CN101811660A - Co-doped nanometer zinc oxide powder body and preparation method thereof - Google Patents
Co-doped nanometer zinc oxide powder body and preparation method thereof Download PDFInfo
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Abstract
The invention discloses a co-doped nanometer zinc oxide powder body and a preparation method thereof. The co-coped elements include a first metal element and a second metal element, wherein the first metal element is titanium, and the second metal element is aluminum, gallium, indium or tin; by total amount of substance, the sum of the first metal element, the second metal element and zinc in zinc oxide is 100 parts, wherein the sum of the first metal element and the second metal element accounts for 0.005-30 parts, and the scope of the part ratio of the first metal element and the second metal element is 1:100 to 100:1. Compared with the prior art, the method has accurately controllable reaction conditions, and the applied device is simple, has low cost, can control pollution conveniently, and is suitable for large-scale industrial production; and the doping uniformity of the obtained co-doped zinc oxide powder body is high, the powder body particles are uniform and in approximate ball shape, and have higher sintering activity, and the single phase property of the nanometer powder body is realized on the premise of high content of doped elements.
Description
Technical field
The invention belongs to field of inorganic nano material, particularly the nanometer Zinc oxide powder of codope and preparation method.
Background technology
(Transparent Conductive Oxide TCO) is a kind of semiconductor material with wide forbidden band with higher free carrier concentration to transparent conductive oxide, and its free carrier comes from the defective of material or external doping.CdO is the TCO material of inventing the earliest, subsequently, and SnO
2And In
2O
3The research work of base transparent conducting film moves to maturity technically and comes into the market, and becomes main flow TCO material gradually and be used widely.Rise the eighties in 20th century, and the basic TCO thin film study of zinc oxide (ZnO) progressively rises.Market mainstream TCO material is tin indium oxide (Indium Tin Oxide, ITO), but, because the indium among the ITO is a kind of rare metal, reserves are limited, because market is sharply soaring for the demand of TCO material, zno-based TCO material begins to become the substitution material that enjoys expectation and becomes the research focus simultaneously, (Aluminum Doped Zinc Oxide, electrical conductivity AZO) has reached 10 to the aluminum current doping zinc-oxide
-5Ω cm magnitude, and its transmitance at visible-range has surpassed 85%, has begun market-oriented application.Except electrical conductivity and transmitance, the characteristics such as influence of refractive index, heat endurance, doped chemical also are the research emphasis of zno-based TCO material, these The Characteristic Study to the application of promoting the zno-based transparent conductive film, to improve film characteristics significant.Studies show that the zinc oxide (single doping zinc-oxide) that has only single-element to mix is difficult to satisfy in the practical application area requirement to above-mentioned each characteristic.
As far back as 1984, T.Minami took the lead in having reported that to utilize rf magnetron sputtering be that target prepares resistivity and is better than 2 * 10 with the oxide
-4The AZO film of the Ω cm order of magnitude.Up to now, rf magnetron sputtering remains the preparation method that zno-based TCO film is the most effective, be suitable for industrial large-scale application, has film density height, good uniformity, is easy to the large tracts of land high speed deposition, repeats advantages such as reliable.When utilizing this method to prepare film, the quality of target is directly connected to the stability and the film performance of sputtering technology in the sputter procedure.When the preparation doped ZnO-based film, the target of generally selecting for use has ceramic target or alloys target.Nankai University discloses at Chinese invention patent ublic specification of application CN101572279A in November, 2009 and adopts Al or Ga doping ZnO ceramic target, or Zn-Al, Zn-Ga alloys target prepare the method for doped ZnO-based TCO film as sputtering target material.
Compare with alloys target, ceramic target is the sputtering target material that industrial quarters more extensively adopts.Generally, ceramic target is by the pressure forming of target powder, high temperature sintering are obtained, and wherein the quality of target powder has a significant impact for the performance of ceramic target.The preparation of most of doping ZnO powder is Zinc oxide powder and adulterated powder to be carried out ball milling mix, and is prepared in conjunction with pressure forming and high-sintering process again.This method preparation technology is simple relatively, but also comes with some shortcomings: at first, adopt the mode of ball milling to be difficult to a small amount of adulterated powder evenly is mixed in the Zinc oxide powder, especially be difficult to realize nano level even mixing; Secondly, in the process of ball milling, introduce other impurity easily, reduce the purity of target, even influence the quality of target thus; Once more, used powder body material mostly is micron dimension greatly, its sintering activity is lower, need high temperature to carry out sintering above 1300 ℃, and alloy and zinc oxide easily react and generate nonconducting segregation (as generate the zinc aluminate phase in aluminium-doped zinc oxide) mutually under this temperature, cause the inhomogeneities of target electrical conductivity, thereby influence the stability of aura in the sputter procedure, and then influence film quality.Therefore how obtaining evenly doping and the high nanoscale doping zinc-oxide powder of sintering activity is the important topic that improves doping zinc-oxide ceramic target performance.
Summary of the invention
First technical problem that the present invention will solve is the nanometer Zinc oxide powder that a kind of codope is provided at above-mentioned prior art.
Second technical problem that the present invention will solve provides a kind of preparation method of nanometer Zinc oxide powder of codope.
The present invention solves the technical scheme that above-mentioned first technical problem adopts: a kind of nanometer Zinc oxide powder of codope, the element that comprises zinc oxide and codope, the element of codope comprises first metallic element and second metallic element, first metallic element is a titanium elements, and second metallic element is aluminium, gallium, indium or tin element; By amount of substance, the summation of first metallic element, second metallic element and zinc in zinc oxide element is 100 parts, wherein the summation of first metallic element and second metallic element accounts for 0.005～30 part, and the portion rate scope of first metallic element and second metallic element is 1: 100 to 100: 1.
The present invention solves above-mentioned second technical scheme that technical problem adopted: a kind of method for preparing the nanometer Zinc oxide powder of codope comprises the steps:
Step 1: titanium tetrachloride is dissolved in 0～5 ℃ of deionized water, forms the aqueous solution of 0.1～5mol/L;
Step 3: the slaine and the zinc salt that will comprise second metallic element are dissolved into the salting liquid that forms 0.5～6mol/L in the deionized water at normal temperature jointly, by amount of substance, wherein the portion rate scope between the second metallic element ion and the zinc ion is 0.005: 100 to 1: 10;
Step 3: fully with two kinds of aqueous solution in step 1 and the step 2, stirring, form the aqueous metal salt of 0.5～3mol/L, by amount of substance, the summation of titanium ion, the second metallic element ion and zinc ion is 100 parts, wherein the summation of the titanium ion and the second metallic element ion accounts for 0.005～30 part, and the portion rate scope of the titanium elements and second metallic element is 1: 100 to 100: 1.
Step 4: precipitating reagent is dissolved into the precipitant solution that forms 1～6mol/L in the deionized water;
Step 5: be under 300～800 rev/mins the stirring condition at rotating speed, the aqueous metal salt in the step 3 is splashed in the reaction vessel that adds deionized water in advance by different dropping passages simultaneously with precipitant solution in the step 4; In the dropping process, the drop rate of control aqueous metal salt and precipitant solution, the pH value that makes solution in the reaction vessel are between 5～10, and temperature obtains coprecipitated product between 10～60 ℃.
Step 6: the coprecipitate ageing that obtains in the step 5 after 4～48 hours, is spent deionised water 2～5 times, use absolute ethanol washing again 1～3 time, in 80～110 ℃ of baking ovens, dry then and obtained dry white product in 4～24 hours.
Step 7: the white product in the step 6 300～800 ℃ of temperature lower calcinations 1～5 hour, is promptly obtained the nanometer Zinc oxide powder of first metallic element and the second metallic element codope.
For optimizing technique scheme, the measure of taking also comprises:
The above-mentioned second metallic element ion is aluminium ion, gallium ion, indium ion or tin ion.
The above-mentioned slaine that comprises second metallic element is aluminum nitrate, gallium nitrate, indium nitrate or stannic chloride.
Above-mentioned zinc salt is zinc sulfate, zinc nitrate, zinc acetate or zinc chloride.
Above-mentioned precipitating reagent is ammoniacal liquor, ammonium carbonate, carbonic hydroammonium or urea.
Compared with prior art, the invention provides a kind of preparation method of codope zinc oxide nano-powder, this method reaction condition is accurately controlled, and device therefor is simple, with low cost, is convenient to pollute control, is easy to large-scale industrial production; Adopt the implant uniformity height of the codope Zinc oxide powder that preparation method of the present invention obtains, it is subsphaeroidal that powder granule evenly is, and has higher sintering activity, realized the single phase property of nano-powder under the prerequisite that the high-load doped chemical is mixed; So the powder of the present invention's preparation can be used for the preparation of high-performance zinc oxide base transparent conducting film sputtering target material.
Description of drawings
Fig. 1 is the morphology microstructure and the grain-size graph of the codope zinc oxide base nano powder of embodiment 1 (mol ratio of titanium elements and aluminium element is 18: 9);
Fig. 2 is the XRD thing collection of illustrative plates mutually of embodiment 1 (titanium elements is 18: 9 with the mol ratio of aluminium element).
The specific embodiment
Embodiment describes in further detail the present invention below in conjunction with accompanying drawing.
Illustrated in figures 1 and 2 is schematic diagram of the present invention.
Embodiment 1:
Titanium tetrachloride is added dropwise in 5 ℃ the deionized water, is made into 1mol/L solution; Zinc nitrate and aluminum nitrate are dissolved in the deionized water at room temperature, are made into the 1mol/L aqueous solution, wherein mol ratio is 9: 73 between aluminium ion and the zinc ion; Above-mentioned two solution are mixed and the adding appropriate amount of deionized water, and the ion concentration of wiring solution-forming is the salting liquid of 0.5mol/L, and wherein the mol ratio between titanium ion, aluminium ion, the zinc ion is 18: 9: 73; Under 400 rev/mins stirring so that the speed of above-mentioned salting liquid with 50mL/min is added drop-wise in the reaction vessel that deionized water is housed in advance by different dropping passages simultaneously with the ammonia spirit of 1mol/L, regulate in the dropping process ammonia spirit drop rate, the pH value of solution in the reaction vessel is remained between 7.0～7.2, solution temperature is 25 ℃, obtains coprecipitated product; Behind sediment ageing 10h, spend deionised water 3 times, use absolute ethanol washing again 2 times, oven dry 6h obtains dry white product in 110 ℃ of baking ovens then; At 500 ℃ of temperature lower calcination 3h, the mol ratio that is titanium elements and aluminium element is 18: 9 a codope zinc oxide nano-powder with white product.
When using field emission scanning electron microscope (SEM) to observe this titanium aluminium codope zinc oxide nano-powder, the pattern of powder and particle diameter are as shown in Figure 1.As can be seen from the figure, it is subsphaeroidal that uniform particles is, and particle diameter is about 30nm.Use x-ray diffractometer (XRD) that this titanium aluminium codope zinc oxide nano-powder is carried out thing phase atlas analysis, judge when having or not the second phase impurity, obtain Fig. 2.Among Fig. 2, abscissa is 2 θ angles, and ordinate is a relative intensity, and as can be seen from Figure 2, this titanium aluminium codope zinc oxide nano-powder is the buergerite phase structure of zinc oxide, does not have the second phase dephasign.
Embodiment 2:
Titanium tetrachloride is added dropwise in 0 ℃ the deionized water, is made into 3mol/L solution; Zinc nitrate and aluminum nitrate are dissolved in the deionized water at room temperature, are made into the 3mol/L aqueous solution, wherein mol ratio is 1: 44 between aluminium ion and the zinc ion; Above-mentioned two solution are mixed and the adding appropriate amount of deionized water, be made into the salting liquid that ion concentration is 1mol/L, wherein the mol ratio between titanium ion, aluminium ion, the zinc ion is 10: 2: 88; Under 500 rev/mins stirring so that the speed of above-mentioned salting liquid with 30mL/min is added drop-wise in the reaction vessel that deionized water is housed in advance by different dropping passages simultaneously with the ammonia spirit of 3mol/L, regulate in the dropping process ammonia spirit drop rate, the pH value of solution in the reaction vessel is remained between 8.0～8.2, solution temperature is 30 ℃, obtains coprecipitated product; Behind sediment ageing 24h, spend deionised water 3 times, use absolute ethanol washing again 1 time, in 100 ℃ of baking ovens, obtain dry white product behind the oven dry 4h then; At 400 ℃ of temperature lower calcination 2h, the mol ratio that is titanium elements and aluminium element is 10: 2 a codope zinc oxide nano-powder with white product.
When using SEM to observe this titanium aluminium codope zinc oxide nano-powder, the pattern of powder and particle diameter and Fig. 1 are similar, and it is subsphaeroidal that uniform particles is, and particle diameter is about 20nm.Use XRD that this titanium aluminium codope zinc oxide nano-powder is carried out thing phase atlas analysis, judge when having or not the second phase impurity, obtain similar result, show that this titanium aluminium codope zinc oxide nano-powder is the buergerite phase structure of zinc oxide, does not exist the second phase dephasign with Fig. 2.
Embodiment 3:
Titanium tetrachloride is added dropwise in 0 ℃ the deionized water, is made into 5mol/L solution; Zinc nitrate and aluminum nitrate are dissolved in the deionized water at room temperature, are made into the 6mol/L aqueous solution, wherein mol ratio is 9: 82 between aluminium ion and the zinc ion; Above-mentioned two solution are mixed and the adding appropriate amount of deionized water, and the ion concentration of wiring solution-forming is the salting liquid of 2mol/L, and wherein the mol ratio between titanium ion, aluminium ion, the zinc ion is 9: 9: 82; Under 600 rev/mins stirring so that the speed of above-mentioned salting liquid with 40mL/min is added drop-wise in the reaction vessel that deionized water is housed in advance by different dropping passages simultaneously with the ammonia spirit of 3mol/L, regulate in the dropping process ammonia spirit drop rate, the pH value of solution in the reaction vessel is remained between 7.5～7.7, solution temperature is 30 ℃, obtains coprecipitated product; Behind sediment ageing 12h, spend deionised water 5 times, use absolute ethanol washing again 2 times, oven dry 10h obtains dry white product in 100 ℃ of baking ovens then; At 300 ℃ of temperature lower calcination 4h, the mol ratio that is titanium elements and aluminium element is 9: 9 a codope zinc oxide nano-powder with white product.
When using SEM to observe this titanium aluminium codope zinc oxide nano-powder, the pattern of powder and particle diameter and Fig. 1 are similar, and it is subsphaeroidal that uniform particles is.Use XRD that this titanium aluminium codope zinc oxide nano-powder is carried out thing phase atlas analysis, judge when having or not the second phase impurity, obtain similar result, show that this titanium aluminium codope zinc oxide nano-powder is the buergerite phase structure of zinc oxide, does not exist the second phase dephasign with Fig. 2.
Embodiment 4:
Titanium tetrachloride is added dropwise in 3 ℃ the deionized water, is made into 4mol/L solution; Zinc nitrate and aluminum nitrate are dissolved in the deionized water at room temperature, are made into the 4mol/L aqueous solution, wherein mol ratio is 8: 75 between aluminium ion and the zinc ion; Above-mentioned two solution are mixed and the adding appropriate amount of deionized water, and the ion concentration of wiring solution-forming is the salting liquid of 1.5mol/L, and wherein the mol ratio between titanium ion, aluminium ion, the zinc ion is 17: 8: 75; Under 700 rev/mins stirring so that the speed of above-mentioned salting liquid with 35mL/min is added drop-wise in the reaction vessel that deionized water is housed in advance by different dropping passages simultaneously with the ammonia spirit of 2.5mol/L, regulate in the dropping process ammonia spirit drop rate, the pH value of solution in the reaction vessel is remained between 7.4～7.6, solution temperature is 20 ℃, obtains coprecipitated product; Behind sediment ageing 24h, spend deionised water 4 times, use absolute ethanol washing again 2 times, oven dry 10h obtains dry white product in 90 ℃ of baking ovens then; At 400 ℃ of temperature lower calcination 4h, the mol ratio that is titanium elements and aluminium element is 17: 8 a codope zinc oxide nano-powder with white product.
When using SEM to observe this titanium aluminium codope zinc oxide nano-powder, the pattern of powder and particle diameter and Fig. 1 are similar, and it is subsphaeroidal that uniform particles is.Use XRD that this titanium aluminium codope zinc oxide nano-powder is carried out thing phase atlas analysis, judge when having or not the second phase impurity, obtain similar result, show that this titanium aluminium codope zinc oxide nano-powder is the buergerite phase structure of zinc oxide, does not exist the second phase dephasign with Fig. 2.
Embodiment 5:
Titanium tetrachloride is added dropwise in 2 ℃ the deionized water, is made into 1mol/L solution; Zinc nitrate and aluminum nitrate are dissolved in the deionized water at room temperature, are made into the 6mol/L aqueous solution, wherein mol ratio is 3: 94 between aluminium ion and the zinc ion; Above-mentioned two solution are mixed and the adding appropriate amount of deionized water, and the ion concentration of wiring solution-forming is the salting liquid of 3mol/L, and wherein the mol ratio between titanium ion, aluminium ion, the zinc ion is 3: 3: 94; Under 800 rev/mins stirring so that the speed of above-mentioned salting liquid with 60mL/min is added drop-wise in the reaction vessel that deionized water is housed in advance by different dropping passages simultaneously with the ammonia spirit of 3mol/L, regulate in the dropping process ammonia spirit drop rate, the pH value of solution in the reaction vessel is remained between 8.5～8.7, the liquid in containers temperature is 30 ℃, obtains coprecipitated product; Behind sediment ageing 48h, spend deionised water 3 times, use absolute ethanol washing again 3 times, oven dry 24h obtains dry white product in 110 ℃ of baking ovens then; At 600 ℃ of temperature lower calcination 5h, the mol ratio that is titanium elements and aluminium element is 3: 3 a codope zinc oxide nano-powder with white product.
When using SEM to observe this titanium aluminium codope zinc oxide nano-powder, the pattern of powder and particle diameter and Fig. 1 are similar, and it is subsphaeroidal that uniform particles is.Use XRD that this titanium aluminium codope zinc oxide nano-powder is carried out thing phase atlas analysis, judge when having or not the second phase impurity, obtain similar result, show that this titanium aluminium codope zinc oxide nano-powder is the buergerite phase structure of zinc oxide, does not exist the second phase dephasign with Fig. 2.
Embodiment 6:
Titanium tetrachloride is added dropwise in 0 ℃ the deionized water, is made into 2mol/L solution; Zinc nitrate and aluminum nitrate are dissolved in the deionized water at room temperature, are made into the 4mol/L aqueous solution, wherein mol ratio is 4: 94 between aluminium ion and the zinc ion; Above-mentioned both solution are mixed and the adding appropriate amount of deionized water, and the ion concentration of wiring solution-forming is the salting liquid of 2.5mol/L, and wherein the mol ratio between titanium ion, aluminium ion, the zinc ion is 2: 4: 94; Under 800 rev/mins stirring so that the speed of above-mentioned salting liquid with 60mL/min is added drop-wise in the reaction vessel that deionized water is housed in advance by different dropping passages simultaneously with the ammonia spirit of 2mol/L, regulate in the dropping process ammonia spirit drop rate, the pH value of solution in the reaction vessel is remained between 8.4～8.6, solution temperature is 20 ℃, obtains coprecipitated product; Behind sediment ageing 36h, spend deionised water 5 times, use absolute ethanol washing again 3 times, oven dry 24h obtains dry white product in 80 ℃ of baking ovens then; At 500 ℃ of temperature lower calcination 3h, the mol ratio that is titanium elements and aluminium element is 2: 4 a codope zinc oxide nano-powder with white product.
When using SEM to observe this titanium aluminium codope zinc oxide nano-powder, the pattern of powder and particle diameter and Fig. 1 are similar, and it is subsphaeroidal that uniform particles is.Use XRD that this titanium aluminium codope zinc oxide nano-powder is carried out thing phase atlas analysis, judge when having or not the second phase impurity, obtain similar result, show that this titanium aluminium codope zinc oxide nano-powder is the buergerite phase structure of zinc oxide, does not exist the second phase dephasign with Fig. 2.
Embodiment 7:
Titanium tetrachloride is added dropwise in 0 ℃ the deionized water, is made into 5mol/L solution; Zinc nitrate and aluminum nitrate are dissolved in the deionized water at room temperature, are made into the 6mol/L aqueous solution, wherein mol ratio is 1: 9 between aluminium ion and the zinc ion; Above-mentioned both solution are mixed and the adding appropriate amount of deionized water, and the ion concentration of wiring solution-forming is the salting liquid of 3mol/L, and wherein the mol ratio between titanium ion, aluminium ion, the zinc ion is 29.7: 0.3: 70; Under 800 rev/mins stirring so that the speed of above-mentioned salting liquid with 30mL/min is added drop-wise in the reaction vessel that deionized water is housed in advance by different dropping passages simultaneously with the ammonia spirit of 6mol/L, regulate in the dropping process ammonia spirit drop rate, the pH value of solution in the reaction vessel is remained between 9.8～10, solution temperature is 60 ℃, obtains coprecipitated product; Behind sediment ageing 48h, spend deionised water 5 times, use absolute ethanol washing again 3 times, oven dry 24h obtains dry white product in 110 ℃ of baking ovens then; At 800 ℃ of temperature lower calcination 5h, the mol ratio that is titanium elements and aluminium element is 29.7: 0.3 a codope zinc oxide nano-powder with white product.
When using SEM to observe this titanium aluminium codope zinc oxide nano-powder, the pattern of powder and particle diameter and Fig. 1 are similar, and it is subsphaeroidal that uniform particles is.Use XRD that this titanium aluminium codope zinc oxide nano-powder is carried out thing phase atlas analysis, judge when having or not the second phase impurity, obtain similar result, show that this titanium aluminium codope zinc oxide nano-powder is the buergerite phase structure of zinc oxide, does not exist the second phase dephasign with Fig. 2.
Embodiment 8:
Titanium tetrachloride is added dropwise in 0 ℃ the deionized water, is made into 0.1mol/L solution; Zinc nitrate and aluminum nitrate are dissolved in the deionized water at room temperature, are made into 0.5mol/L solution, wherein mol ratio is 0.005: 99.995 between aluminium ion and the zinc ion; Above-mentioned two solution are mixed and add appropriate amount of deionized water, the ion concentration of wiring solution-forming is the salting liquid of 0.5mol/L, wherein mol ratio is 1: 100 between titanium ion and the aluminium ion, and the mol ratio between titanium, aluminium ion sum and the zinc ion is 0.005: 99.995; Under 300 rev/mins stirring so that the speed of above-mentioned salting liquid with 10mL/min is added drop-wise in the reaction vessel that deionized water is housed in advance by different dropping passages simultaneously with the ammonia spirit of 1mol/L, regulate in the dropping process ammonia spirit drop rate, the pH value of solution in the reaction vessel is remained between 5.0～5.2, the liquid in containers temperature is 10 ℃, obtains coprecipitated product; Behind sediment ageing 4h, spend deionised water 2 times, use absolute ethanol washing again 1 time, oven dry 4h obtains dry white product in 80 ℃ of baking ovens then; At 300 ℃ of temperature lower calcination 1h, the mol ratio that is titanium elements and aluminium element is the codope zinc oxide nano-powder with white product, its XRD result and shown in Figure 2 similar.
When using SEM to observe this titanium aluminium codope zinc oxide nano-powder, the pattern of powder and particle diameter and Fig. 1 are similar, and it is subsphaeroidal that uniform particles is.Use XRD that this titanium aluminium codope zinc oxide nano-powder is carried out thing phase atlas analysis, judge when having or not the second phase impurity, obtain similar result, show that this titanium aluminium codope zinc oxide nano-powder is the buergerite phase structure of zinc oxide, does not exist the second phase dephasign with Fig. 2.
Embodiment 9:
Other condition is with embodiment 2, different is with among the embodiment 1 with behind the sediment ageing 36h, spend deionised water 5 times, use absolute ethanol washing again 2 times, oven dry 15h obtains dry white product in 80 ℃ of baking ovens then; At 800 ℃ of temperature lower calcination 1h, the mol ratio that is titanium elements and aluminium element is 10: 2 a codope zinc oxide nano-powder with white product.
When using SEM to observe this titanium aluminium codope zinc oxide nano-powder, the pattern of powder and particle diameter and Fig. 1 are similar, and it is subsphaeroidal that uniform particles is.Use XRD that this titanium aluminium codope zinc oxide nano-powder is carried out thing phase atlas analysis, judge when having or not the second phase impurity, obtain similar result, show that this titanium aluminium codope zinc oxide nano-powder is the buergerite phase structure of zinc oxide, does not exist the second phase dephasign with Fig. 2.
Embodiment 10:
Other condition is with embodiment 3, different is with among the embodiment 1 with behind the sediment ageing 24h, spend deionised water 4 times, use absolute ethanol washing again 3 times, oven dry 8h obtains dry white product in 90 ℃ of baking ovens then; At 400 ℃ of temperature lower calcination 4h, the mol ratio that is titanium elements and aluminium element is 9: 9 a codope zinc oxide nano-powder with white product.
When using SEM to observe this titanium aluminium codope zinc oxide nano-powder, the pattern of powder and particle diameter and Fig. 1 are similar, and it is subsphaeroidal that uniform particles is.Use XRD that this titanium aluminium codope zinc oxide nano-powder is carried out thing phase atlas analysis, judge when having or not the second phase impurity, obtain similar result, show that this titanium aluminium codope zinc oxide nano-powder is the buergerite phase structure of zinc oxide, does not exist the second phase dephasign with Fig. 2.
In the above-mentioned embodiment, aluminum nitrate can be substituted by gallium nitrate or indium nitrate or stannic chloride, precipitating reagent ammoniacal liquor can be respectively ammonium carbonate, carbonic hydroammonium, urea and substitute, zinc nitrate can be substituted by zinc sulfate, zinc acetate or zinc chloride, repeat the foregoing description 1～8, make the codope zinc oxide nano-powder equally, obtain the result of similar Fig. 1 when using SEM to observe this codope zinc oxide nano-powder equally, when using XRD that this codope zinc oxide nano-powder is carried out thing phase atlas analysis, obtain the result of similar Fig. 2 equally.
Most preferred embodiment of the present invention is illustrated, and various variations or the remodeling made by those of ordinary skills can not depart from the scope of the present invention.
Claims (6)
1. the nanometer Zinc oxide powder of a codope, the element that comprises zinc oxide and codope, it is characterized in that: the element of codope comprises first metallic element and second metallic element, and first metallic element is a titanium elements, and second metallic element is aluminium, gallium, indium or tin element; By amount of substance, the summation of first metallic element, second metallic element and zinc in zinc oxide element is 100 parts, wherein the summation of first metallic element and second metallic element accounts for 0.005～30 part, and the portion rate scope of first metallic element and second metallic element is 1: 100 to 100: 1.
2. method for preparing the nanometer Zinc oxide powder of the described a kind of codope of claim 1, it is characterized in that: this method comprises the steps:
Step 1: titanium tetrachloride is dissolved in 0～5 ℃ of deionized water, forms the aqueous solution of 0.1～5mol/L;
Step 2: the slaine and the zinc salt that will comprise second metallic element are dissolved into the salting liquid that forms 0.5～6mol/L in the deionized water at normal temperature jointly, by amount of substance, wherein the portion rate scope between the second metallic element ion and the zinc ion is 0.005: 100 to 1: 10;
Step 3: fully with two kinds of aqueous solution in step 1 and the step 2, stirring, form the aqueous metal salt of 0.5～3mol/L, by amount of substance, the summation of titanium ion, the second metallic element ion and zinc ion is 100 parts, wherein the summation of the titanium ion and the second metallic element ion accounts for 0.005～30 part, and the portion rate scope of the titanium elements and second metallic element is 1: 100 to 100: 1.
Step 4: precipitating reagent is dissolved into the precipitant solution that forms 1～6mol/L in the deionized water;
Step 5: be under 300～800 rev/mins the stirring condition at rotating speed, the aqueous metal salt in the step 3 is splashed in the reaction vessel that adds deionized water in advance by different dropping passages simultaneously with precipitant solution in the step 4; In the dropping process, the drop rate of control aqueous metal salt and precipitant solution, the pH value that makes solution in the reaction vessel are between 5～10, and temperature obtains coprecipitated product between 10～60 ℃.
Step 6: the coprecipitate ageing that obtains in the step 5 after 4～48 hours, is spent deionised water 2～5 times, use absolute ethanol washing again 1～3 time, in 80～110 ℃ of baking ovens, dry then and obtained dry white product in 4～24 hours.
Step 7: the white product in the step 6 300～800 ℃ of temperature lower calcinations 1～5 hour, is promptly obtained the nanometer Zinc oxide powder of the titanium elements and the second metallic element codope.
3. a kind of method for preparing the nanometer Zinc oxide powder of codope according to claim 2 is characterized in that: the described second metallic element ion is aluminium ion, gallium ion, indium ion or tin ion.
4. a kind of method for preparing the nanometer Zinc oxide powder of codope according to claim 2 is characterized in that: the described slaine that comprises second metallic element is aluminum nitrate, gallium nitrate, indium nitrate or stannic chloride.
5. a kind of method for preparing the nanometer Zinc oxide powder of codope according to claim 2 is characterized in that: described zinc salt is zinc sulfate, zinc nitrate, zinc acetate or zinc chloride.
6. a kind of method for preparing the nanometer Zinc oxide powder of codope according to claim 2 is characterized in that: described precipitating reagent is ammoniacal liquor, ammonium carbonate, carbonic hydroammonium or urea.
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Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN102154696A (en) * | 2011-03-17 | 2011-08-17 | 上海大学 | Preparation method of magnesium-silver co-doped zinc oxide nanocrystals |
| CN102586736A (en) * | 2012-02-23 | 2012-07-18 | 西北稀有金属材料研究院 | Doped ZnO-based sputtering target material and preparation method thereof |
| CN102757676A (en) * | 2012-05-10 | 2012-10-31 | 中国人民解放军总后勤部军需装备研究所 | Low-emissivity nano-coating and preparation method and application thereof |
| CN105197981A (en) * | 2015-09-14 | 2015-12-30 | 大连瑞源动力有限公司 | Preparation of high-activity nano zinc oxide |
| CN106676487A (en) * | 2016-10-09 | 2017-05-17 | 宁波森利电子材料有限公司 | Zinc oxide-based ceramic sputtering target material and preparation method and application thereof |
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| JPH11279525A (en) * | 1998-03-30 | 1999-10-12 | Sakai Chem Ind Co Ltd | Clear heat-ray-intercepting material |
| CN1590302A (en) * | 2003-08-29 | 2005-03-09 | 中国科学院过程工程研究所 | Coprecipitation method for preparing ultra fine zinc oxide powder possessing high electric conductivity |
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| JPH11279525A (en) * | 1998-03-30 | 1999-10-12 | Sakai Chem Ind Co Ltd | Clear heat-ray-intercepting material |
| CN1590302A (en) * | 2003-08-29 | 2005-03-09 | 中国科学院过程工程研究所 | Coprecipitation method for preparing ultra fine zinc oxide powder possessing high electric conductivity |
Cited By (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102154696A (en) * | 2011-03-17 | 2011-08-17 | 上海大学 | Preparation method of magnesium-silver co-doped zinc oxide nanocrystals |
| CN102154696B (en) * | 2011-03-17 | 2013-01-09 | 上海大学 | Preparation method of magnesium-silver co-doped zinc oxide nanocrystals |
| CN102586736A (en) * | 2012-02-23 | 2012-07-18 | 西北稀有金属材料研究院 | Doped ZnO-based sputtering target material and preparation method thereof |
| CN102586736B (en) * | 2012-02-23 | 2013-10-16 | 西北稀有金属材料研究院 | Doped ZnO-based sputtering target material and preparation method thereof |
| CN102757676A (en) * | 2012-05-10 | 2012-10-31 | 中国人民解放军总后勤部军需装备研究所 | Low-emissivity nano-coating and preparation method and application thereof |
| CN102757676B (en) * | 2012-05-10 | 2014-03-26 | 中国人民解放军总后勤部军需装备研究所 | Low-emissivity nano-coating and preparation method and application thereof |
| CN105197981A (en) * | 2015-09-14 | 2015-12-30 | 大连瑞源动力有限公司 | Preparation of high-activity nano zinc oxide |
| CN106676487A (en) * | 2016-10-09 | 2017-05-17 | 宁波森利电子材料有限公司 | Zinc oxide-based ceramic sputtering target material and preparation method and application thereof |
| CN106676487B (en) * | 2016-10-09 | 2019-03-08 | 宁波森利电子材料有限公司 | A kind of zinc oxide-based ceramic sputtering target material and its preparation method and application |
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| CN101811660B (en) | 2012-09-19 |
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