CN101844917A - Preparation method of doped zinc oxide nano powder - Google Patents
Preparation method of doped zinc oxide nano powder Download PDFInfo
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- CN101844917A CN101844917A CN 201010166473 CN201010166473A CN101844917A CN 101844917 A CN101844917 A CN 101844917A CN 201010166473 CN201010166473 CN 201010166473 CN 201010166473 A CN201010166473 A CN 201010166473A CN 101844917 A CN101844917 A CN 101844917A
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Abstract
The invention discloses a preparation method of doped zinc oxide nano powder, which comprises the following steps that: doped metal salt and zinc salt are dissolved in water to form salt solution; under intense stirring, the salt solution is uniformly dripped into precipitant solution, the pH value of a mixed system is kept to be 5 to 10 and the temperature is kept to be 10 to 80DEG C during the dripping process to obtain a coprecipitation product; after the coprecipitation product is aged for 10 to 30h, precipitate is sequentially washed by deionzied water and absolute ethyl alcohol and is dried to obtain a white product; and the white product is calcined for 1 to 5h at 400 to 800DEG C to prepare the doped zinc oxide nano powder. The method has the advantages of low cost, simple used equipment and easy large-scale industrial production, and the prepared doped zinc oxide nano powder has the advantages of uniform distribution, high purity and no non-conductive second phase, and can be used for preparing high-quality zinc oxide-based sputtering targets.
Description
Technical field
The present invention relates to the photoelectric material technical field, relate in particular to a kind of preparation method of doped zinc oxide nano powder.
Background technology
Transparent conductive oxide film because have that the forbidden band is wide, characteristic such as visible range transmitance height and resistivity are low and being used widely in fields such as flat pannel display and thin-film solar cells.At present people have developed the transparent conductive oxide film material of different series, wherein, the Zinc oxide-base material owing to have low cost, nontoxic characteristic has caused that people greatly pay close attention to.Zinc oxide itself is the not high semi-conductor of electric conductivity (specific conductivity about 10
-14S/cm), (specific conductivity is 10 but its electroconductibility of doping back such as process aluminium, gallium are greatly improved
3-10
4S/cm), and the visible region transmitance is higher than 85%, can substitute tin indium oxide (ITO) transparent conductive material comparatively commonly used at present.
Magnetron sputtering deposition transparent conductive film technology is comparatively sophisticated film, and it is owing to have film density height, homogeneity, good reproducibility and be easy to advantage such as big area high speed deposition and accepted by industry member and extensively adopt.In magnetron sputtering process, ceramic sputtering target material plays crucial effects, and the characteristic of its performance and sputter stability and final rete is closely related.Ceramic sputtering target material generally obtains by the technology of powder pressure forming, high temperature sintering, and wherein the quality of powder raw material has close influence to the performance of sputtering target material.
Publication number is to disclose a kind of ZAO semiconductor nano conductive film and preparation method thereof in the Chinese patent application of CN 101481790A.It is to deposit the layer of transparent protective membrane on the nesa coating again at ZAO, makes it to guarantee that this composite membrane has the reflectivity of the transmissivity of low-resistivity, high visible, high IR line, moisture resistance and be not subjected to Effect of Environmental.ZAO is a nesa coating for the continuous growth big area, specialized designs many targets spirally wound high vacuum sputtering unit.At high vacuum chamber domestic demand cooling system, make the temperature of flexible substrates remain on 60 ℃～150 ℃.Power supply uses the asymmetry pulse flow directing device, can make target material surface not " poisoning " when work, and the net horsepower of power supply is higher more than 2 times than conventional power supply.Sputter gas is high-purity Ar and O
2, higher and good Film Optics and electrology characteristic arranged with the sputtering sedimentation rate that guarantees film.
Publication number is the sputtering target that discloses a kind of Zinc oxide doped aluminium and boron in the Japanese patent application of the flat 6-293956A of JP, and its doping ratio is 0.1～10a.%Al, 0.1～10a.%B.
Publication number is to disclose the method that a kind of ion beam enhanced depositing prepares p type zinc-oxide film in the Chinese patent application of CN 1752269A, it is with high purity ZnO powder, or atomic ratio is that the oxide compounds such as Al, In of 1-5% evenly mix the ZnO powder, with waiting static pressure compression moulding, reburn and form sputtering target, and use pure N
2Or Ar: N
2The ion beam mixing that is 1: 3～1: 10 mixing high-purity gas generation bombards deposited film, vertically be injected on the sputtering sedimentation film, utilize the revolution and the sample strip rotation of sample table to realize evenly injecting, guarantee that film obtains uniform, high oriented ZnO polycrystalline structure after follow-up heat of crystallization is handled.
Publication number is to disclose a kind of zinc oxide transparent conductor and this transparent conductor in the Chinese patent application of CN 101490766A to form manufacture method with sputtering target and this sputtering target, with zinc oxide (ZnO) is principal constituent, contain the element that becomes N type doping agent with respect to zinc oxide, and contain with respect to all atoms metals be that the parameter P of the wettability of the expression of 0.05～2.0 atom % and zinc oxide is below 6, resistivity is less than the metal of the resistivity of the zinc oxide that has added N type doping agent, wherein, P=(G+H
MIX)/RT, G: the Gibbs free energy of metal under the temperature T, H
MIX: the enthalpy of mixing of zinc oxide and metal under the temperature T, R: gas law constant, T: temperature.
Publication number is the preparation method who discloses a kind of nano-level zinc oxide powder of low temperature easy-sintering in the Chinese patent application of CN 1389404A, adopting the inorganic salt of zinc is raw material, with carbonate or supercarbonate is precipitation agent, under violent stirring, make the inorganic salt of zinc and the highly concentrated solution hybrid reaction of carbonate or supercarbonate generate basic zinc salt precipitation.
Present most of investigator adopt Zinc oxide powder and adulterated powder ball milling mutually the blended method prepare the doping zinc-oxide powder, and then be used to prepare ceramic sputtering target material.Be to disclose a kind of zinc gallium oxide ceramic target and its production and application in 02156898.7 the Chinese patent application as application number, it adopts Zinc oxide powder and gallium oxide powder to be mixed even mutually, the employing method moulding of colding pressing, become closely knit block with normal pressure, normal atmosphere sintering, as sputtering target material, and be applied to the preparation of zinc gallium oxide transparent conductive film.Reported in " doping is to ZnO ceramic target Study on Influence " (" artificial lens journal " 2009 38 volume the third phase 772 pages) literary composition employing Zinc oxide powder and adulterated powder ball milling mutually the blended method prepare the doping zinc-oxide powder.Though it is comparatively simple that aforesaid method is seen from preparation technology's angle, but preparation high quality target is seemed particularly not enough: at first, be difficult to obtain uniform doping, because the powder amount of doping oxide less (be generally zinc oxide quality 0.5%～6%), be difficult to the uniform mixing that assurance can reach the atom magnitude between the two by ball milling method, cause the inhomogeneous of target composition, and then have influence on the homogeneity of sputtered film photoelectric properties; Secondly, in mechanical milling process between the abrading-ball and between abrading-ball and the tank body contact and wear and tear can be in system a large amount of impurity of introducing, cause the reduction of target purity; In addition, the particle diameter of used powder raw material mostly is micron dimension greatly, sintering activity is lower, need be higher than the sintering temperature more than 1300 ℃, and hotchpotch and zinc oxide react and form nonconducting second (as: the adulterated zinc oxide of aluminium can produce the Zinc aluminate phase) mutually under this temperature, these second are met and cause the uneven distribution of target specific conductivity, and then have influence on the stability of sputter procedure.Therefore, do the even adulterated ZnO nano-powder of acquisition from raw material and for preparation high quality sputtering target material, seem particularly important.
Summary of the invention
Technical problem to be solved by this invention is: fundamentally solve to adopt doping zinc-oxide powder skewness, foreign matter content height that existing doping zinc-oxide powder preparation method makes, exist nonconducting second to equate problem.
In order to solve the problems of the technologies described above, the invention provides a kind of preparation method of doped zinc oxide nano powder, can make be evenly distributed, purity is high and do not have the doping zinc-oxide powder of the second non-conductive phase.
A kind of preparation method of doped zinc oxide nano powder comprises step:
(1) doped metal salt and zinc salt are dissolved into to form the salt total concn in the deionized water be the salts solution of 0.5mol/L～3mol/L, wherein, the metal ion in the doped metal salt and the mol ratio of the zine ion in the zinc salt were smaller or equal to 0.18: 1;
(2) precipitation agent is dissolved into the precipitant solution that forms 1mol/L～6mol/L in the deionized water;
(3) under rotating speed is 400 rev/mins～800 rev/mins violent stirring, the speed of the middle salts solution of preparing of step (1) with 5mL/min～50mL/min is dropped in the precipitant solution of step (2) preparation equably, keeping the pH value of mixed system in the dropping process is 5～10,10 ℃～80 ℃ of temperature obtain coprecipitated product;
(4) with behind above-mentioned coprecipitated product ageing 10h～30h, throw out is used deionized water and absolute ethanol washing after drying successively, obtains white product;
(5) above-mentioned white product is calcined 1h～5h at 400 ℃～800 ℃, make doped zinc oxide nano powder;
Described doped metal salt is one or more in aluminium salt, gallium salt, indium salt, pink salt, boron salt, chromic salts, the vanadic salts.
As preferably:
Described doped metal salt is selected from one or both in aluminum nitrate, gallium nitrate, indium nitrate, tin chloride, boric acid, chromium nitrate, the nitric acid vanadium.
The molar ratio of two kinds of doped metal ions in described two kinds of doped metal salt is 0.05～1: 1.
Described zinc salt is selected from a kind of in zinc sulfate, zinc nitrate, zinc acetate or the zinc chloride.
Described precipitation agent is selected from a kind of in ammoniacal liquor, volatile salt, bicarbonate of ammonia or the urea.
In the step (4), described throw out is 3 times～5 times with the number of times of deionized water wash, and the number of times of absolute ethanol washing is 1 time～3 times.
In the step (4), described drying temperature is 80 ℃～110 ℃, and be 5h～15h time of drying.
The present invention uses field emission scanning electron microscope (SEM) to observe grain-size and microstructure, utilizes the distribution situation of electronic spectrum (EDS) analysis doped element, the sign judgement of adopting x-ray diffractometer (XRD) to carry out phase structure to have or not second dephasign doped zinc oxide nano powder.
Compared with prior art, the present invention has following beneficial effect:
Coprecipitation method is a kind of method of utilizing precipitation agent that two kinds and two or more metal ions are precipitated simultaneously, can prepare even adulterated zinc oxide nano-powder effectively, be implemented in the even doping that keeps pantogen sub level under the constant situation of zinc oxide hexagonal wurtzite structure.The preparation method of this method and other doped zinc oxide nano powders such as sol-gel, physics method compare have equipment simple, be easy to large-scale industrial production and low cost and other advantages.
The doping zinc-oxide powder granule of the inventive method preparation evenly is subsphaeroidal, particle diameter is 10～70nm, doped metal ion is evenly distributed, the wurtzite structure that presents ZnO, and do not observe the diffraction peak of nonconducting second dephasign, the purity height can be used to prepare high-quality zinc oxide-based sputtering target material.
The doping zinc-oxide powder element doping good uniformity of the inventive method preparation and have higher sintering activity can be used for the preparation of high-performance ZnO base transparent conducting film sputtering target material.
Description of drawings
Fig. 1 is the SEM picture of the aluminum-doped zinc oxide nanometer powder of embodiment 1 preparation;
Fig. 2 is the element mapping of EDS collection of illustrative plates of the aluminum-doped zinc oxide nanometer powder of embodiment 1 preparation;
Fig. 3 is the XRD thing phase collection of illustrative plates of doped zinc oxide nano powder; Wherein, (a) being the XRD thing phase collection of illustrative plates of the aluminum-doped zinc oxide nanometer powder of embodiment 1 preparation, (b) is the XRD thing phase collection of illustrative plates of the Ga-doped zinc oxide nano-powder of embodiment 4 preparations; Wherein, X-coordinate is 2 θ angles, and ordinate zou is relative intensity (intensity);
Fig. 4 is the SEM picture of the Ga-doped zinc oxide nano-powder of embodiment 4 preparations;
Fig. 5 is the element mapping of EDS collection of illustrative plates of the Ga-doped zinc oxide nano-powder of embodiment 4 preparation.
Embodiment
Embodiment 1
Aluminum nitrate and zinc nitrate be dissolved into jointly to form the salt total concn in the deionized water be the salts solution of 1mol/L, wherein mol ratio is 0.032: 1 between aluminum ion and the zine ion, under being 600 rev/mins violent stirring, rotating speed is added drop-wise to equably in the ammonia soln (solvent is a deionized water) of 3mol/L with the speed of 20mL/min, keeping the pH value of system in the dropping process is 7.5 ± 0.5, temperature is 30 ℃, obtains coprecipitated product; Behind coprecipitated product ageing 24h, throw out deionized water wash 3 times are used absolute ethanol washing 1 time again, and dry 10h in 100 ℃ of baking ovens obtains the exsiccant white product then; White product at 600 ℃ of temperature lower calcination 2h, is obtained aluminum-doped zinc oxide nanometer powder, and wherein, mol ratio is 0.032: 1 between aluminum ion and the zine ion.
After testing, SEM photo such as Fig. 1 of above-mentioned doped zinc oxide nano powder, EDS collection of illustrative plates doped element face distributes as Fig. 2, and XRD figure is composed shown in (a) among Fig. 3.
Compose the result as can be known from the SEM photo, the distribution of EDS collection of illustrative plates doped element face, the XRD figure that obtain, the doped zinc oxide nano powder uniform particles is subsphaeroidal, and particle diameter is 30～40nm, and the adulterated al element is evenly distributed, the wurtzite structure that presents ZnO, and do not observe the diffraction peak of other dephasign.
Embodiment 2
Aluminum nitrate and zinc nitrate be dissolved into jointly to form the salt total concn in the deionized water be the salts solution of 0.5mol/L, wherein mol ratio is 0.032: 1 between aluminum ion and the zine ion, under being 400 rev/mins violent stirring, rotating speed is added drop-wise to equably in the ammonia soln (solvent is a deionized water) of 2mol/L with the speed of 5mL/min, keeping the pH value of system in the dropping process is 8.3 ± 0.3, temperature is 20 ℃, obtains coprecipitated product; Behind coprecipitated product ageing 24h, throw out deionized water wash 4 times are used absolute ethanol washing 2 times again, and dry 10h in 100 ℃ of baking ovens obtains the exsiccant white product then; White product at 500 ℃ of temperature lower calcination 2h, is obtained aluminum-doped zinc oxide nanometer powder, and wherein, mol ratio is 0.032: 1 between aluminum ion and the zine ion.
After testing, compose as can be known from SEM photo, the distribution of EDS collection of illustrative plates doped element face, the XRD figure of above-mentioned doped zinc oxide nano powder, the doped zinc oxide nano powder uniform particles is subsphaeroidal, particle diameter is 50～60nm, the adulterated al element is evenly distributed, the wurtzite structure that presents ZnO, and do not observe the diffraction peak of other dephasign.
Embodiment 3
Aluminum nitrate and zinc nitrate be dissolved into jointly to form the salt total concn in the deionized water be the salts solution of 3mol/L, wherein mol ratio is 0.02: 1 between aluminum ion and the zine ion, under being 400 rev/mins violent stirring, rotating speed is added drop-wise to equably in the ammonia soln (solvent is a deionized water) of 5mol/L with the speed of 50mL/min, keeping the pH value of system in the dropping process is 9.6 ± 0.4, temperature is 50 ℃, obtains coprecipitated product; Behind coprecipitated product ageing 30h, throw out deionized water wash 5 times are used absolute ethanol washing 2 times again, and dry 15h in 100 ℃ of baking ovens obtains the exsiccant white product then; White product at 700 ℃ of temperature lower calcination 3h, is obtained aluminum-doped zinc oxide nanometer powder, and wherein, mol ratio is 0.02: 1 between aluminum ion and the zine ion.
After testing, compose as can be known from SEM photo, the distribution of EDS collection of illustrative plates doped element face, the XRD figure of above-mentioned doped zinc oxide nano powder, the doped zinc oxide nano powder uniform particles is subsphaeroidal, particle diameter is 40～50nm, the adulterated al element is evenly distributed, the wurtzite structure that presents ZnO, and do not observe the diffraction peak of other dephasign.
Embodiment 4
Gallium nitrate and zinc nitrate be dissolved into jointly to form the salt total concn in the deionized water be the salts solution of 1mol/L, wherein mol ratio is 0.02: 1 between gallium ion and the zine ion, under being 600 rev/mins violent stirring, rotating speed is added drop-wise to equably in the ammonia soln (solvent is a deionized water) of 3mol/L with the speed of 30mL/min, keeping the pH value of system in the dropping process is 7.3 ± 0.3, temperature is 30 ℃, obtains coprecipitated product; Behind coprecipitated product ageing 24h, throw out deionized water wash 3 times are used absolute ethanol washing 1 time again, and dry 10h in 100 ℃ of baking ovens obtains the exsiccant white product then; White product at 600 ℃ of temperature lower calcination 2h, is obtained the Ga-doped zinc oxide nano-powder, and wherein, mol ratio is 0.02: 1 between gallium ion and the zine ion.
After testing, SEM photo such as Fig. 4 of above-mentioned doped zinc oxide nano powder, EDS collection of illustrative plates doped element face distributes as Fig. 5, and XRD figure is composed shown in (b) among Fig. 3.
Compose the result as can be known from the SEM photo, the distribution of EDS collection of illustrative plates doped element face, the XRD figure that obtain, the doped zinc oxide nano powder uniform particles is subsphaeroidal, and particle diameter is 20～30nm, and the doped gallium element is evenly distributed, the wurtzite structure that presents ZnO, and do not observe the diffraction peak of other dephasign.
Embodiment 5
Gallium nitrate and zinc nitrate be dissolved into jointly to form the salt total concn in the deionized water be the salts solution of 0.5mol/L, wherein mol ratio is 0.02: 1 between gallium ion and the zine ion, under being 400 rev/mins violent stirring, rotating speed is added drop-wise to equably in the ammonia soln (solvent is a deionized water) of 2mol/L with the speed of 5mL/min, keeping the pH value of system in the dropping process is 8.6 ± 0.5, temperature is 20 ℃, obtains coprecipitated product; Behind coprecipitated product ageing 24h, throw out deionized water wash 4 times are used absolute ethanol washing 2 times again, and dry 10h in 100 ℃ of baking ovens obtains the exsiccant white product then; White product at 500 ℃ of temperature lower calcination 2h, is obtained the Ga-doped zinc oxide nano-powder, and wherein, mol ratio is 0.02: 1 between gallium ion and the zine ion.
After testing, compose as can be known from SEM photo, the distribution of EDS collection of illustrative plates doped element face, the XRD figure of above-mentioned doped zinc oxide nano powder, the doped zinc oxide nano powder uniform particles is subsphaeroidal, particle diameter is 20～30mm, the doped gallium element is evenly distributed, the wurtzite structure that presents ZnO, and do not observe the diffraction peak of other dephasign.
Embodiment 6
Gallium nitrate and zinc nitrate be dissolved into jointly to form the salt total concn in the deionized water be the salts solution of 3mol/L, wherein mol ratio is 0.04: 1 between gallium ion and the zine ion, under being 800 rev/mins violent stirring, rotating speed is added drop-wise to equably in the ammonia soln (solvent is a deionized water) of 5mol/L with the speed of 50mL/min, keeping the pH value of system in the dropping process is 9.6 ± 0.4, temperature is 70 ℃, obtains coprecipitated product; Behind coprecipitated product ageing 30h, throw out deionized water wash 5 times are used absolute ethanol washing 2 times again, and dry 15h in 100 ℃ of baking ovens obtains the exsiccant white product then; White product at 700 ℃ of temperature lower calcination 3h, is obtained the Ga-doped zinc oxide nano-powder, and wherein, mol ratio is 0.04: 1 between gallium ion and the zine ion.
After testing, compose as can be known from SEM photo, the distribution of EDS collection of illustrative plates doped element face, the XRD figure of above-mentioned doped zinc oxide nano powder, the doped zinc oxide nano powder uniform particles is subsphaeroidal, particle diameter is 20～40nm, the doped gallium element is evenly distributed, the wurtzite structure that presents ZnO, and do not observe the diffraction peak of other dephasign.
Embodiment 7
Gallium nitrate, aluminum nitrate and zinc nitrate be dissolved into jointly in the deionized water to form the salt total concn be the salts solution of 2mol/L, wherein the mol ratio of gallium ion and aluminum ions mole number sum and zine ion is 0.04: 1, gallium ion and aluminum ions mol ratio are 1: 1, under being 600 rev/mins violent stirring, rotating speed is added drop-wise to equably in the ammonia soln (solvent is a deionized water) of 4mol/L with the speed of 40mL/min, keeping the pH value of system in the dropping process is 8.3 ± 0.2, temperature is 50 ℃, obtains coprecipitated product; Behind coprecipitated product ageing 30h, throw out deionized water wash 5 times are used absolute ethanol washing 2 times again, and dry 15h in 100 ℃ of baking ovens obtains the exsiccant white product then; White product at 800 ℃ of temperature lower calcination 4h, is obtained gallium and aluminum-doped zinc oxide nanometer powder, and wherein, mol ratio is 0.02: 0.02: 1 between gallium ion, aluminum ion and the zine ion.
After testing, compose as can be known from SEM photo, the distribution of EDS collection of illustrative plates doped element face, the XRD figure of above-mentioned doped zinc oxide nano powder, the doped zinc oxide nano powder uniform particles is subsphaeroidal, particle diameter is 10～20nm, doped gallium element and aluminium element are evenly distributed, the wurtzite structure that presents ZnO, and do not observe the diffraction peak of other dephasign.
Gallium nitrate, aluminum nitrate and zinc nitrate be dissolved into jointly in the deionized water to form the salt total concn be the salts solution of 1mol/L, wherein the mol ratio of gallium ion and aluminum ions mole number sum and zine ion is 0.03: 1, gallium ion and aluminum ions mol ratio are 0.8: 1, under being 800 rev/mins violent stirring, rotating speed is added drop-wise to equably in the ammonia soln (solvent is a deionized water) of 3mol/L with the speed of 30mL/min, keeping the pH value of system in the dropping process is 8.5 ± 0.2, temperature is 40 ℃, obtains coprecipitated product; Behind coprecipitated product ageing 30h, throw out deionized water wash 5 times are used absolute ethanol washing 2 times again, and dry 15h in 100 ℃ of baking ovens obtains the exsiccant white product then; White product at 600 ℃ of temperature lower calcination 2h, is obtained gallium and aluminum-doped zinc oxide nanometer powder, and wherein, mol ratio is 0.0133: 0.0167: 1 between gallium ion, aluminum ion and the zine ion.
After testing, compose as can be known from SEM photo, the distribution of EDS collection of illustrative plates doped element face, the XRD figure of above-mentioned doped zinc oxide nano powder, the doped zinc oxide nano powder uniform particles is subsphaeroidal, particle diameter is 20～30nm, doped gallium element and aluminium element are evenly distributed, the wurtzite structure that presents ZnO, and do not observe the diffraction peak of other dephasign.
Embodiment 9～11
Except replacing the zinc nitrate with zinc sulfate, zinc acetate or zinc chloride respectively, all the other are operated with embodiment 8, make gallium and aluminum-doped zinc oxide nanometer powder, and wherein, mol ratio is 0.0133: 0.0167: 1 between gallium ion, aluminum ion and the zine ion.
After testing, compose as can be known from SEM photo, the distribution of EDS collection of illustrative plates doped element face, the XRD figure of above-mentioned doped zinc oxide nano powder, the doped zinc oxide nano powder uniform particles is subsphaeroidal, particle diameter is 20～30nm, doped gallium element and aluminium element are evenly distributed, the wurtzite structure that presents ZnO, and do not observe the diffraction peak of other dephasign.
Embodiment 12～14
Except substituting the ammoniacal liquor with volatile salt, bicarbonate of ammonia or urea respectively, all the other are operated with embodiment 7, make gallium and aluminum-doped zinc oxide nanometer powder, and wherein, mol ratio is 0.02: 0.02: 1 between gallium ion, aluminum ion and the zine ion.
After testing, compose as can be known from SEM photo, the distribution of EDS collection of illustrative plates doped element face, the XRD figure of above-mentioned doped zinc oxide nano powder, the doped zinc oxide nano powder uniform particles is subsphaeroidal, particle diameter is 10～20nm, doped gallium element and aluminium element are evenly distributed, the wurtzite structure that presents ZnO, and do not observe the diffraction peak of other dephasign.
Embodiment 15～16
Except substituting the gallium nitrate with indium nitrate or tin chloride respectively, all the other are operated with embodiment 4, make indium or tin mixed with zinc oxide nano-powder, and wherein, mol ratio is 0.02: 1 between indium ion or tin ion and the zine ion.
After testing, compose as can be known from SEM photo, the distribution of EDS collection of illustrative plates doped element face, the XRD figure of above-mentioned doped zinc oxide nano powder, the doped zinc oxide nano powder uniform particles is subsphaeroidal, particle diameter is 10～30nm, doped indium element or tin element are evenly distributed, the wurtzite structure that presents ZnO, and do not observe the diffraction peak of other dephasign.
Embodiment 17～18
Except substituting the aluminum nitrate with indium nitrate or tin chloride respectively, all the other are operated with embodiment 1, make indium or tin mixed with zinc oxide nano-powder, and wherein, mol ratio is 0.032: 1 between indium ion or tin ion and the zine ion.
After testing, compose as can be known from SEM photo, the distribution of EDS collection of illustrative plates doped element face, the XRD figure of above-mentioned doped zinc oxide nano powder, the doped zinc oxide nano powder uniform particles is subsphaeroidal, particle diameter is 20～40nm, doped indium element or tin element are evenly distributed, the wurtzite structure that presents ZnO, and do not observe the diffraction peak of other dephasign.
Obviously, those skilled in the art can carry out various changes and modification with the preparation method of doped zinc oxide nano powder to sputtering target material of the present invention and not break away from the spirit and scope of the present invention.Like this, if these of those skilled in the art are revised and modification belongs within the scope of claim of the present invention and equivalent technologies thereof, then the present invention also is intended to comprise these changes and modification interior.
Claims (8)
1. the preparation method of a doped zinc oxide nano powder comprises step:
(1) doped metal salt and zinc salt are dissolved into to form the salt total concn in the deionized water be the salts solution of 0.5mol/L～3mol/L, wherein, the metal ion in the doped metal salt and the mol ratio of the zine ion in the zinc salt were smaller or equal to 0.18: 1;
(2) precipitation agent is dissolved into the precipitant solution that forms 1mol/L～6mol/L in the deionized water;
(3) under rotating speed is 400 rev/mins～800 rev/mins violent stirring, the speed of the middle salts solution of preparing of step (1) with 5mL/min～50mL/min is dropped in the precipitant solution of step (2) preparation equably, keeping the pH value of mixed system in the dropping process is 5～10,10 ℃～80 ℃ of temperature obtain coprecipitated product;
(4) with behind above-mentioned coprecipitated product ageing 10h～30h, throw out is used deionized water and absolute ethanol washing after drying successively, obtains white product;
(5) above-mentioned white product is calcined 1h～5h at 400 ℃～800 ℃, make doped zinc oxide nano powder;
Described doped metal salt is one or more in aluminium salt, gallium salt, indium salt, pink salt, boron salt, chromic salts, the vanadic salts.
2. preparation method according to claim 1 is characterized in that, described doped metal salt is selected from one or both in aluminum nitrate, gallium nitrate, indium nitrate, tin chloride, boric acid, chromium nitrate, the nitric acid vanadium.
3. preparation method according to claim 1 and 2 is characterized in that, the molar ratio of two kinds of doped metal ions in described two kinds of doped metal salt is 0.05～1: 1.
4. preparation method according to claim 1 is characterized in that, described zinc salt is selected from a kind of in zinc sulfate, zinc nitrate, zinc acetate or the zinc chloride.
5. preparation method according to claim 1 is characterized in that, described precipitation agent is selected from a kind of in ammoniacal liquor, volatile salt, bicarbonate of ammonia or the urea.
6. preparation method according to claim 1 is characterized in that, in the step (4), described throw out is 3 times～5 times with the number of times of deionized water wash, and the number of times of absolute ethanol washing is 1 time～3 times.
7. preparation method according to claim 1 is characterized in that, in the step (4), described drying temperature is 80 ℃～110 ℃, and be 5h～15h time of drying.
8. doped zinc oxide nano powder that makes according to each described preparation method of claim 1～7.
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| CN102653413A (en) * | 2012-05-11 | 2012-09-05 | 北京化工大学 | Zinc-doped indium oxide nano gas sensitive material and preparation method thereof |
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| CN112218840A (en) * | 2018-06-06 | 2021-01-12 | 杰富意矿物股份有限公司 | Zinc oxide powder for use in zinc oxide sintered body, and processes for producing these |
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| CN112824323A (en) * | 2019-11-21 | 2021-05-21 | 中国科学院大连化学物理研究所 | Indium-doped zinc oxide composite reduced graphene oxide material, and preparation and application thereof |
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