CN108911707A - The preparation method of high-density ITO targe material - Google Patents
The preparation method of high-density ITO targe material Download PDFInfo
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Abstract
The present invention relates to a kind of preparation methods of high-density ITO targe material, using high purity indium, tin tetrachloride as raw material, indium are dissolved in nitric acid, generates In (NO3)3, tin tetrachloride is dissolved in distilled water, then generates In (OH) with after ammonium hydroxide reaction respectively3With Sn (OH)4Precipitating, by two kinds of sediment agings, filter, be sufficiently mixed, clean after calcine after obtain ito powder, then will be added appropriate dispersing agent and adhesive ito powder grinding, be granulated, pre-molding, using isostatic cool pressing, ITO target then is sintered into Low Pressure Oxygen atmosphere calcining furnace.Due to this invention ensures that the ito powder of preparation component and partial size high uniformity, be conducive to that follow-up sintering is functional, with this ito powder and the method for this patent preparation ITO target, obtained sintered body ingredient and grain structure is uniform, and oxygen content and density are high.
Description
Technical field：
The present invention relates to ITO target preparation technical field more particularly to a kind of preparation methods of high-density ITO targe material.
Background technique：
The main component of ITO (tin indium oxide) is the composite oxides of different proportion tin oxide, indium oxide, and ITO's is thin
Film has high conductivity and visible light transmission, is widely used in the fields such as touch screen, solar energy and two-d display panel.Preparation
The method of ito thin film has sputtering method, vapour deposition method, sol-gel method, PLD method etc..
The common method for preparing ito thin film has magnetron sputtering method, vacuum vapour deposition, when preparing ito film with both methods,
It first has to prepare ito powder, then powder is prepared into ITO target.The granularity of ito powder, the density of uniformity and ITO target,
Oxygen content is an important factor for influencing ito thin film performance.If the granularity of ito powder, uniformity cannot be guaranteed, ito powder
Easily there is phenomena such as density is small, density variation becomes larger or crystal grain difference is big in follow-up sintering, and the density of ITO target, oxygen content be not up to
To requirement, the bad phenomenons such as arc discharge, Particle be excessive, the decline of ito thin film quality can be generated in coating process.
In general ito powder is using following preparation method：It is utilized respectively indium metal and metallic tin obtains indium oxide powder
With stannic oxide powder, indium oxide powder is then mixed into dispersion with stannic oxide powder.Due to as basic raw material indium metal and
The control conditions such as solution rate, solution temperature, neutralization pH value, neutralization temperature and the mixing speed of metallic tin are difficult to fully achieve
Sameization affects ITO so that the density variation of the partial size and prepared target of indium oxide powder and stannic oxide powder is larger
The quality of film.
In the prior art, preparing ito powder using coprecipitation is a kind of common method, for example, Japan Patent is literary
It offers (JP-A) 7-21831 and 7-247162 and discloses the process that coprecipitation prepares ito powder, i.e., be dissolved in InCl3 and SnCl4
Aqueous slkali such as ammonium hydroxide etc. is added dropwise into the aqueous solution as the aqueous solution containing indium ion and tin ion for the aqueous solution formed in water
It to obtain the sediment containing indium and tin, then filters, calcines the sediment, obtain ito powder.However distinguish in that patent
Using InCl3 and SnCl4 as raw material, uniformity and the sintering character for easily leading to the ito powder of preparation are poor.For another example Japanese
Patent document special open H6-329415 and special open 2001-303239, which are reported, prepares indium tin co-precipitation oxygen using indium stannum alloy
The method of the powder of compound, using indium stannum alloy as anode, ammonium nitrate solution is as electrolyte.But utilizing electrolysis legal system
In standby indium tin co-precipitation oxide process, easily there is the phenomenon that metastannic acid is precipitated and solidifies in the surface of indium stannum alloy electrode, thus
The particle size uniformity of the ito powder of preparation is influenced, and is difficult continually and steadily to operate.In addition, Japanese patent document special opening 63-
Indium stannum alloy is heated to 1300 DEG C and is allowed to evaporation oxidation by a kind of No. 199862 preparation methods for reporting ito powder, thus
To ito powder.But since this method equipment investment scale is big, heat source higher cost, and the partial size of the ito powder prepared
Uniformity cannot be guaranteed.
The preparation method of general ITO target has：China patent CN200910117332.7, utilizes indium oxide and tin oxide system
At ito powder, ITO is packed into special die sleeve, in 900-1100 DEG C of hot isostatic pressing vacuum environment, keeps the temperature 2-3 hour, pressure maintaining pressure
ITO sintered body is made in power 9-15MPa.This method investment is big at high cost, and manufactured ITO target Density inhomogeneity, oxygen content is not
It is high.For another example patent CN200980102084.7, powder prepared by coprecipitation method, mixed dispersant, adhesive and height after calcining
Density promoting agent slurrying, then filling is poured into special porous mold under a certain pressure, and 80 DEG C are dried 3-5 days, then
1000-1750 DEG C of sintering generates ITO sintered body under high purity oxygen environment.This method monolithic production cycle is long, and ITO raw embryo is held
Easy to crack, longitudinally there is a density variation in section, and target is easy dross when use.
Summary of the invention：
The present invention for the defects in the prior art, provides a kind of sintered body ingredient and grain structure is uniform, oxygen content and
The preparation method of the high high-density ITO targe material of density.
The present invention is achieved through the following technical solutions：
A kind of preparation method of high-density ITO targe material, includes the following steps：
A. indium grain is mixed with nitric acid, mixed solution is obtained after reaction, ammonium hydroxide is added into solution, it is heavy that reaction obtains white
Starch indium hydroxide, by indium hydroxide aging, filtering, cleaning, drying；
B. tin tetrachloride solution and ammonium hydroxide are reacted, flocky precipitate stannic hydroxide is obtained, by stannic hydroxide aging, mistake
Filter, cleaning, drying；
C. both the above sediment is mixed, by indium hydroxide：The mass ratio 9 of stannic hydroxide：1, it cleans, is dry, sufficiently
Ground and mixed；
D. ito powder will be obtained after the powder calcining after grinding；
E. slurries, gained slurry will be obtained after ito powder, distilled water, polycarboxylic acid dispersant, wax based adhesive mixed grinding
Liquid is dry with spray drying process；
F. the ito powder after drying is packed into mold pre-molding, is then pressed into ITO target embryo with cold isostatic press again
Material；
G. degreasing removes dispersing agent, adhesive in above-mentioned embryo material, and ITO burning is then sintered into Low Pressure Oxygen atmosphere calcining furnace
Knot body obtains ITO target after machining.
In order to guarantee that subsequent ITO grain structure is uniform, it is preferred that the indium grain is prepared using following methods：Surface is attached
There is the indium metal block of glycerol, it is cooling after being dissolved at 150-230 DEG C, circulating cooling is dropped to by the stainless steel nozzle of 2mm diameter
In distilled water, indium grain is obtained, indium partial size is 2-5mm, and the concentration of nitric acid is 50-70wt%, and the reaction temperature for dissolving indium is 50-
110 DEG C, the reaction time is 24 hours, ammonia concn 20-28wt%, and neutralization-precipitation reaction and ageing time are 18-32 hours.
Preferably, in the step b, the concentration of tin ion is 20g/L-60g/L, the concentration of ammonium hydroxide in tin tetrachloride solution
For 20wt%-28wt%, for the pH value of stannic hydroxide precipitation solution in 7-10, reaction and ageing time are 12-36 hours.
Preferably, after cleaning in the step c, chloride ion content is less than 80-10ppm in raffinate, and drying time is 24 small
When, mixed grinding 4-8 hours.
Preferably, in the step d, calcination temperature is 300-1100 DEG C, and calcination time is 3-12 hours.
It was found that the unsuitable excessive addition of polycarboxylic acid dispersant, wax based adhesive, the step e in actual experiment
In, in ITO slurries, ito powder, distilled water, polycarboxylic acid dispersant, wax based adhesive weight ratio be preferably 100：85：
0.5：1.
Preferably, pre-molding pressure is 30-250kg/cm2 in the step f, and isostatic cool pressing pressure is 150-
300MPa。
Actual experiment surface degreasing time is unsuitable too short, and therefore, skimming temp is preferably 100-600 DEG C in step g, degreasing
Time 80-100 hour, and temperature, pressure, flow and the time calcined directly affect the performance of ITO sintered body, therefore, as
It is preferred that Low Pressure Oxygen atmosphere calcining furnace 1.1-1.5 atmospheric pressure of pressure, flow 0.5-5L/m2/ minute, calcination temperature 300-1600
DEG C, calcination time is 36-48 hours.
In addition, concentrated hydrochloric acid (HCl) can also be used for dissolving the nitric acid of indium grain in the present invention；NaOH aqueous slkali can also
To substitute ammonium hydroxide, but after cleaning sediment, need to examine Na in residual water+Content；The dispersing agent that is used when preparing ITO slurry and
Other kinds of raw material also can be used in adhesive, but may will affect target density, or have residual impurity to cause target contamination.
The beneficial effects of the invention are as follows：The present invention is with high purity indium (In), tin tetrachloride (SnCl4) it is raw material, indium is molten
Solution generates In (NO in nitric acid3)3, tin tetrachloride is dissolved in distilled water, then respectively with ammonium hydroxide (NH4OH In is generated after) reacting
(OH)3With Sn (OH)4Precipitating, by two kinds of sediment agings, filter, be sufficiently mixed, clean after calcining after obtain ito powder, then
By the ito powder grinding that appropriate dispersing agent and adhesive is added, it is granulated, pre-molding, using isostatic cool pressing, then in low pressure
Sinter ITO target into oxygen atmosphere calcining furnace, compared with prior art, due to this invention ensures that preparation ito powder component
With partial size high uniformity, it is functional to be conducive to follow-up sintering, the experimental results showed that, the crystal grain of ito powder prepared by the present invention
D90/D50 is not more than 3.5-4.0, specific surface area 6-11m2/ g, with this ito powder and the side of this patent preparation ITO target
Method, obtained sintered body ingredient and grain structure is uniform, and oxygen content and density are high.
Detailed description of the invention：
Fig. 1 is the micro-structure diagram of ITO target produced by the present invention.
Specific embodiment：
Hereinafter the technical solution of the embodiment of the present invention define, meticulously be described, it is clear that described embodiment is only
It is only a part of the embodiment of the present invention, instead of all the embodiments.Based on the embodiments of the present invention, those skilled in the art
Every other embodiment obtained without creative efforts, shall fall within the protection scope of the present invention.
The present invention provides a kind of preparation method of high-density ITO targe material, includes the following steps：
A. indium grain is mixed with nitric acid, mixed solution is obtained after reaction, ammonium hydroxide is added into solution, it is heavy that reaction obtains white
Starch indium hydroxide, by indium hydroxide aging, filtering, cleaning, drying；
B. tin tetrachloride solution and ammonium hydroxide are reacted, flocky precipitate stannic hydroxide is obtained, by stannic hydroxide aging, mistake
Filter, cleaning, drying；
C. both the above sediment is mixed, by indium hydroxide：The mass ratio 9 of stannic hydroxide：1, it cleans, is dry, sufficiently
Ground and mixed；
D. ito powder will be obtained after the powder calcining after grinding；
E. slurries, gained slurry will be obtained after ito powder, distilled water, polycarboxylic acid dispersant, wax based adhesive mixed grinding
Liquid is dry with spray drying process；
F. the ito powder after drying is packed into mold pre-molding, is then pressed into ITO target embryo with cold isostatic press again
Material；
G. degreasing removes dispersing agent, adhesive in above-mentioned embryo material, and ITO burning is then sintered into Low Pressure Oxygen atmosphere calcining furnace
Knot body obtains ITO target after machining.
Indium grain of the invention is that water quenching is prepared into graininess after melting indium metal, on the one hand convenient for preparation, on the other hand
The reaction time for being conducive to control with nitric acid guarantees going on smoothly for reaction；Preferable particle size is 2-5mm.The indium grain is preferably pressed
It is prepared according to following methods：Surface is had to the indium metal block of glycerol, it is cooling after being dissolved at 150-230 DEG C, pass through 2mm diameter
Stainless steel nozzle drops in circulating cooling distilled water, obtains indium grain.During the preparation process, solution temperature is preferably 150-230 DEG C,
More preferably 160-200 DEG C, which does not aoxidize while ensure that indium metal dissolution.
Indium grain obtained is mixed with nitric acid and is reacted, indium nitrate In (NO is obtained3)3Solution.Then to indium nitrate In
(NO3)3Ammonium hydroxide is added dropwise in solution, obtains indium hydroxide precipitating.In this step, the concentration of nitric acid is preferably 50-70wt%, most preferably
It is 70%.The nitric acid dissolution indium reaction temperature of step a is preferably 50-110 DEG C, and more preferably 70~100 DEG C, most preferably 80~
90℃.Reaction time is preferably 24 hours.Ammonia concn is preferably 20-28wt% in this step a, most preferably 28wt%, is neutralized
Precipitation reaction temperature is preferably 30-80 DEG C, and most preferably 50 DEG C, ageing time is preferably 18-36 hours, more preferably 24-28
Hour, the granule size and agglomeration of reaction temperature and time effects indium hydroxide, temperature is high, and the reaction time is long, indium hydroxide
Grain size number is big, otherwise granularity is smaller, is unfavorable for subsequent filtering when granularity is smaller.
Tin tetrachloride solution is instilled into ammonia spirit stirring, generates fluffy white precipitate.In this step b, Sn4+Concentration is preferred
For 20-60g/L, more preferably 40-50g/L, ammonia concn is preferably 20-28wt%, most preferably 25wt%, and hydroxide is heavy
Shallow lake pH value is preferably 7-10, more preferably 8-9, and reaction and ageing time are preferably 12-36 hours, and most preferably 24 hours, always
Change is in order to which precipitation reaction is sufficiently complete, and crystal grain is complete；Step a and b is preferably by automation control, to avoid generation
Deviation.
It is dry by the indium hydroxide of generation and the filtering of stannic hydroxide precipitating, cleaning, according to indium oxide, tin oxide mass ratio
9：1 mixing, grinding.In this step c, stannic hydroxide cleans Cl in raffinate-Preferred content be lower than 80-10ppm, most preferably
10ppm, exceeded Cl-Content will affect the purity of subsequent ito powder and the characteristic of ito thin film.60 DEG C of drying temperature,
Drying time is preferably 24 hours, and powder mix time is preferably 4-12 hours, preferably 6-10 hours, most preferably 8 hours,
Incorporation time influences the indium tin distribution consistency degree of ito powder and the electric conductivity of ito thin film.The present invention utilizes ball mill pair
It after mixed sediment is ground, is classified at 100um, classification is non-for ito powder particle size distribution before powder calcining
It is often important.
Mixed powder is calcined, ito powder is obtained.In this step d, calcination temperature is preferably 300-1100
DEG C, more preferably 300-900 DEG C, calcination time is preferably 3-12 hours, more preferably 9-10 hours.Calcination temperature directly affects
The grain size of ito powder, in the embodiment of the present invention, the specific surface area that different calcination temperatures obtain ito powder is distributed as
500-1200m2/ g, preferably temperature sintering, obtained ito powder crystal grain D90/50 are 3.5-4.0.
Distilled water, polycarboxylic acids base dispersing agent and wax class adhesive is added in the pistac ito powder obtained after sintering,
Abundant ball milling in ball mill, then drying and crushing is granulated, and is automatically controlled preferably by sponging granulator.In this step e, ITO slurry
In liquid, ito powder, distilled water, dispersing agent, adhesive weight ratio most preferably 100：85：0.5：1, Ball-milling Time is preferably
8-24 hours, it was preferably 60-80um that then mist projection granulating, which obtains ito powder agglomerated particle,.Most preferably Ball-milling Time can pass through
Slurry viscosity obtains, and slurry viscosity is preferably smaller than 500cps.
Ito powder particle is put into pre-pressing die pre-molding, then the embryo material after going out precompressed in mold, is put into corresponding
In plastics gum cover, ITO sintering raw embryo is pressed into cold isostatic press.Pre-molding pressure time is 5 minutes in this step f, pressure
It is by force 30-250kg/cm2, more preferably 100-200kg/cm2, most preferably 150kg/cm2；Isostatic cool pressing pressure time is 2 points
Clock, pressure are preferably 150-300MPa, more preferably 180-250MPa, most preferably 220Mpa.
Pressed ITO raw embryo is put into debinding furnace, makes adhesive in raw embryo, dispersing agent and residual moisture removing, so
After be put into Low Pressure Oxygen atmosphere furnace and sinter ITO sintered body into, it is last machined to be shaped to ITO target.Skimming temp in this step g
Preferably 100-600 DEG C, degreasing time is preferably 80-100 hours, and Low Pressure Oxygen atmosphere calcining furnace pressure is preferably 1.1-1.5 big
Air pressure, flow are preferably 0.5-5L/m2/ minute, calcination temperature are preferably 300-1600 DEG C, and calcination time is preferably 36-48 small
When.Calcination atmosphere of the present invention is oxygen, can improve ITO target density and oxygen content by a relatively large margin, and this target preparation ITO is thin
The electric conductivity of film is high.
According to the present invention, it is 2.0-5.0 that the sub- diameter of the crystallization of the ito powder obtained after calcining, which is D90/D50, it is preferred that is forged
The sub- diameter of the crystallization of the ito powder obtained after burning is that D90/D50 is controllable to 3.5, and powder diameter is evenly distributed, favorable dispersibility,
Sintered ITO sintered density is high, and high oxygen content conducts electricity very well.
The sub- diameter of the crystallization of ito powder in the present invention is measured with TEM, and size distribution is measured with laser particle analyzer, specific surface
Product is measured with specific-surface area detection instrument；The scanning electron microscope Observe and measure of the crystallite dimension in sintered body in the present invention,
For specific instrument model without particular requirement, typical microstructure is as shown in Figure 1.
Embodiment 1：
By 1500g high pure metal indium (purity is not less than 99.999%), under the covering of glycerol, dissolves, lead at 200 DEG C
The stainless steel nozzle stream for crossing 2mm diameter drops in recirculated cooling water, obtains 2mm indium grain, takes out drying；
Granular indium gold is equipped in the reaction kettle that 6000mL mass concentration is 65wt% nitric acid with being added, controls solution temperature
It is 100 DEG C, dissolution time is 24 hours, and solution ph is 0.8 after adjusting reaction；Then the ammonia of 28wt% is added dropwise into reaction kettle
Water, while adjusting blender 200rpm and starting to stir, 50 DEG C of reaction temperature or so are controlled, ammonium hydroxide is adjusted after reaction and is added,
It controls pH value to stopping after 7 and ammonium hydroxide is added, after persistently stirring 2 hours, stand aging 18 hours；White depositions are taken out, with steaming
Distilled water is dry after being cleaned multiple times, and crushes powdering.
500g is analyzed pure stannic chloride pentahydrate to be dissolved in 4000ml distilled water, is then added dropwise 26wt%'s into reaction kettle
Ammonium hydroxide, while adjusting blender 240rpm and starting to stir, 40 DEG C of reaction temperature or so are controlled, ammonium hydroxide is adjusted after reaction and adds
Enter, stop that ammonium hydroxide is added after control pH value to 8, after persistently stirring 2 hours, stands aging 18 hours；White depositions are taken out, are used
Distilled water is dry after being cleaned multiple times, and crushes powdering.Cl is remained in detection cleaning raffinate-When concentration is less than 10ppm, illustrate to precipitate
Object cleans up.
2148.93g indium hydroxide powder and 247.64g indium hydroxide powder are weighed, is put into ball mill, is ground 8 hours
Afterwards, it is sieved with 100mesh sieve.
Powder is put into Low Pressure Oxygen atmosphere calcining furnace, is calcined in 900 DEG C and obtains yellow green ito powder in 6 hours, weighs and is
1998.5g.The ito powder of preparation is detected, as a result as shown in the table：
| Test item | BET | Average grain diameter | D50 | D90 | Crystallinity |
| Unit | M2/g | um | um | um | -- |
| Numerical value | 8.1 | 3.8 | 1.8 | 4.5 | C |
1000gITO powder is weighed, in proportion 100：85：0.5：1 is added 174g distilled water, 7.5g polycarboxylate dispersant
D305 and 8.5g wax class adhesive WF804, mixing and ball milling 24 hours in the ball mill, until slurry viscosity is less than 500cps, then
Mist projection granulating obtains the ito powder particle of 74um.
50gITO powder particle is weighed, is put into the cylindrical die of diameter 40mm, with 120kg/cm2Pressure precompressed 5
Minute, it is packed into thin gum cover after taking-up, then in cold isostatic press, is taken out after being suppressed 2 minutes with the pressure of 250MPa, places drying
Then place makes 4 pieces of sample again with same precompressed and suppression process.
Will compacting obtain 4 pieces of ITO compacting raw embryo be put into debinding furnace, 600 DEG C degreasing 80 hours；It is then placed in low pressure
In oxygen atmosphere furnace, 1500 DEG C are calcined 46 hours, 1.1 atmospheric pressure of furnace pressure, oxygen flow 1.5L/m2/min。
The property of the ITO sintered body of above-mentioned preparation is detected, as a result as shown in the table：
Embodiment 2：
By 1500g high pure metal indium (purity is not less than 99.999%), under the covering of glycerol, dissolves, lead at 185 DEG C
The stainless steel nozzle stream for crossing 2mm diameter drops in recirculated cooling water, obtains 3mm indium grain, takes out drying；
Granular indium gold is equipped in the reaction kettle that 6000mL mass concentration is 70wt% nitric acid with being added, controls solution temperature
It is 85 DEG C, dissolution time is 24 hours, and solution ph is 0.7 after adjusting reaction；Then the ammonia of 28wt% is added dropwise into reaction kettle
Water, while adjusting blender 200rpm and starting to stir, 50 DEG C of reaction temperature or so are controlled, ammonium hydroxide is adjusted after reaction and is added,
It controls pH value to stopping after 7 and ammonium hydroxide is added, after persistently stirring 2 hours, stand aging 26 hours；White depositions are taken out, with steaming
Distilled water is dry after being cleaned multiple times, and crushes powdering.
500g is analyzed pure stannic chloride pentahydrate to be dissolved in 4000ml distilled water, is then added dropwise 28wt%'s into reaction kettle
Ammonium hydroxide, while adjusting blender 240rpm and starting to stir, 40 DEG C of reaction temperature or so are controlled, ammonium hydroxide is adjusted after reaction and adds
Enter, stop that ammonium hydroxide is added after control pH value to 8, after persistently stirring 2 hours, stands aging 24 hours；White depositions are taken out, are used
Distilled water is dry after being cleaned multiple times, and crushes powdering.Cl is remained in detection cleaning raffinate-When concentration is less than 10ppm, illustrate to precipitate
Object cleans up.
2265.75g indium hydroxide powder and 252.31g indium hydroxide powder are weighed, is put into ball mill, is ground 8 hours
Afterwards, it is sieved with 100mesh sieve.
Powder is put into Low Pressure Oxygen atmosphere calcining furnace, is calcined in 800 DEG C and obtains yellow green ito powder in 10 hours, weighs and is
2049.9g.The ito powder of preparation is detected, as a result as shown in the table：
| Test item | BET | Average grain diameter | D50 | D90 | Crystallinity |
| Unit | M2/g | um | um | um | -- |
| Numerical value | 8.1 | 3.5 | 1.6 | 4.2 | C |
1000gITO powder is weighed, in proportion 100：85：0.5：1 is added 181g distilled water, 6.9g polycarboxylate dispersant
D305 and 7.6g wax class adhesive WF804, mixing and ball milling 24 hours in the ball mill, until slurry viscosity is less than 500cps, then
Mist projection granulating obtains the ito powder particle of 64um.
50gITO powder particle is weighed, is put into the cylindrical die of diameter 40mm, with 150kg/cm2Pressure precompressed 5
Minute, it is packed into thin gum cover after taking-up, then in cold isostatic press, is taken out after being suppressed 2 minutes with the pressure of 220MPa, places drying
Then place makes 4 pieces of sample again with same precompressed and suppression process.
Will compacting obtain 4 pieces of ITO compacting raw embryo be put into debinding furnace, 600 DEG C degreasing 90 hours；It is then placed in low pressure
In oxygen atmosphere furnace, 1600 DEG C are calcined 40 hours, 1.3 atmospheric pressure of furnace pressure, oxygen flow 2.3L/m2/min。
The property of the ITO sintered body of above-mentioned preparation is detected, as a result as shown in the table：
Embodiment 3：
By 1500g high pure metal indium (purity is not less than 99.999%), under the covering of glycerol, dissolves, lead at 175 DEG C
The stainless steel nozzle stream for crossing 2mm diameter drops in recirculated cooling water, obtains 4mm indium grain, takes out drying；
Granular indium gold is equipped in the reaction kettle that 6000mL mass concentration is 60wt% nitric acid with being added, controls solution temperature
It is 110 DEG C, dissolution time is 24 hours, and solution ph is 1 after adjusting reaction；Then the ammonia of 25wt% is added dropwise into reaction kettle
Water, while adjusting blender 200rpm and starting to stir, 80 DEG C of reaction temperature or so are controlled, ammonium hydroxide is adjusted after reaction and is added,
It controls pH value to stopping after 8 and ammonium hydroxide is added, after persistently stirring 2 hours, stand aging 30 hours；White depositions are taken out, with steaming
Distilled water is dry after being cleaned multiple times, and crushes powdering.
500g is analyzed pure stannic chloride pentahydrate to be dissolved in 4000ml distilled water, is then added dropwise 25wt%'s into reaction kettle
Ammonium hydroxide, while adjusting blender 240rpm and starting to stir, 40 DEG C of reaction temperature or so are controlled, ammonium hydroxide is adjusted after reaction and adds
Enter, stop that ammonium hydroxide is added after control pH value to 8, after persistently stirring 2 hours, stands aging 30 hours；White depositions are taken out, are used
Distilled water is dry after being cleaned multiple times, and crushes powdering.Cl is remained in detection cleaning raffinate-When concentration is less than 10ppm, illustrate to precipitate
Object cleans up.
2134.47g indium hydroxide powder and 240.71g indium hydroxide powder are weighed, is put into ball mill, is ground 8 hours
Afterwards, it is sieved with 100mesh sieve.
Powder is put into Low Pressure Oxygen atmosphere calcining furnace, is calcined in 500 DEG C and obtains yellow green ito powder in 8 hours, weighs and is
1987.9g.The ito powder of preparation is detected, as a result as shown in the table：
| Test item | BET | Average grain diameter | D50 | D90 | Crystallinity |
| Unit | M2/g | um | um | um | -- |
| Numerical value | 8.2 | 3.7 | 1.9 | 4.4 | C |
1000gITO powder is weighed, in proportion 100：85：0.5：1 is added 189g distilled water, 9.6g polycarboxylate dispersant
D305 and 6.8g wax class adhesive WF804, mixing and ball milling 12 hours in the ball mill, until slurry viscosity is less than 500cps, then
Mist projection granulating obtains the ito powder particle of 74um.
50gITO powder particle is weighed, is put into the cylindrical die of diameter 40mm, with 180kg/cm2Pressure precompressed 5
Minute, it is packed into thin gum cover after taking-up, then in cold isostatic press, is taken out after being suppressed 2 minutes with the pressure of 280MPa.Place drying
Place.Then 4 pieces of sample are being made with same precompressed and suppression process.
Will compacting obtain 4 pieces of ITO compacting raw embryo be put into debinding furnace, 300 DEG C degreasing 85 hours；It is then placed in low pressure
In oxygen atmosphere furnace, 1400 DEG C are calcined 48 hours, 1.4 atmospheric pressure of furnace pressure, oxygen flow 3L/m2/min。
The property of the ITO sintered body of above-mentioned preparation is detected, as a result as shown in the table：
The embodiments described above only express several embodiments of the present invention, and the description thereof is more specific and detailed, but simultaneously
It cannot therefore be construed as limiting the scope of the patent.It should be pointed out that coming for those of ordinary skill in the art
It says, without departing from the inventive concept of the premise, various modifications and improvements can be made, these belong to protection of the invention
Range.
Claims (9)
1. a kind of preparation method of high-density ITO targe material, which is characterized in that include the following steps：
A. indium grain is mixed with nitric acid, mixed solution is obtained after reaction, ammonium hydroxide is added into solution, reaction obtains white depositions
Indium hydroxide, by indium hydroxide aging, filtering, cleaning, drying；
B. tin tetrachloride solution and ammonium hydroxide are reacted, obtains flocky precipitate stannic hydroxide, by stannic hydroxide aging, filtering, clearly
It washes, dry；
C. both the above sediment is mixed, by indium hydroxide：The mass ratio 9 of stannic hydroxide：1, cleaning, is fully ground drying
Mixing；
D. ito powder will be obtained after the powder calcining after grinding；
E. slurries will be obtained after ito powder, distilled water, polycarboxylic acid dispersant, wax based adhesive mixed grinding, gained slurries are used
Spray drying process is dry；
F. the ito powder after drying is packed into mold pre-molding, is then pressed into ITO target embryo material with cold isostatic press again；
G. degreasing removes dispersing agent, adhesive in above-mentioned embryo material, and ITO sintering is then sintered into Low Pressure Oxygen atmosphere calcining furnace
Body obtains ITO target after machining.
2. the preparation method of high-density ITO targe material according to claim 1, which is characterized in that in step a, the indium grain
It is prepared using following methods：Surface is had to the indium metal block of glycerol, it is cooling after being dissolved at 150-230 DEG C, pass through 2mm diameter
Stainless steel nozzle drop in circulating cooling distilled water, obtain indium grain.
3. the preparation method of high-density ITO targe material according to claim 1, which is characterized in that in the step a, indium grain
Diameter is 2-5mm, and the concentration of nitric acid is 50-70wt%, and the reaction temperature for dissolving indium is 50-110 DEG C, and the reaction time is 24 hours,
Ammonia concn is 20-28wt%, and neutralization-precipitation reaction and ageing time are 18-32 hours.
4. the preparation method of high-density ITO targe material according to claim 1, which is characterized in that in the step b, tetrachloro
The concentration for changing tin ion in solution of tin is 20g/L-60g/L, and the concentration of ammonium hydroxide is 20wt%-28wt%, and stannic hydroxide precipitating is molten
For the pH value of liquid in 7-10, reaction and ageing time are 12-36 hours.
5. the preparation method of high-density ITO targe material according to claim 1, which is characterized in that cleaned in the step c
Afterwards, chloride ion content is less than 80-10ppm in raffinate, and drying time is 24 hours, mixed grinding 4-8 hours.
6. the preparation method of high-density ITO targe material according to claim 1, which is characterized in that in the step d, calcining
Temperature is 300-1100 DEG C, and calcination time is 3-12 hours.
7. the preparation method of high-density ITO targe material according to claim 1, which is characterized in that in the step e, ITO slurry
In liquid, ito powder, distilled water, polycarboxylic acid dispersant, wax based adhesive weight ratio 100：85：0.5：1.
8. the preparation method of high-density ITO targe material according to claim 1, which is characterized in that be pressed into advance in the step f
Type pressure is 30-250kg/cm2, and isostatic cool pressing pressure is 150-300MPa.
9. the preparation method of high-density ITO targe material according to claim 1, which is characterized in that degreasing temperature in the step g
Degree be 100-600 DEG C, degreasing time 80-100 hours, Low Pressure Oxygen atmosphere calcining furnace 1.1-1.5 atmospheric pressure of pressure, flow 0.5-
5L/m2/ minutes, 300-1600 DEG C of calcination temperature, calcination time was 36-48 hours.
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| CN112521164A (en) * | 2020-12-15 | 2021-03-19 | 株洲火炬安泰新材料有限公司 | Process for preparing ITO powder |
| CN112626342A (en) * | 2020-12-15 | 2021-04-09 | 株洲火炬安泰新材料有限公司 | Method for reproducing ITO powder by using ITO waste target |
| WO2021169418A1 (en) * | 2020-02-25 | 2021-09-02 | 基迈克材料科技（苏州）有限公司 | Itio rotary target and preparation method therefor |
| CN113697848A (en) * | 2021-07-13 | 2021-11-26 | 芜湖映日科技股份有限公司 | Method for manufacturing tin oxide powder of ITO target material |
| CN113800900A (en) * | 2021-08-17 | 2021-12-17 | 芜湖映日科技股份有限公司 | Method for processing high-density ITO target material powder |
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