CN101830498A - Preparation method of ITO (Indium Tin Oxide) powder and ITO sintering body - Google Patents
Preparation method of ITO (Indium Tin Oxide) powder and ITO sintering body Download PDFInfo
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- CN101830498A CN101830498A CN200910118196A CN200910118196A CN101830498A CN 101830498 A CN101830498 A CN 101830498A CN 200910118196 A CN200910118196 A CN 200910118196A CN 200910118196 A CN200910118196 A CN 200910118196A CN 101830498 A CN101830498 A CN 101830498A
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Abstract
The invention discloses a preparation method of ITO (Indium Tin Oxide) powder, comprising the following steps of: (a) adding an aqueous alkaline solution with the concentration of 10-30 percent by weight to an indium tin solution to obtain an indium tin hydroxide precipitation solution, and controlling the temperature of an initial precipitation solution between 18 DEG C and 30 DEG C in the process of adding the aqueous alkaline solution; (b) separating precipitations and liquid contained the indium tin hydroxide precipitation solution; (c) washing the separated precipitations; and (d) calcining the precipitations to obtain the ITO powder. The invention is beneficial to enhancing the sintering property of the ITO powder by selecting proper aqueous alkaline solution concentration and precipitation temperature according to that the aqueous alkaline solution concentration and the precipitation temperature have a great impact on the sintering property of the ITO powder when the indium tin solution is added to the aqueous alkaline solution; an ITO sintering body prepared by the ITO powder has at least 7.08 g/cm<3> of density, bulk resistivity lower than 1.90*10<-4> ohm.cm and maximum crystallite dimension of the sintering body, which is smaller than 10 micrometers.
Description
Technical field
The present invention relates to metal oxide, be specifically related to the preparation method of ito powder and ITO sintered compact.
Background technology
The main component of ITO (tin indium oxide) is that stannic oxide is solid-solubilized in the composite oxides in the Indium sesquioxide.ITO has good photoelectric properties, and the film that contains ITO has high electroconductibility and visible light transmission, is widely used in various fields such as solar cell, liquid crystal indicator, touch-control electroplax.The method for preparing ito thin film has sputtering method, vacuum vapour deposition, sol-gel method, cluster sedimentation, PLD method etc.
When adopting vacuum evaporation or magnetron sputtering to prepare the ITO film, at first to prepare ito powder, sinter this powder compression into the ITO target again, wherein the density of ITO sintered compact is the important parameter of decision ITO target photoelectric properties.High more ITO sintered density helps improving the photoelectric properties of ITO sintered compact more, improves sintering character and sintering process that the ITO sintered density depends on ito powder.
When ito powder sintering character difference, in the agglomerating process,, therefore be difficult to obtain the ITO target of structural constituent homogeneous, and prepared sintered density is difficult to reach 7.08g/cm because Indium sesquioxide and stannic oxide can not form sufficient sosoloid
3, and body resistivity is difficult to drop to 2.0 * 10
-4Below.Owing to have a large amount of unsintered powder particles and hole in the low-density sintered compact, the target that uses this sintered compact processing dross very easily in the spatter film forming process not only influences spatter film forming speed, but also can have a strong impact on the quality of film.Therefore, people have proposed the whole bag of tricks and have prepared ito powder to improve its sintering character.
In the prior art, adopting coprecipitation method to prepare ito powder is a kind of method commonly used.Japanese Patent (JP-A) 7-21831 and 7-247162 disclose the process that coprecipitation method prepares ito powder, are about to InCl
3And SnCl
4The aqueous solution of formation soluble in water drips alkaline solution such as ammoniacal liquor etc. so that obtain to contain the throw out of indium and tin then as the aqueous solution that contains indium ion and tin ion in this aqueous solution, filter then, calcines this throw out, obtains ito powder.Yet in this patent, just simply alkaline solution is dripped to enter in the indium tin aqueous solution and precipitate, owing to fail to control any deposition condition, therefore the sintering character of the ito powder for preparing by above-mentioned patent is relatively poor, and the density of the ITO sintered compact that finally obtains is lower.
Chinese patent application file CN1495129A has carried out further qualification to the method in the above-mentioned patent, and promptly the ratio that the control divalent tin ion accounts for the tin ion total amount in the solution that contains indium ion and tin ion is equal to or greater than 50 weight %.Though in this application file, the ITO sintered compact that obtains has higher density, has met or exceeded 7.08g/cm
3Yet,, divalent tin ion itself can not stable existence in solution, is easy to be reduced, and therefore, this method is difficult to control in the operating process of reality, is difficult for the ito powder of the good sintering character of preparation.
Therefore, need provide a kind of preparation method with ito powder of good sintering character.
Summary of the invention
The technical problem that the present invention solves is, a kind of preparation method of the ito powder with good sintering character and the preparation method of ITO sintered compact are provided.
In order to solve above technical problem, the invention provides a kind of preparation method of ito powder, comprise step:
A) adding concentration in the indium solution of tin is that the alkaline aqueous solution of 10 weight %～30 weight % obtains the indium tin hydroxide precipitation solution, and in the process that adds alkaline aqueous solution, the temperature of control initial precipitation solution is at 16 ℃～30 ℃;
B) throw out and the liquid in the precipitation separation solution;
C) throw out that obtains after the washing separation;
D) the calcining throw out obtains ito powder.
Preferably, described step c) comprises
C1) use the ammonia scrubbing throw out;
C2) use the spirituous solution washing precipitate.
Preferably, obtain ito powder at 700 ℃～1300 ℃ calcining throw outs in the described step d).
Preferably, the alkaline aqueous solution in the step a) is ammonia soln and/or sodium hydroxide solution and/or potassium hydroxide solution.
Preferably, alkaline solution is that concentration is the ammonia soln of 22 weight %～28 weight % in the described step a).
Preferably, control the pH value of this indium tin hydroxide precipitation solution in the step a) 8～10.
Preferred point, the specific surface area of described ito powder are 3m
2/ g～20m
2/ g, median size is 0.1～1 μ m.
The present invention also provides a kind of ito powder that utilizes the arbitrary technical scheme of above technology to provide to prepare the method for ITO sintered compact, it is characterized in that, comprises step:
1) with described ito powder with make particulate after binding agent mixes;
2) utilize described particulate to prepare formed body;
3) binding agent in the removal formed body;
4) the described formed body of sintering obtains the ITO sintered compact.
Preferably, described binding agent is selected from one or more in polyvinyl alcohol, paraffin, the acrylate.
Preferably, in the step d) in 1300 ℃～1650 ℃ scope, the described formed body of sintering obtains the ITO sintered compact in normal pressure oxygen atmosphere or pressurised oxygen atmosphere.
The invention provides the preparation method of a kind of ito powder and sintered compact.The present invention is that the alkaline aqueous solution of 10 weight %～50 weight % obtains the indium tin hydroxide precipitation solution by add concentration in the indium tin aqueous solution, and the temperature of control initial precipitation solution is at 16 ℃～30 ℃.By selecting suitable deposition condition, the nucleus formation speed when adjusting precipitation and with crystal grain-growth speed, thereby make the good ito powder of sintering character.The ito powder granularity of the present invention's preparation is at 3m
2/ g～20m
2Between/the g, median size is between 0.1～1 μ m, has good sintering character.Adopt the ITO target sintered density of the ito powder preparation of the present invention's preparation to be at least 7.08g/cm
3, body resistivity is lower than 1.90 * 10
-4Ω cm, sintered compact largest grain size are lower than 10 μ m.
A kind of preferred embodiment in, after making throw out, adopt the weak ammonia washing precipitate earlier, adopt Diluted Alcohol solution washing throw out again, can improve sedimentary dispersiveness, thereby make the ito powder of favorable dispersity, prevent that ito powder from producing reunion, finally improves the performance of ITO target.
Description of drawings
Fig. 1 is the ito powder stereoscan photograph of the embodiment of the invention 1 preparation;
Fig. 2 is the ito powder stereoscan photograph of the embodiment of the invention 5 preparations;
Fig. 3 is the ito powder stereoscan photograph of comparative example 4 preparations of the present invention.
Embodiment
The specific embodiments of a preparation tin indium oxide powder of the present invention comprises step:
A) adding concentration in the indium solution of tin is that the alkaline aqueous solution of 10 weight %～30 weight % obtains the indium tin hydroxide precipitation solution, and in the process that adds alkaline aqueous solution, the temperature of control initial precipitation solution is at 18 ℃～30 ℃;
B) throw out and the liquid in the precipitation separation solution;
C) throw out that obtains after the washing separation;
D) the calcining throw out obtains ito powder.
According to the present invention, described indium solution of tin is meant the aqueous solution that contains indium ion and tin ion.This indium solution of tin can be by water miscible indium salt of dissolving such as Indium-111 chloride (InCl in water
3) or indium nitrate (In (NO
3)
3) and water-soluble pink salt such as tin protochloride (SnCl
4) or tin sulphate (Sn (SO
4)
2) prepare.Also can prepare by mixed indium salt brine solution and tin salt aqueous solution.The indium salt brine solution can by as above-mentioned in water dissolving indium salt method or in hydrochloric acid, sulfuric acid or nitric acid the method for dissolution of metals indium prepare; The tin solution of indium can by as above-mentioned in water the dissolving pink salt method or in hydrochloric acid, sulfuric acid or nitric acid the method for dissolution of metals tin prepare.
Described indium solution of tin also can prepare by dissolution of metals indium and metallic tin in hydrochloric acid, sulfuric acid or nitric acid; Perhaps dissolved oxygen indium and stannic oxide prepare in hydrochloric acid, sulfuric acid or nitric acid; Perhaps in hydrochloric acid, sulfuric acid or nitric acid, dissolve ito powder, ITO target waste material waits and prepares, to this present invention and without particular limitation.
Contain in the indium solution of tin above-mentioned, according to the weight ratio of Indium sesquioxide that tin ion and indium ion converted and stannic oxide 90: 10.
In the step a) in aforesaid method, adding concentration in the indium solution of tin is the alkaline aqueous solution of 10 weight %～30% weight, and preferred, the concentration of the alkaline aqueous solution of adding is 18% weight～28 weight %, preferred, the concentration of the alkaline aqueous solution of adding is 22 weight %～28 weight %.Described alkaline aqueous solution can be sodium hydroxide solution, potassium hydroxide solution, ammoniacal liquor etc., and preferred, described alkaline aqueous solution is that concentration is the ammonia soln of 22 weight %～28 weight %.In this step a), when indium solution of tin adding alkaline aqueous solution obtained the indium tin hydroxide precipitation solution, the temperature of control initial precipitation solution was at 18 ℃～30 ℃, and preferred, the temperature of controlling this indium tin hydroxide precipitation solution is at 20 ℃～25 ℃.
In order to improve the yield of ito powder, in step a), when adding alkaline aqueous solution in the indium tin aqueous solution, the pH value of test precipitation solution and the add-on control precipitation pH value of adjusting alkaline aqueous solution are 8～10.If the precipitation pH value is lower than 8 and can not fully carries out precipitin reaction, if the pH value of slurries is higher than 10 then can reduce the yield of ito powder.
In step a), after the adding alkaline aqueous solution finishes in the indium tin aqueous solution, can continue to stir precipitation solution, precipitin reaction is fully carried out; After the stirring, preferably precipitation solution can also be left standstill heavyization processing, the time of leaving standstill heavyization processing is preferably more than 12 hours.
After the indium tin hydroxide precipitation solution left standstill heavyization processing, need carry out step b) and be about to throw out and separate with liquid.When throw out is separated with liquid, can adopt modes such as suction filtration, press filtration, centrifugation, pressure filter to carry out, to this present invention and without particular limitation.
By the throw out that obtains after the solid-liquid separation, can carry out step c) and promptly wash this throw out.Washing can utilize distilled water, deionized water, ammoniacal liquor, alcohol to wash removal impurity.In order further to improve the dispersiveness of ito powder, reduce the generation of powder agglomeration.Preferably, the invention provides following washing scheme: c1) adopt ammoniacal liquor to wash earlier; C2) with behind the ammonia scrubbing, wash with spirituous solution again, wash specific conductivity to filtrate less than 150 μ s/cm, preferred, wash specific conductivity to filtrate less than 100 μ s/cm.
At step c1) in, can working concentration be that the ammonia soln of 10 weight %～80 weight % washs, preferred, working concentration is the ammonia soln washing of 15 weight %～40 weight %.At step c2) in, can working concentration be that the spirituous solution of 10 weight %～80 weight % washs, preferred, working concentration is the spirituous solution washing of 15 weight %～40 weight %.When adopting ammonia scrubbing earlier, sour effect, common-ion effcet and Complex effect by in the washing of precipitate process can reduce the impurity absorption in the washing of precipitate process, improve the efficient and the sedimentary purity of washing of precipitate, thereby improve the purity of calcined powder.With after the spirituous solution washing, can improve sedimentary dispersiveness, thereby obtain the ito powder of favorable dispersity again, prevent the ito powder reunion, finally improve the performance of ITO target; In addition, adopt the washing of ammonia soln and spirituous solution, can also suppress resolution of precipitate degree in the washing process, improve yield.
After the throw out washing, a preferred step provided by the invention is carried out drying with the liquid in the further removal throw out for the throw out after will washing, and drying can spraying drying or lyophilize or the drying that heats up.Preferably, throw out is warming up to 90 ℃～200 ℃, preferred, be warming up in 90～150 ℃ the scope and carry out drying sinking to the bottom thing.
Dried throw out can carry out step d), and soon this throw out is calcined in 700～1300 ℃ scope and obtained ito powder, and preferred, calcining temperature is 750 ℃～1000 ℃.For calcination time the present invention and without particular limitation.For calcination atmosphere, the present invention does not have special restriction, can carry out hydrogen halide and can be hydrogenchloride, hydrogen bromide, hydrogen iodide etc. under the atmosphere of hydrogen halide, halogen, air, oxygen, nitrogen or argon gas.Halogen is chlorine, bromine, iodine etc.Preferably, calcining is carried out under air atmosphere.
According to the present invention, the median size of the ito powder that obtains after the calcining is at 0.1～1 μ m, and specific surface area is at 3m
2/ g～20m
2/ g, preferred, the median size of the ito powder that obtains after the calcining is at 0.1～0.7 μ m, and specific surface area is at 5m
2/ g～12m
2/ g.Ito powder provided by the invention has good dispersiveness, and it is few to reunite, and has sintering character preferably.
The present invention also provides a kind of method of utilizing above-mentioned ito powder to prepare the ITO sintered compact, and a kind of concrete embodiment comprises step:
1) described ito powder is mixed back preparation particulate with binding agent;
2) utilize described particulate to prepare formed body;
3) binding agent in the removal formed body;
4) sintered moulded body obtains the ITO sintered compact.
Wherein, the binding agent in the step 1) can use all mineral binder bonds well known by persons skilled in the art, organically-modified inorganic or organic binder bond or their mixture.Organic binder bond can be polyvinyl resin, as polyolefine, PVC, polyvinyl alcohol, polyvinyl ester or polystyrene, acrylic resin, as acrylate or methacrylic ester; Alkyd resin; Urethane, urea, trimeric cyanamide, resol or cellulose ester are as cellulosic acetic ester or butyric ester.Organically-modified inorganic adhesive can be organopolysiloxane.
After with ito powder and binding agent mixed slurry, can adopt spray-dired method to make the particulate of 1～100 μ m.Behind the spraying preparation particulate, utilize this particulate to prepare formed body.The preparation formed body can adopt mould compression moulding, also can adopt casting, to this present invention and without particular limitation.
Behind the preparation formed body, can adopt the exsiccant mode to remove binding agent in the formed body.
After removing binding agent, obtain the ITO sintered compact at 1300～1650 ℃ of sintered moulded bodies, sintering time was at least 5 hours, can or have at the normal pressure oxygen atmosphere to carry out sintering under the pressurised oxygen atmosphere.Preferably, under the oxygen atmosphere of 0.1～1.0MPa, carry out sintering, help improving the density of ITO sintered compact more.
According to the present invention, the density of the ITO sintered compact of preparation is at least 7.08g/cm
3, the largest grain size of sintered compact is lower than 10 μ m, and body resistivity is lower than 1.90 * 10
-4Ω cm; Preferably, the density of sintered compact is 7.11g/cm
3, the largest grain size of sintered compact is lower than 8 μ m.
The ASAP2021 type specific surface area instrument that the BET specific surface area of the ito powder among the present invention adopts Micrometities company to produce is measured, and the median size of powder adopts LS-230 type laser particle size distribution instrument that BECKMANCOLOUR company produces recording after 60 seconds with ultrasonic vibration; Grain-size in the sintered compact among the present invention is measured with the JSM-5610LV sem observation; The ITO sintered density is measured with Archimedes's method; The body resistance of ITO sintered compact is measured with electrical resistance method.
In order further to understand the present invention, the preparation method to ito powder provided by the invention and sintered compact is described below in conjunction with embodiment and comparative example.
Indium metal and metallic tin are dissolved in the solution that preparation in the hydrochloric acid contains indium ion and tin ion, and to become the mass ratio of Indium sesquioxide and stannic oxide be 90: 10 to the mass conversion of indium ion and tin ion in this solution.
Above-mentioned solution is placed in the encloses container, the ammoniacal liquor that in this solution, adds 25 weight %, stir this precipitation solution, the add-on of adjusting ammoniacal liquor makes that sedimentary pH value is 8.8, the temperature of control initial precipitation solution is about 30 ℃, back continuation stirring fully 2 hours is carried out in precipitin reaction, leaves standstill heavyization 12 hours.
With sedimentation and filtration, is the ammonia soln washing precipitation of 25 weight % earlier with concentration, again with concentration be the spirituous solution of 22 weight % wash to the filtrate specific conductivity less than 100 μ s/cm.The washing after-filtration, again with throw out in 105 ℃ of oven dry, with the oven dry after throw out be sintered into ito powder in 850 ℃.
Measuring above-mentioned ito powder BET specific surface area is 12m
2/ g, median size is 0.3 μ m, powder favorable dispersity, powder morphology are as shown in Figure 1.
Above-mentioned powder spray is made the particle that granularity is 10～100 μ m, be pressed into formed body with forming mould, after the formed body degreasing, under the 0.5MPa oxygen atmosphere, 1500 ℃ of sintering 10 hours obtain the ITO sintered compact of 500 * 200 * 10mm.
Measuring this sintered density is 7.130g/cm
3
Take a sample from sintered compact, after the processing, surveying its body resistivity is 1.74 * 10
-4Ω cm, largest grain size is 5 μ m in the scanning electron microscopic observation sintered compact.
Embodiment 2
Indium metal and metallic tin are dissolved in the solution that preparation in the hydrochloric acid contains tin ion and indium ion, and to become the mass ratio of Indium sesquioxide and stannic oxide be 90: 10 to the mass conversion of indium ion and tin ion in this solution.
Above-mentioned solution is placed in the encloses container, in this solution, adds the ammoniacal liquor of 25 weight %, stir, the pH value of adjusting this precipitation solution is 8.2, the temperature of control initial precipitation solution is about 30 ℃, and back continuation stirring fully 2 hours is carried out in precipitin reaction, leaves standstill heavyization 12 hours.
With sedimentation and filtration, is the ammonia soln washing precipitation of 35 weight % earlier with concentration, again with concentration be the spirituous solution of 21 weight % wash to the filtrate specific conductivity less than 100 μ s/cm.The washing after-filtration, again with throw out in 105 ℃ of oven dry, with the oven dry after throw out be sintered into ito powder in 1050 ℃.
Measuring above-mentioned ito powder BET specific surface area is 9m
2/ g, median size is 0.3 μ m.
Above-mentioned powder spray is made the particle that granularity is 10～100 μ m, be pressed into formed body with forming mould, after the formed body degreasing, under the 0.5MPa oxygen atmosphere, 1500 ℃ of sintering 10 hours obtain the ITO sintered compact of 500 * 200 * 10mm.
Measuring this sintered density is 7.130g/cm
3
Take a sample from sintered compact, after the processing, surveying its body resistivity is 1.71 * 10
-4Ω cm, largest grain size is 5 μ m in the scanning electron microscopic observation sintered compact.
Embodiment 3
Indium metal and metallic tin are dissolved in the solution that preparation in the hydrochloric acid contains tin ion and indium ion, and to become the mass ratio of Indium sesquioxide and stannic oxide be 90: 10 to the mass conversion of indium ion and tin ion in this solution.
Above-mentioned solution is placed in the encloses container, the ammoniacal liquor that in this solution, adds 20 weight %, stir this precipitation solution, the add-on of adjusting ammoniacal liquor makes that the pH value of precipitation solution is 8.8, the temperature of control initial precipitation solution is about 30 ℃, back continuation stirring fully 2 hours is carried out in precipitin reaction, leaves standstill heavyization 12 hours.
With sedimentation and filtration, is the ammonia soln washing precipitation of 36 weight % earlier with concentration, again with concentration be the spirituous solution of 28 weight % wash to the filtrate specific conductivity less than 100 μ s/cm.。The washing after-filtration, again with throw out in 105 ℃ of oven dry, with the oven dry after throw out be sintered into ito powder in 950 ℃.
Measuring above-mentioned ito powder BET specific surface area is 8.5m
2/ g, median size is 0.5 μ m.
Above-mentioned powder spray is made the particle that granularity is 10～100 μ m, be pressed into formed body with forming mould, after the formed body degreasing, under the 0.5MPa oxygen atmosphere, 1500 ℃ of sintering 10 hours obtain the ITO sintered compact of 500 * 200 * 10mm.
Measuring this sintered density is 7.140g/cm
3
Take a sample from sintered compact, after the processing, surveying its body resistivity is 1.76 * 10
-4Ω cm, largest grain size is 5 μ m in the scanning electron microscopic observation sintered compact.
Embodiment 4
Indium metal and metallic tin are dissolved in the solution that preparation in the hydrochloric acid contains tin ion and indium ion, and to become the mass ratio of Indium sesquioxide and stannic oxide be 90: 10 to the mass conversion of indium ion and tin ion in this solution.
Above-mentioned solution is placed in the encloses container, the ammoniacal liquor that in this solution, adds 18 weight %, stir this precipitation solution, the add-on of adjusting ammoniacal liquor makes that the pH value of precipitation solution is 8.8, the temperature of control initial precipitation solution is about 25 ℃, back continuation stirring fully 2 hours is carried out in precipitin reaction, leaves standstill heavyization 12 hours.
With sedimentation and filtration, is the ammonia soln washing precipitation of 25 weight % earlier with concentration, again with concentration be the spirituous solution of 18 weight % wash to the filtrate specific conductivity less than 100 μ s/cm.。The washing after-filtration, again with throw out in 105 ℃ of oven dry, with the oven dry after throw out be sintered into ito powder in 1000 ℃.
Measuring above-mentioned ito powder BET specific surface area is 7.5m
2/ g, median size is 0.5 μ m.
Above-mentioned powder spray is made the particle that granularity is 10～100 μ m, be pressed into formed body with forming mould, after the formed body degreasing, under the 0.5MPa oxygen atmosphere, 1500 ℃ of sintering 10 hours obtain the ITO sintered compact of 500 * 200 * 10mm.
Measuring this sintered density is 7.130g/cm
3
Take a sample from sintered compact, after the processing, surveying its body resistivity is 1.72 * 10
-4Ω cm, largest grain size is 5 μ m in the scanning electron microscopic observation sintered compact.
Embodiment 5
Indium metal and metallic tin are dissolved in the solution that preparation in the hydrochloric acid contains tin ion and indium ion, and to become the mass ratio of Indium sesquioxide and stannic oxide be 90: 10 to the mass conversion of indium ion and tin ion in this solution.
Above-mentioned solution is placed in the encloses container, in this solution, adds the ammoniacal liquor of 18 weight %, stir, the pH value of adjusting this precipitation solution is 8.8, the temperature of control initial precipitation solution is about 25 ℃, and back continuation stirring fully 2 hours is carried out in precipitin reaction, leaves standstill heavyization 12 hours.
With sedimentation and filtration, is the ammonia soln washing precipitation of 36 weight % earlier with concentration, again with concentration be the spirituous solution of 30 weight % wash to the filtrate specific conductivity less than 100 μ s/cm.The washing after-filtration, again with throw out in 105 ℃ of oven dry, with the throw out after the oven dry in 730 ℃ of once calcinings, and then in 1300 ℃ of secondary clacinings.
Powder BET is 5m behind the secondary clacining
2/ g, median size is 0.7 μ m, powder favorable dispersity, powder morphology are as shown in Figure 1.
Above-mentioned powder spray is made the particle that granularity is 10～100 μ m, be pressed into formed body with forming mould, after the formed body degreasing, under the 0.5MPa oxygen atmosphere, 1500 ℃ of sintering 10 hours obtain the ITO sintered compact of 500 * 200 * 10mm.
Measuring this sintered density is 7.140g/cm
3
Take a sample from sintered compact, after the processing, surveying its body resistivity is 1.70 * 10
-4Ω cm, largest grain size is 5 μ m in the scanning electron microscopic observation sintered compact.
Comparative example 1
Indium metal and metallic tin are dissolved in the solution that preparation in the hydrochloric acid contains tin ion and indium ion, and to become the mass ratio of Indium sesquioxide and stannic oxide be 90: 10 to the mass conversion of indium ion and tin ion in this solution.
The above-mentioned tin indium aqueous solution is placed in the encloses container, in this container, adds the ammoniacal liquor of 25 weight %, stir this precipitation solution, the pH value of adjusting this precipitation solution is 8.8, the temperature of controlling this precipitation solution is about 16 ℃, and back continuation stirring fully 2 hours is carried out in precipitin reaction, leaves standstill heavyization 12 hours.
With sedimentation and filtration, is the ammonia soln washing precipitation of 30 weight % earlier with concentration, again with concentration be the spirituous solution of 25 weight % wash to the filtrate specific conductivity less than 100 μ s/cm.。The washing after-filtration, again with throw out in 105 ℃ of oven dry, with the oven dry after throw out be sintered into ito powder in 850 ℃.
Measuring above-mentioned ito powder BET specific surface area is 25m
2/ g, median size is 0.2 μ m.
Above-mentioned powder spray is made the particle that granularity is 10～100 μ m, be pressed into formed body with forming mould, after the formed body degreasing, under the 0.5MPa oxygen atmosphere, 1500 ℃ of sintering 10 hours obtain the ITO sintered compact of 500 * 200 * 10mm.
Measuring this sintered density is 7.01g/cm
3
Take a sample from sintered compact, after the processing, surveying its body resistivity is 2.06 * 10
-4Ω cm.
Comparative example 2
Indium metal and metallic tin are dissolved in the solution that preparation in the hydrochloric acid contains tin ion and indium ion, and to become the mass ratio of Indium sesquioxide and stannic oxide be 90: 10 to the mass conversion of indium ion and tin ion in this solution.
The above-mentioned tin indium aqueous solution is placed in the encloses container, the ammoniacal liquor that in this container, adds 25 weight %, stir this precipitation solution, the pH value of adjusting this precipitation solution is 8.8, the temperature of control initial precipitation solution is about 35 ℃, back continuation stirring fully 2 hours is carried out in precipitin reaction, leaves standstill heavyization 12 hours.
With sedimentation and filtration, is the ammonia soln washing precipitation of 30 weight % earlier with concentration, again with concentration be the spirituous solution of 25 weight % wash to the filtrate specific conductivity less than 100 μ s/cm.。The washing after-filtration, again with throw out in 105 ℃ of oven dry, with the oven dry after throw out be sintered into ito powder in 850 ℃.
Measuring above-mentioned ito powder BET specific surface area is 3m
2/ g, median size is 1.2 μ m.
Above-mentioned powder spray is made the particle that granularity is 10～100 μ m, be pressed into formed body with forming mould, after the formed body degreasing, under the 0.5MPa oxygen atmosphere, 1500 ℃ of sintering 10 hours obtain the ITO sintered compact of 500 * 200 * 10mm.
Measuring this sintered density is 6.98g/cm
3
Take a sample from sintered compact, after the processing, surveying its body resistivity is 2.14 * 10
-4Ω cm.
Comparative example 3
Indium metal and metallic tin are dissolved in the solution that preparation in the hydrochloric acid contains tin ion and indium ion, and to become the mass ratio of Indium sesquioxide and stannic oxide be 90: 10 to the mass conversion of indium ion and tin ion in this solution.
The above-mentioned tin indium aqueous solution is placed in the encloses container, the ammoniacal liquor that in this container, adds 35 weight %, stir this precipitation solution, the pH value of adjusting this precipitation solution is 8.8, the temperature of control initial precipitation solution is about 30 ℃, back continuation stirring fully 2 hours is carried out in precipitin reaction, leaves standstill heavyization 12 hours.
With sedimentation and filtration, is the ammonia soln washing precipitation of 30 weight % earlier with concentration, again with concentration be the spirituous solution of 25 weight % wash to the filtrate specific conductivity less than 100 μ s/cm.The washing after-filtration, again with throw out in 105 ℃ of oven dry, with the oven dry after throw out be sintered into ito powder in 850 ℃.
Measuring above-mentioned ito powder BET specific surface area is 28m
2/ g, median size is 0.2 μ m.
Above-mentioned powder spray is made the particle that granularity is 10～100 μ m, be pressed into formed body with forming mould, after the formed body degreasing, under the 0.5MPa oxygen atmosphere, 1500 ℃ of sintering obtained the ITO sintered compact of 500 * 200 * 10mm more than 10 hours.
Measuring this sintered density is 7.01g/cm
3
Take a sample from sintered compact, after the processing, surveying its body resistivity is 2.1 * 10
-4Ω cm.
Comparative example 4
Indium metal and metallic tin are dissolved in the solution that preparation in the hydrochloric acid contains tin ion and indium ion, and to become the mass ratio of Indium sesquioxide and stannic oxide be 90: 10 to the mass conversion of indium ion and tin ion in this solution.
The above-mentioned tin indium aqueous solution is placed in the encloses container, the ammoniacal liquor that in this container, adds 25 weight %, stir this precipitation solution, the pH value of adjusting this precipitation solution is 8.8, the temperature of control initial precipitation solution is about 30 ℃, back continuation stirring fully 2 hours is carried out in precipitin reaction, leaves standstill heavyization 12 hours.
With sedimentation and filtration, be that the ammonia scrubbing precipitation filtrate specific conductivity of 30 weight % is less than 100 μ s/cm with concentration.The washing after-filtration, again with throw out in 105 ℃ of oven dry, with the oven dry after throw out be sintered into ito powder in 850 ℃.
Measuring above-mentioned ito powder BET specific surface area is 12m
2/ g, median size is 0.3 μ m, and powder agglomeration is serious, and powder morphology is as shown in Figure 3.
Above-mentioned powder spray is made the particle that granularity is 10～100 μ m, be pressed into formed body with forming mould, after the formed body degreasing, under the 0.5MPa oxygen atmosphere, 1500 ℃ of sintering 10 hours obtain the ITO sintered compact of 500 * 200 * 10mm.
Measuring this sintered density is 7.13g/cm
3
Take a sample from sintered compact, after the processing, surveying its body resistivity is 1.94 * 10
-4Ω cm, maximum crystal grain is 7 μ m in the scanning electron microscopic observation sintered compact, processing back target material surface has a large amount of holes.
Comparison diagram 1, Fig. 2 and Fig. 3 as can be known, when with throw out earlier with ammonia scrubbing again with the ethanolic soln washing after, the powder favorable dispersity is not reunited substantially.And when only adopting ammonia scrubbing, powder agglomeration is serious, though the ITO target density of making is unaffected substantially, target material surface has more hole, has reduced the quality of target.
More than the preparation method of ito powder provided by the invention and sintered compact is described in detail, gone detailed introduction.Used specific case herein principle of the present invention and embodiment are set forth, the explanation of above embodiment just is used for helping to understand method of the present invention and core concept thereof.Should be pointed out that for those skilled in the art, under the prerequisite that does not break away from the principle of the invention, can also carry out some improvement and modification to the present invention, these improvement and modification also fall in the protection domain of claim of the present invention.
Claims (10)
1. the preparation method of an ito powder comprises step:
A) adding concentration in the indium solution of tin is that 10 weight %～30 weight % alkaline aqueous solutions obtain the indium tin hydroxide precipitation solution, and in the process that adds alkaline aqueous solution, the temperature of control initial precipitation solution is at 18 ℃～30 ℃;
B) throw out and the liquid in the precipitation separation solution;
C) throw out that obtains after the washing separation;
D) the calcining throw out obtains ito powder.
2. method according to claim 1 is characterized in that described step c) comprises
C1) use the ammonia soln washing precipitate;
C2) use the spirituous solution washing precipitate.
3. method according to claim 1 and 2 is characterized in that obtaining ito powder at 700 ℃～1300 ℃ calcining throw outs in the described step d).
4. method according to claim 1 is characterized in that the step a) neutral and alkali aqueous solution is ammonia soln and/or sodium hydroxide solution and/or potassium hydroxide solution.
5. method according to claim 4 is characterized in that the described step a) neutral and alkali aqueous solution is that concentration is the ammonia soln of 22 weight %～28 weight %.
6. method according to claim 1 and 2, the pH value that it is characterized in that this indium tin hydroxide precipitation solution of control in the described step a) is 8～10.
7. method according to claim 1 and 2, the specific surface area that it is characterized in that described ito powder is 3m
2/ g～20m
2/ g, median size is 0.1 μ m～1 μ m.
8. a method of using each described ito powder of claim 1 to 7 to prepare the ITO sintered compact is characterized in that, comprises step:
1) with described ito powder with make particulate after binding agent mixes;
2) utilize described particulate to prepare formed body;
3) binding agent in the removal formed body;
4) the described formed body of sintering obtains the ITO sintered compact.
9. method according to claim 8 is characterized in that described binding agent is selected from one or more in polyvinyl alcohol, paraffin, the CALCIUM ACRYLATE.
10. method according to claim 8 is characterized in that in the step 4) in 1300 ℃～1650 ℃ scopes, sintering obtains the ITO sintered compact in normal pressure oxygen atmosphere or pressurised oxygen atmosphere.
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| CN102627454A (en) * | 2012-04-24 | 2012-08-08 | 西北稀有金属材料研究院 | Preparation method for indium tin oxide (ITO) powder and preparation method for ITO sintering body |
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| CN108002427B (en) * | 2017-11-29 | 2019-05-24 | 广西生富锑业科技股份有限公司 | A kind of preparation method of tin indium oxide nano-powder |
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