amount of pure water into the centrifuge bottles, weighing by using a balance special for a centrifuge, ensuring that the masses of the two centrifuge bottles are basically consistent, controlling the error to be about 1g, uniformly shaking, then putting into the centrifuge, setting the first centrifugation speed to be 2500rpm for 5min, pouring out the supernatant after finishing, adding the pure water again, uniformly stirring, centrifuging, repeating the step for 6 times, setting the centrifugation speed to be 3000rpm for the first two times, increasing the middle two times to 3500rpm, and finally increasing the centrifugation speed to 4000rpm for 5min each time; then washing with anhydrous ethanol for 2 times, and centrifuging at 4000rpm for 5min each time;
transferring the powder obtained after the last centrifugation to a beaker, and drying in a numerical control electric heating oven, wherein the drying temperature is set to 85 ℃, and the drying heat preservation time is set to 24 hours, so as to obtain a powder precursor;
placing the dried powder precursor into a corundum crucible, heating the temperature of a resistance furnace to 700 ℃ at a heating rate of 3 ℃/min, preserving the heat for 20min, heating the temperature to 1000 ℃ at the same heating rate, preserving the heat for 1h, cooling the resistance furnace to 200 ℃ at a cooling rate of 3 ℃/min after the heat preservation is finished, cooling the resistance furnace to room temperature, and taking out the resistance furnace to obtain the InGaZnO4Single-phase nano powder.
For the InGaZnO prepared in this example 24The single-phase nano powder is tested, and the result shows that the InGaZnO4The single-phase nano powder has small granularity, good dispersibility, typical particle size of about 30-70 nm, narrow particle size distribution range, uniform particle size, high powder purity and good crystallization property.
Example 3
Example 3 preparation of InGaZnO4The method for preparing the single-phase nano powder comprises the following steps:
according to a molar ratio of 1:1:1 weighing a certain amount of indium particles, gallium particles and zinc particles, putting the indium particles, the gallium particles and the zinc particles into a beaker, selecting a 60% nitric acid solution, adding nitric acid in several times, controlling the dissolution of metal, dissolving metal zinc firstly, and then dissolving metal indium and metal gallium, wherein the whole dissolving process is carried out on a constant-temperature magnetic stirrer; specifically, a nitric acid solution for dissolving metal zinc is added, the zinc is dissolved when the temperature of the nitric acid solution is 30 ℃, and the rotating speed of a magnetic stirrer does not need to be adjusted; after dissolving the metal zinc, adding a nitric acid solution for dissolving the metal indium, then adjusting the temperature to 70 ℃ to dissolve the metal indium, controlling the rotating speed to be 250rpm, after dissolving the metal indium, adding a nitric acid solution for dissolving the metal gallium, raising the temperature of the nitric acid solution to 90 ℃, and dissolving the metal gallium at the rotating speed of 300 rpm; after complete dissolution, performing constant volume by using a volumetric flask, firstly, folding filter paper into a flower shape, putting the flower shape into a funnel, then pouring the solution to filter impurities in the solution, and finally, adding pure water to the scale mark of the volumetric flask to obtain 0.6mol/L metal ion solution;
pouring the prepared metal ion solution into a beaker, placing the beaker on a constant-temperature magnetic stirrer, slowly dropwise adding a sodium hydroxide aqueous solution into the solution by using a dropping funnel, slowly generating white precipitate, simultaneously measuring the pH value of the solution by using a pH meter, controlling the rotating speed of the stirrer to be 500rpm through the pH control precipitation process when the pH value is less than 4.5, stopping dropwise adding when the pH value reaches 4.5, keeping the precipitation reaction for 1 hour, continuously increasing the precipitate along with the dropwise adding of the sodium hydroxide aqueous solution when the pH value is within the range of 4.5-6 to form paste, increasing the viscosity, manually stirring by using a glass rod until the pH value reaches 6.0, stopping dropwise adding at the moment, continuously keeping the reaction for 1 hour, controlling the rotating speed of the stirrer to be 500rpm when the pH value is more than 8.8, stopping dropwise adding after stirring for 2 hours, aging for 24 hours at room temperature, and inoculating crystal grains;
pouring out the supernatant, uniformly stirring by using a glass rod, averagely transferring to two 1L centrifuge bottles, then adding a proper amount of pure water into the centrifuge bottles, weighing by using a balance special for a centrifuge, ensuring that the masses of the two centrifuge bottles are basically consistent, controlling the error to be about 1g, uniformly shaking, then putting into the centrifuge, setting the first centrifugation speed to be 2500rpm for 5min, pouring out the supernatant after finishing, adding the pure water again, uniformly stirring, centrifuging, repeating the step for 6 times, setting the centrifugation speed to be 3000rpm for the first two times, increasing the middle two times to 3500rpm, and finally increasing the centrifugation speed to 4000rpm for 5min each time; then washing with anhydrous ethanol for 2 times, and centrifuging at 4000rpm for 5min each time;
transferring the powder obtained after the last centrifugation to a beaker, and drying in a numerical control electric heating oven, wherein the drying temperature is set to be 110 ℃, and the drying heat preservation time is set to be 18h, so as to obtain a powder precursor;
placing the dried powder precursor into a corundum crucible, heating the temperature of a resistance furnace to 800 ℃ at a heating rate of 3 ℃/min, preserving the heat for 40min, heating the temperature to 1100 ℃ at the same heating rate, preserving the heat for 2h, cooling the resistance furnace to 200 ℃ at a cooling rate of 5 ℃/min after the heat preservation is finished, cooling the resistance furnace to room temperature, and taking out the resistance furnace to obtain the InGaZnO4Single-phase nano powder.
For the InGaZnO prepared in this example 34The single-phase nano powder is tested, and the result shows that the InGaZnO4The single-phase nano powder has small granularity, good dispersibility, typical particle size of about 20-70 nm, narrow particle size distribution range, uniform particle size, high powder purity and good crystallization property.
The embodiment of the application discloses InGaZnO4The preparation method of the single-phase nano powder comprises the following steps of: 1:1, dissolving indium, gallium and zinc in a nitric acid solution to form a metal ion solution with three metal ions uniformly distributed, performing fractional precipitation on the three metal ions at different pH values to obtain IGZO co-precipitated starch, and calcining to obtain the InGaZnO with small initial grain size, narrow particle size distribution range and high purity4Single-phase nano powder, simple preparation method, low cost, easily controlled preparation conditions, short process period and the application of the InGaZnO4Has important application value in the preparation of single-phase nano powder.
The technical solutions and the technical details disclosed in the embodiments of the present application are only examples to illustrate the inventive concept of the present application, and do not constitute a limitation on the technical solutions of the present application, and all the conventional changes, substitutions, combinations, and the like made to the technical details disclosed in the present application have the same inventive concept as the present application and are within the protection scope of the claims of the present application.
Claims (8)
1.InGaZnO4Single-phase nano powderThe method for preparing (1), characterized in that the method comprises:
the molar ratio is 1:1:1, putting the metal indium particles, the metal gallium particles and the metal zinc particles into a container, adding a nitric acid solution with the mass concentration of 50-60% into the container in a grading manner, and dissolving the metal indium, the metal gallium and the metal zinc to obtain a metal ion solution with the ion concentration of 0.1-0.6 mol/L;
dropwise adding a precipitator into the metal ion solution, stirring, and monitoring the pH value of the solution, wherein when the pH value of the solution is less than 4, the stirring speed is controlled to be 400-450 rpm; stopping dripping the precipitator when the pH value of the solution is between 4 and 4.5, and keeping the reaction for 0.5 to 1 hour; then continuously dropwise adding a precipitator, stopping dropwise adding the precipitator when the pH value of the solution is between 5.5 and 6, and keeping the reaction for 0.5 to 1 hour; when the pH value is more than 6, the stirring speed is controlled to be 450-500 rpm; stopping dripping the precipitator when the pH is more than 7.5-8.8, continuously stirring for 1-2 h, and then aging for 18-24 h at room temperature;
washing the product aged at room temperature, and drying the washed product to obtain a powder precursor;
placing the powder precursor in a corundum crucible, heating to 700-800 ℃ at a heating rate of 2-3 ℃/min, calcining, preserving heat for 20-40 min, heating to 1000-1150 ℃ at the same heating rate, calcining again, preserving heat for 1-4 h, cooling to 200 ℃ at a cooling rate of 3-5 ℃/min, and naturally cooling to room temperature to obtain the InGaZnO4Single-phase nano powder.
2. The InGaZnO of claim 14The preparation method of the single-phase nano powder is characterized in that the dissolving process of the metal indium, gallium and zinc comprises the following steps:
firstly, controlling the temperature of the solution to be 20-30 ℃ to dissolve metal zinc; then controlling the temperature of the solution to be 55-70 ℃, stirring the solution at a rotating speed of 200-350 rpm, and dissolving the metal indium; and then raising the temperature of the solution to 75-90 ℃, stirring the solution at the rotating speed of 250-300 rpm, and dissolving the metal gallium.
3. The InGaZnO of claim 14Preparation method of single-phase nano powderThe method is characterized in that the washing process of the product after aging at room temperature comprises the following steps:
centrifuging and washing twice by pure water at the rotating speed of 2500rpm, wherein the centrifuging time is 5min each time;
centrifuging and washing twice by pure water at the rotating speed of 3500rpm, wherein the centrifuging time is 5min each time;
centrifuging and washing twice by pure water at the rotating speed of 4000rpm, wherein the centrifuging time is 5min each time;
the mixture is centrifugally washed twice by absolute ethyl alcohol at the rotating speed of 4000rpm, and the centrifugal treatment time is 5min each time.
4. The InGaZnO of claim 14The preparation method of the single-phase nano powder is characterized in that in the drying process of a washing product, the drying temperature is set to be 85-115 ℃, and the heat preservation time is 18-24 hours.
5. The InGaZnO of claim 14The preparation method of the single-phase nano powder is characterized in that the precipitator is ammonia water or sodium hydroxide solution.
6. The InGaZnO of claim 14The preparation method of the single-phase nano powder is characterized in that the nitric acid solution is added into a container at least three times.
7. InGaZnO according to claim 24The preparation method of the single-phase nano powder is characterized in that a nitric acid solution with the same chemical equivalent as that of metal zinc is added in the process of dissolving metal zinc, a nitric acid solution with the same chemical equivalent as that of metal indium is added in the process of dissolving metal indium, and a nitric acid solution with the same chemical equivalent as that of metal gallium is added in the process of dissolving metal gallium.
8. The InGaZnO of claim 74The preparation method of the single-phase nano powder is characterized in that nitric acid solution with the same chemical equivalent as the metal zinc is added for multiple times in the process of dissolving the metal zinc, and the process of dissolving the metal indium is carried outAdding nitric acid solution with the same chemical equivalent as that of the metal indium for multiple times, and adding nitric acid solution with the same chemical equivalent as that of the metal gallium for multiple times in the process of dissolving the metal gallium.
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