A kind of method of the sintering integrated formula production ITO target of degreasing-
Technical field
The present invention relates to a kind of methods of the sintering integrated formula production ITO target of degreasing-.
Background technique
ITO target is the sintered body of N-type oxide semiconductor tin indium oxide, is the critical material for preparing ito thin film.With
ITO target has excellent translucency and electric conductivity, and excellent machining performance, hardness by the ito thin film that magnetron sputtering obtains
High, wear-and corrosion-resistant, shows (LCD), solar battery, automobile solar heat protection antifog glass etc. in thin film transistor (TFT) (TFT), flat panel Liquid Crystal
Field is widely applied.
ITO target requires to carry out the densification of ITO target blankss in process of production, and the ITO target finally obtained just has height
Consistency.Prior art be all mostly by target carry out degreasing and sintering come realize ITO target blankss densify, and degreasing and
Sintering is separated and independently performed, and there are following both sides disadvantages:1) time-consuming, production efficiency is low:Need the target that will first handle well
Base is carried into debinding furnace and carries out heating degreasing (about 2 days), after degreasing furnace temperature drops to room temperature from degreasing operating temperature (at least
4 days), then target blankss are transported to sintering furnace from debinding furnace and are sintered (about 5 days);2) yield rate is low:Target blankss are after degreasing
Mechanical strength substantially reduces, and is easy in temperature-fall period to crack because uneven heating is even, and target blankss are transported to sintering from debinding furnace
It is also easy to be shaken and crack during furnace.Such as:CN 105712703A discloses a kind of high-purity high-density degree ITO target
Preparation method is first spray-dried ito powder, is granulated, being molded precompressed and cold isostatic compaction obtains target blankss, then by target blankss
It is transferred to debinding furnace and carries out degreasing, then target blankss are transferred to sintering furnace and are sintered, degreasing and be sintered to independent two successive
It is easy to that vibration cracking occurs during process flow, time-consuming for process flow, and target blankss are transferred to sintering furnace from debinding furnace.
In addition, also there is researcher not add binder straight forming preparation target blankss in ito powder, it is intended to simplified technique,
Shorten the time of ITO target blankss densification, reduce breakage caused by the transfer of ITO target blankss.Such as:102173817 A of CN discloses one
The preparation method of kind ITO target, directly forms ito powder, is cold-pressed to obtain target blankss, binder is not added, so being not required to
Target blankss are carried out with degreasing, direct sintering, but since ito powder plasticity is low, target blankss are easy to appear layering or cracking etc. and lack
It falls into, yield rate is low.
Summary of the invention
The purpose of the present invention is to provide a kind of methods of the sintering integrated formula production ITO target of degreasing-.
The technical solution adopted by the present invention is that:
A kind of method of the sintering integrated formula production ITO target of degreasing-, includes the following steps:
1) ITO powder, dispersing agent and water are mixed, carry out ball milling, add binder, carry out ultrasound and vacuum defoamation,
Obtain slurry;
2) slurry is injected into mold, is formed, obtain target blankss, demoulded, target blankss are dried;
3) target blankss are placed on the load bearing board in the sintering integrated formula furnace of degreasing-, are densified, concrete operations are:
A) 100~200 DEG C are raised to from room temperature with the rate of 0.15~0.5 DEG C/min, at the same be passed through flow be 100~
The dry air of 300L/min;
B) 350~400 DEG C are raised to the rate of 0.2~0.4 DEG C/min, keep the temperature 2~4h, at the same be passed through flow be 100~
The dry air of 300L/min;
C) 500~700 DEG C are raised to the rate of 1~3 DEG C/min, keep the temperature 1~3h, while being passed through flow is 100~300L/
The dry air of min;
D) 900~1100 DEG C are raised to the rate of 2~3 DEG C/min, keep the temperature 1~2h, at the same be passed through flow be 300~
The oxygen of 800L/min, oxygen pressure is normal pressure in furnace;
E) 1180~1400 DEG C are raised to the rate of 1~3 DEG C/min, keep the temperature 1~2h, at the same be passed through flow be 300~
The oxygen of 800L/min, oxygen pressure is normal pressure in furnace;
F) 1400~1500 DEG C are raised to the rate of 1.5~2.5 DEG C/min, while being passed through flow is 300~800L/min
Oxygen, oxygen pressure is normal pressure in furnace;
G) 1500~1700 DEG C are raised to the rate of 6~8 DEG C/min, keep the temperature 4~20h, at the same be passed through flow be 300~
The oxygen of 800L/min, oxygen pressure is normal pressure in furnace;
H) 1300~1500 DEG C are dropped to the rate of 1~2 DEG C/min, keep the temperature 1~3h, at the same be passed through flow be 300~
The oxygen of 800L/min, oxygen pressure is normal pressure in furnace;
I) 1100~1300 DEG C are dropped to the rate of 0.5~3 DEG C/min, while being passed through flow is 300~800L/min's
Oxygen, oxygen pressure is normal pressure in furnace;
J) 900~1100 DEG C are dropped to the rate of 0.3~0.5 DEG C/min, keep the temperature 1~2h, at the same be passed through flow be 0~
The oxygen of 300L/min, oxygen pressure is normal pressure in furnace;
K) room temperature is dropped to the rate of 0.1~0.5 DEG C/min, obtains ITO target.
The additive amount of the step 1) dispersing agent is the 0.1%~2.2% of ITO powder quality.
The additive amount of the step 1) water is the 30%~45% of ITO powder quality.
The additive amount of the step 1) binder is the 0.1%~2.1% of ITO powder quality.
The partial size of step 1) the ITO powder is 20~300nm.
Step 1) the dispersing agent is at least one of polycarboxylic acid dispersant, polyacrylic dispersing agent.
Step 1) the binder is at least one of acrylic resin, polyvinyl alcohol.
Step 2) the mold is one of gypsum mold, resin die.
Step 2) the molding concrete operations are:Slurry is injected into mold, control grouting pressure is 0.1~0.3MPa,
3~5h of pressure maintaining.
The temperature of the step 2) drying is 20~80 DEG C, and drying time is 10~48h.
Step 3) the degreasing-sintering integrated formula furnace bottom side is provided with venthole, and top is provided with gas vent.
The gap for discharging stress in process of expansion and contraction is provided on the step 3) load bearing board.
The beneficial effects of the invention are as follows:The present invention is during carrying out target blankss densification, by target blankss from the highest of degreasing
Temperature, which directly heats up, carries out the higher sintering of temperature, cooling after target blankss degreasing is omitted, transfer and temperature-rise period again, degreasing and
The efficiency of sintering significantly improves, and eliminate target blankss shifted between debinding furnace and sintering furnace and caused by cracking, improve life
Benefit is produced, the mass production of ITO target is conducive to.
Specific embodiment
A kind of method of the sintering integrated formula production ITO target of degreasing-, includes the following steps:
1) ITO powder, dispersing agent and water are mixed, carry out ball milling, add binder, carry out ultrasound and vacuum defoamation,
Obtain slurry;
2) slurry is injected into mold, is formed, obtain target blankss, demoulded, target blankss are dried;
3) target blankss are placed on the load bearing board in the sintering integrated formula furnace of degreasing-, are densified, concrete operations are:
A) 100~200 DEG C are raised to from room temperature with the rate of 0.15~0.5 DEG C/min, at the same be passed through flow be 100~
The dry air of 300L/min;
B) 350~400 DEG C are raised to the rate of 0.2~0.4 DEG C/min, keep the temperature 2~4h, at the same be passed through flow be 100~
The dry air of 300L/min;
C) 500~700 DEG C are raised to the rate of 1~3 DEG C/min, keep the temperature 1~3h, while being passed through flow is 100~300L/
The dry air of min;
D) 900~1100 DEG C are raised to the rate of 2~3 DEG C/min, keep the temperature 1~2h, at the same be passed through flow be 300~
The oxygen of 800L/min, oxygen pressure is normal pressure in furnace;
E) 1180~1400 DEG C are raised to the rate of 1~3 DEG C/min, keep the temperature 1~2h, at the same be passed through flow be 300~
The oxygen of 800L/min, oxygen pressure is normal pressure in furnace;
F) 1400~1500 DEG C are raised to the rate of 1.5~2.5 DEG C/min, while being passed through flow is 300~800L/min
Oxygen, oxygen pressure is normal pressure in furnace;
G) 1500~1700 DEG C are raised to the rate of 6~8 DEG C/min, keep the temperature 4~20h, at the same be passed through flow be 300~
The oxygen of 800L/min, oxygen pressure is normal pressure in furnace;
H) 1300~1500 DEG C are dropped to the rate of 1~2 DEG C/min, keep the temperature 1~3h, at the same be passed through flow be 300~
The oxygen of 800L/min, oxygen pressure is normal pressure in furnace;
I) 1100~1300 DEG C are dropped to the rate of 0.5~3 DEG C/min, while being passed through flow is 300~800L/min's
Oxygen, oxygen pressure is normal pressure in furnace;
J) 900~1100 DEG C are dropped to the rate of 0.3~0.5 DEG C/min, keep the temperature 1~2h, at the same be passed through flow be 0~
The oxygen of 300L/min, oxygen pressure is normal pressure in furnace;
K) room temperature is dropped to the rate of 0.1~0.5 DEG C/min, obtains ITO target.
Preferably, the additive amount of the step 1) dispersing agent is the 0.1%~2.2% of ITO powder quality.
Preferably, the additive amount of the step 1) water is the 30%~45% of ITO powder quality.
Preferably, the additive amount of the step 1) binder is the 0.1%~2.1% of ITO powder quality.
Preferably, the partial size of step 1) the ITO powder is 20~300nm.
Preferably, the step 1) dispersing agent is at least one of polycarboxylic acid dispersant, polyacrylic dispersing agent.
Preferably, the step 1) binder is at least one of acrylic resin, polyvinyl alcohol.
Preferably, the step 2) mold is one of gypsum mold, resin die.
Preferably, step 2) the molding concrete operations are:Slurry is injected into mold, control grouting pressure is 0.1~
0.3MPa, 3~5h of pressure maintaining.
Preferably, the temperature of the step 2) drying is 20~80 DEG C, and drying time is 10~48h.
Preferably, the step 3) degreasing-sintering integrated formula furnace bottom side is provided with venthole, and top is provided with exhaust
Hole.
Preferably, the gap for discharging stress in process of expansion and contraction is provided on the step 3) load bearing board.
The present invention will be further explained combined with specific embodiments below and explanation.
Embodiment 1:
A kind of method of the sintering integrated formula production ITO target of degreasing-, includes the following steps:
1) by the ITO powder of 100 mass parts (70~100nm of partial size), the polycarboxylic acid dispersant of 0.5 mass parts and 45 matter
The deionized water mixing of part is measured, ball milling 20h adds the acrylic resin of 0.5 mass parts, carries out ultrasound and vacuum defoamation, obtain
To slurry;
2) slurry being injected into graphite mold, control grouting pressure is 0.23MPa, and pressure maintaining 5h obtains target blankss, it demoulds,
Target blankss are placed at 60 DEG C dry 20h again;
3) target blankss are placed on the load bearing board in the sintering integrated formula furnace of degreasing-, are densified, concrete operations are:
A) 160 DEG C are raised to from room temperature with the rate of 0.18 DEG C/min, while are passed through the dry air that flow is 200L/min;
B) 350 DEG C are raised to the rate of 0.3 DEG C/min, keep the temperature 2h, while being passed through the dry air that flow is 200L/min;
C) 700 DEG C are raised to the rate of 2.5 DEG C/min, keep the temperature 1h, while being passed through the dry air that flow is 200L/min;
D) 1050 DEG C are raised to the rate of 2 DEG C/min, keep the temperature 2h, while being passed through the oxygen that flow is 600L/min, in furnace
Oxygen pressure is normal pressure;
E) 1350 DEG C are raised to the rate of 1 DEG C/min, keep the temperature 1h, while being passed through the oxygen that flow is 600L/min, in furnace
Oxygen pressure is normal pressure;
F) 1480 DEG C are raised to the rate of 2 DEG C/min, while are passed through the oxygen that flow is 600L/min, oxygen pressure in furnace
For normal pressure;
G) 1550 DEG C are raised to the rate of 6 DEG C/min, keep the temperature 8h, while being passed through the oxygen that flow is 600L/min, in furnace
Oxygen pressure is normal pressure;
H) 1300 DEG C are dropped to the rate of 1 DEG C/min, keeps the temperature 3h, while being passed through the oxygen that flow is 600L/min, in furnace
Oxygen pressure is normal pressure;
I) 1125 DEG C are dropped to the rate of 3 DEG C/min, while is passed through the oxygen that flow is 600L/min, oxygen pressure in furnace
For normal pressure;
J) 900 DEG C are dropped to the rate of 0.5 DEG C/min, keeps the temperature 2h, while being passed through the oxygen that flow is 100L/min, in furnace
Oxygen pressure is normal pressure;
K) room temperature is dropped to the rate of 0.5 DEG C/min, obtains ITO target (long 600mm, width 350mm, thickness 10mm).
After tested, the density of ITO target is 7.135g/cm3, purity 99.99%, crystal size is 2~3.5 μm, brilliant
Body it is of uniform size.
Embodiment 2:
A kind of method of the sintering integrated formula production ITO target of degreasing-, includes the following steps:
1) by the ITO powder of 100 mass parts (70~100nm of partial size), the polycarboxylic acid dispersant of 1 mass parts and 40 mass
The deionized water mixing of part, ball milling 20h add the acrylic resin of 0.5 mass parts, carry out ultrasound and vacuum defoamation, obtain
Slurry;
2) slurry being injected into graphite mold, control grouting pressure is 0.23MPa, and pressure maintaining 5h obtains target blankss, it demoulds,
Target blankss are placed at 50 DEG C dry 25h again;
3) target blankss are placed on the load bearing board in the sintering integrated formula furnace of degreasing-, are densified, concrete operations are:
A) 120 DEG C are raised to from room temperature with the rate of 0.18 DEG C/min, while are passed through the dry air that flow is 200L/min;
B) 350 DEG C are raised to the rate of 0.2 DEG C/min, keep the temperature 2h, while being passed through the dry air that flow is 200L/min;
C) 600 DEG C are raised to the rate of 2.5 DEG C/min, keep the temperature 1h, while being passed through the dry air that flow is 200L/min;
D) 1050 DEG C are raised to the rate of 2 DEG C/min, keep the temperature 2h, while being passed through the oxygen that flow is 600L/min, in furnace
Oxygen pressure is normal pressure;
E) 1350 DEG C are raised to the rate of 1 DEG C/min, keep the temperature 2h, while being passed through the oxygen that flow is 600L/min, in furnace
Oxygen pressure is normal pressure;
F) 1480 DEG C are raised to the rate of 2.5 DEG C/min, while are passed through the oxygen that flow is 600L/min, oxygen pressure in furnace
Power is normal pressure;
G) 1550 DEG C are raised to the rate of 6 DEG C/min, keep the temperature 8h, while being passed through the oxygen that flow is 600L/min, in furnace
Oxygen pressure is normal pressure;
H) 1330 DEG C are dropped to the rate of 1 DEG C/min, keeps the temperature 3h, while being passed through the oxygen that flow is 600L/min, in furnace
Oxygen pressure is normal pressure;
I) 1150 DEG C are dropped to the rate of 2 DEG C/min, while is passed through the oxygen that flow is 600L/min, oxygen pressure in furnace
For normal pressure;
J) 900 DEG C are dropped to the rate of 0.5 DEG C/min, keeps the temperature 2h, while being passed through the oxygen that flow is 100L/min, in furnace
Oxygen pressure is normal pressure;
K) room temperature is dropped to the rate of 0.4 DEG C/min, obtains ITO target (long 600mm, width 350mm, thickness 10mm).
After tested, the density of ITO target is 7.145g/cm3, purity 99.99%, crystal size is 2.5~4 μm, brilliant
Body it is of uniform size.
Embodiment 3:
A kind of method of the sintering integrated formula production ITO target of degreasing-, includes the following steps:
1) by the ITO powder of 100 mass parts (70~100nm of partial size), the polycarboxylic acid dispersant of 1.5 mass parts and 35 matter
The deionized water mixing of part is measured, ball milling 28h adds the acrylic resin of 0.5 mass parts, carries out ultrasound and vacuum defoamation, obtain
To slurry;
2) slurry being injected into graphite mold, control grouting pressure is 0.23MPa, and pressure maintaining 4h obtains target blankss, it demoulds,
Target blankss are placed at 50 DEG C dry 20h again;
3) target blankss are placed on the load bearing board in the sintering integrated formula furnace of degreasing-, are densified, concrete operations are:
A) 150 DEG C are raised to from room temperature with the rate of 0.15 DEG C/min, while are passed through the dry air that flow is 250L/min;
B) 380 DEG C are raised to the rate of 0.2 DEG C/min, keep the temperature 2h, while being passed through the dry air that flow is 250L/min;
C) 700 DEG C are raised to the rate of 2.5 DEG C/min, keep the temperature 1h, while being passed through the dry air that flow is 250L/min;
D) 1050 DEG C are raised to the rate of 2 DEG C/min, keep the temperature 2h, while being passed through the oxygen that flow is 500L/min, in furnace
Oxygen pressure is normal pressure;
E) 1350 DEG C are raised to the rate of 1 DEG C/min, keep the temperature 1h, while being passed through the oxygen that flow is 500L/min, in furnace
Oxygen pressure is normal pressure;
F) 1400 DEG C are raised to the rate of 2.5 DEG C/min, while are passed through the oxygen that flow is 500L/min, oxygen pressure in furnace
Power is normal pressure;
G) 1600 DEG C are raised to the rate of 6 DEG C/min, keep the temperature 10h, while being passed through the oxygen that flow is 500L/min, in furnace
Oxygen pressure is normal pressure;
H) 1400 DEG C are dropped to the rate of 1 DEG C/min, keeps the temperature 3h, while being passed through the oxygen that flow is 500L/min, in furnace
Oxygen pressure is normal pressure;
I) 1300 DEG C are dropped to the rate of 2 DEG C/min, while is passed through the oxygen that flow is 500L/min, oxygen pressure in furnace
For normal pressure;
J) 900 DEG C are dropped to the rate of 0.5 DEG C/min, keeps the temperature 2h, while being passed through the oxygen that flow is 100L/min, in furnace
Oxygen pressure is normal pressure;
K) room temperature is dropped to the rate of 0.5 DEG C/min, obtains ITO target (long 600mm, width 350mm, thickness 10mm).
After tested, the density of ITO target is 7.143g/cm3, purity 99.99%, crystal size is 2~3 μm, crystal
It is of uniform size.
Embodiment 4:
A kind of method of the sintering integrated formula production ITO target of degreasing-, includes the following steps:
1) by the ITO powder of 100 mass parts (70~100nm of partial size), the polycarboxylic acid dispersant of 2.2 mass parts and 30 matter
The deionized water mixing of part is measured, ball milling 28h adds the acrylic resin of 0.5 mass parts, carries out ultrasound and vacuum defoamation, obtain
To slurry;
2) slurry being injected into graphite mold, control grouting pressure is 0.23MPa, and pressure maintaining 4h obtains target blankss, it demoulds,
Target blankss are placed at 30 DEG C dry 40h again;
3) target blankss are placed on the load bearing board in the sintering integrated formula furnace of degreasing-, are densified, concrete operations are:
A) 150 DEG C are raised to from room temperature with the rate of 0.15 DEG C/min, while are passed through the dry air that flow is 250L/min;
B) 380 DEG C are raised to the rate of 0.2 DEG C/min, keep the temperature 2h, while being passed through the dry air that flow is 250L/min;
C) 700 DEG C are raised to the rate of 2.5 DEG C/min, keep the temperature 1h, while being passed through the dry air that flow is 250L/min;
D) 1050 DEG C are raised to the rate of 2 DEG C/min, keep the temperature 1h, while being passed through the oxygen that flow is 500L/min, in furnace
Oxygen pressure is normal pressure;
E) 1350 DEG C are raised to the rate of 1 DEG C/min, keep the temperature 2h, while being passed through the oxygen that flow is 500L/min, in furnace
Oxygen pressure is normal pressure;
F) 1400 DEG C are raised to the rate of 2.5 DEG C/min, while are passed through the oxygen that flow is 500L/min, oxygen pressure in furnace
Power is normal pressure;
G) 1600 DEG C are raised to the rate of 6 DEG C/min, keep the temperature 20h, while being passed through the oxygen that flow is 500L/min, in furnace
Oxygen pressure is normal pressure;
H) 1400 DEG C are dropped to the rate of 1 DEG C/min, keeps the temperature 3h, while being passed through the oxygen that flow is 500L/min, in furnace
Oxygen pressure is normal pressure;
I) 1300 DEG C are dropped to the rate of 2 DEG C/min, while is passed through the oxygen that flow is 500L/min, oxygen pressure in furnace
For normal pressure;
J) 900 DEG C are dropped to the rate of 0.5 DEG C/min, keeps the temperature 2h, while being passed through the oxygen that flow is 100L/min, in furnace
Oxygen pressure is normal pressure;
K) room temperature is dropped to the rate of 0.5 DEG C/min, obtains ITO target (long 600mm, width 350mm, thickness 10mm).
After tested, the density of ITO target is 7.140g/cm3, purity 99.99%, crystal size is 2~3 μm, crystal
It is of uniform size.
Embodiment 5:
A kind of method of the sintering integrated formula production ITO target of degreasing-, includes the following steps:
1) by the ITO powder of 100 mass parts (70~100nm of partial size), the polycarboxylic acid dispersant of 0.5 mass parts and 45 matter
The deionized water mixing of part is measured, ball milling 28h adds the acrylic resin of 0.5 mass parts, carries out ultrasound and vacuum defoamation, obtain
To slurry;
2) slurry being injected into graphite mold, control grouting pressure is 0.23MPa, and pressure maintaining 4h obtains target blankss, it demoulds,
Target blankss are placed at 60 DEG C dry 20h again;
3) target blankss are placed on the load bearing board in the sintering integrated formula furnace of degreasing-, are densified, concrete operations are:
A) 150 DEG C are raised to from room temperature with the rate of 0.15 DEG C/min, while are passed through the dry air that flow is 250L/min;
B) 380 DEG C are raised to the rate of 0.2 DEG C/min, keep the temperature 2h, while being passed through the dry air that flow is 250L/min;
C) 700 DEG C are raised to the rate of 2.5 DEG C/min, keep the temperature 1h, while being passed through the dry air that flow is 250L/min;
D) 1050 DEG C are raised to the rate of 2 DEG C/min, keep the temperature 1h, while being passed through the oxygen that flow is 500L/min, in furnace
Oxygen pressure is normal pressure;
E) 1300 DEG C are raised to the rate of 1 DEG C/min, keep the temperature 1h, while being passed through the oxygen that flow is 500L/min, in furnace
Oxygen pressure is normal pressure;
F) 1400 DEG C are raised to the rate of 2.5 DEG C/min, while are passed through the oxygen that flow is 500L/min, oxygen pressure in furnace
Power is normal pressure;
G) 1620 DEG C are raised to the rate of 6 DEG C/min, keep the temperature 20h, while being passed through the oxygen that flow is 500L/min, in furnace
Oxygen pressure is normal pressure;
H) 1400 DEG C are dropped to the rate of 1 DEG C/min, keeps the temperature 3h, while being passed through the oxygen that flow is 500L/min, in furnace
Oxygen pressure is normal pressure;
I) 1300 DEG C are dropped to the rate of 2 DEG C/min, while is passed through the oxygen that flow is 500L/min, oxygen pressure in furnace
For normal pressure;
J) 900 DEG C are dropped to the rate of 0.5 DEG C/min, keeps the temperature 2h, while being passed through the oxygen that flow is 100L/min, in furnace
Oxygen pressure is normal pressure;
K) room temperature is dropped to the rate of 0.5 DEG C/min, obtains ITO target (long 600mm, width 350mm, thickness 10mm).
After tested, the density of ITO target is 7.146g/cm3, purity 99.99%, crystal size is 2~3 μm, crystal
It is of uniform size.
The above embodiment is a preferred embodiment of the present invention, but embodiments of the present invention are not by above-described embodiment
Limitation, other any changes, modifications, substitutions, combinations, simplifications made without departing from the spirit and principles of the present invention,
It should be equivalent substitute mode, be included within the scope of the present invention.