CN109665834A - The controllable indium gallium zinc target and preparation method thereof of phase composition - Google Patents
The controllable indium gallium zinc target and preparation method thereof of phase composition Download PDFInfo
- Publication number
- CN109665834A CN109665834A CN201910156692.1A CN201910156692A CN109665834A CN 109665834 A CN109665834 A CN 109665834A CN 201910156692 A CN201910156692 A CN 201910156692A CN 109665834 A CN109665834 A CN 109665834A
- Authority
- CN
- China
- Prior art keywords
- target
- preparation
- controllable
- ball
- phase composition
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
Classifications
-
- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B35/00—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
- C04B35/01—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on oxide ceramics
- C04B35/453—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on oxide ceramics based on zinc, tin, or bismuth oxides or solid solutions thereof with other oxides, e.g. zincates, stannates or bismuthates
- C04B35/457—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on oxide ceramics based on zinc, tin, or bismuth oxides or solid solutions thereof with other oxides, e.g. zincates, stannates or bismuthates based on tin oxides or stannates
-
- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B35/00—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
- C04B35/622—Forming processes; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
-
- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B2235/00—Aspects relating to ceramic starting mixtures or sintered ceramic products
- C04B2235/02—Composition of constituents of the starting material or of secondary phases of the final product
- C04B2235/30—Constituents and secondary phases not being of a fibrous nature
- C04B2235/32—Metal oxides, mixed metal oxides, or oxide-forming salts thereof, e.g. carbonates, nitrates, (oxy)hydroxides, chlorides
- C04B2235/3286—Gallium oxides, gallates, indium oxides, indates, thallium oxides, thallates or oxide forming salts thereof, e.g. zinc gallate
-
- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B2235/00—Aspects relating to ceramic starting mixtures or sintered ceramic products
- C04B2235/02—Composition of constituents of the starting material or of secondary phases of the final product
- C04B2235/30—Constituents and secondary phases not being of a fibrous nature
- C04B2235/32—Metal oxides, mixed metal oxides, or oxide-forming salts thereof, e.g. carbonates, nitrates, (oxy)hydroxides, chlorides
- C04B2235/3293—Tin oxides, stannates or oxide forming salts thereof, e.g. indium tin oxide [ITO]
Abstract
The invention discloses a kind of indium gallium zinc targets and preparation method thereof that phase composition is controllable.Preparation method includes: indium oxide powder, gallium oxide powder, Zinc oxide powder according to the molar ratio mixing of setting, obtains mixed-powder；Mixed-powder is mixed with the dispersing agent of set amount, binder, ball-milling medium, using ball-milling device, is controlled ball milling parameter, is carried out ball milling mixing, obtain mixed material；Mixed material carries out mist projection granulating on pelletizer；The product compression molding that mist projection granulating obtains, obtains target biscuit；Target biscuit is sintered, and obtains the controllable IGZO target of phase composition.Pass through effective control to technological parameter in preparation process, the high-quality IGZO target that object is mutually single and object is mutually controllable is obtained according to material molar ratio, other miscellaneous phase ingredients are not contained in target, secondary phase constitution is not present in intercrystalline and inside, intercrystalline combines fine and close, target consistency is high, value of industrial utilization with higher.
Description
Technical field
The application belongs to metal oxide target material technical field, and in particular to a kind of indium gallium zinc that phase composition is controllable
Target and preparation method thereof.
Background technique
Indium gallium zinc oxide (Indium Gallium Zinc Oxide, abbreviation IGZO) or indium gallium zinc are a kind of
Novel semiconductor material is made of tetra- kinds of elements of In~Ga~Zn~O, and conduction type is N-shaped, and forbidden bandwidth is in 3.5eV
Left and right.IGZO thin-film material has many advantages, such as high mobility, relatively easy compared with extensive chemical stability and preparation process.Compared to
The most commonly used α~Si the material of thin film transistor (TFT) (TFT), the cloud density of metal ion is in ball under noncrystalline state in IGZO
It is symmetrical and insensitive to the variation in direction, so that IGZO material still maintains higher electronics under noncrystalline state and moves
Shifting rate, thus can the uniform application and preparation of large area at low temperature, both possess the picture much higher than traditional amorphous silicon (α~Si) panel
Face clarity in turn avoids the defects of polysilicon (LTPS) panel is difficult to large area production.In addition to this, IGZO~TFT is exclusive
High on-off ratio performance also superior to α~Si and LTPS, this point is most important for mobile display device.Therefore in electronics work
There is important role in the fields such as industry, become the strong candidate material of display technology of new generation.
IGZO~TFT is to have used IGZO film in its channel layer, and IGZO film is to be sintered ceramic target by IGZO to splash
Made of after penetrating, therefore there is higher requirement to the performance for the IGZO target that can be applied to sputtered film.Due to IGZO target category
In heterogeneous sintering, therefore easily occurs the phenomenon of component distributing unevenness during the sintering process.In addition, in sintering densification process
In, IGZO target might have a variety of phase constituents and generate, such as Ga2ZnO4、InGaZnO4、InGaZn3O6、InGaZn4O7、
InGaZn5O8、InGaZn6O9Deng, and include that the IGZO target targets of a variety of secondary phases can have a significant impact to the performance of film.
As the presence of the uneven and a variety of secondary phase of IGZO target material composition can seriously affect the ingredient and structure of its film, and then influence
To the performance of thin-film device, the application of IGZO target is hindered.So how to obtain the mutually controllable IGZO target of object as IGZO
Sputtering target material is able to widely apply and a difficult point needing to solve.
Summary of the invention
At least for one of problems described above, the present disclosure provides a kind of indium gallium zinc targets that phase composition is controllable
The preparation method of material, this method comprises:
(a) indium oxide powder, gallium oxide powder, Zinc oxide powder are mixed according to the molar ratio of setting, obtain mixed powder
End；
(b) dispersing agent of mixed-powder and set amount, binder, ball-milling medium carry out ball milling mixing using ball-milling device,
Obtain mixed material；
(c) mixed material carries out mist projection granulating on pelletizer；
(d) the product compression molding that mist projection granulating obtains, obtains target biscuit；
(e) target biscuit is sintered, and obtains the controllable indium gallium zinc target of phase composition.
The preparation method of the controllable indium gallium zinc target of phase composition disclosed in some embodiments of the invention, indium oxide powder
End, gallium oxide powder, Zinc oxide powder molar ratio be set as 1:1:m, wherein m be 1~8.
The preparation method of the controllable indium gallium zinc target of phase composition disclosed in some embodiments of the invention, indium oxide powder
Partial size be set as 50~200nm, the partial size of gallium oxide powder is set as 2~10 μm, and the partial size of Zinc oxide powder is set as 80
~200nm.
The preparation method of the controllable indium gallium zinc target of phase composition disclosed in some embodiments of the invention, the amount of dispersing agent
It is set as 0.3~2.0%, the amount of binder is set as 0.1~1%, and the amount of ball-milling medium is set as 50~60%.
The preparation method of the controllable indium gallium zinc target of phase composition disclosed in some embodiments of the invention, ball milling mixing
Process includes:
(b1) mixed-powder, part dispersing agent ball-milling medium are mixed, the time T1 that ball milling is set on ball mill；
(b2) part dispersing agent is added again, continues the time T2 of ball milling setting；
(b3) dispersing agent of remainder is added, continues the time T3 of ball milling setting；
(b4) binder is added, carries out the time T4 of ball milling setting.
Further, the preparation method of the controllable indium gallium zinc target of phase composition disclosed in some embodiments of the invention, ball
Mill mixing specifically includes:
(b1) mixed-powder, 0.1~1% dispersing agent, 50~60% ball-milling medium are mixed, the ball milling on ball mill
Time T1 be set as 24 hours；
(b2) 0.1~0.3% dispersing agent is added again, the time T2 for continuing ball milling is set as 24 hours；
(b3) dispersing agent of remainder is added, the time T3 for continuing ball milling is set as 1~3 hour；
(b4) binder is added, the time T4 for carrying out ball milling is set as 1~3 hour.
The preparation method of the controllable indium gallium zinc target of phase composition disclosed in some embodiments of the invention, mist projection granulating
In the process, prilling temperature is set as 180~210 DEG C, and charging rate is set as 5~15RPM.
The preparation method of the controllable indium gallium zinc target of phase composition disclosed in some embodiments of the invention, compression molding tool
Body includes:
(d1) product of mist projection granulating is molded under hydraulic press, and molding pressure is set as 25~100MPa, and the dwell time sets
It is set to 2~10min；
(d2) it demoulds, biscuit is coated with flexible die, is further suppressed in isostatic pressing machine, pressing pressure is set as
230~300MPa.
The preparation method of the controllable indium gallium zinc target of phase composition disclosed in some embodiments of the invention, target are sintered
Journey specifically includes:
(e1) target biscuit is put into sintering furnace, with the heating rate of 0.5~1 DEG C/min, is warming up to skimming temp 600
DEG C, make the complete degreasing of biscuit；
(e2) with the heating rate of 2~5 DEG C/min, 1300~1500 DEG C of sintering temperature is warming up to, is passed through in temperature-rise period
Oxygen keeps the temperature 6 hours under the sintering temperature；
(e3) stop heating, with the rate of temperature fall of 1~3 DEG C/min, be cooled to room temperature to get the oxidation controllable to phase composition
Indium gallium zinc target.
On the other hand, some embodiments of the invention also disclose a kind of indium gallium zinc target that phase composition is controllable, the target
Material is obtained by the preparation method of the controllable indium gallium zinc target of phase composition disclosed by the embodiments of the present invention.
Using the preparation method of the controllable indium gallium zinc target of phase composition ingredient disclosed by the embodiments of the present invention, by right
Effective control of technological parameter in preparation process can obtain the height that object is mutually single and object is mutually controllable by controlling material molar ratio
Quality indium gallium zinc target, does not contain other miscellaneous phase ingredients in target, intercrystalline and internal secondary phase constitution, crystal grain is not present
Between combine densification, target consistency is high, value of industrial utilization with higher.
Detailed description of the invention
The controllable indium gallium zinc target preparation method flow chart of Fig. 1 phase composition disclosed by the embodiments of the present invention；
The XRD diagram of indium gallium zinc target in Fig. 2 embodiment 1；
The scanning electron microscope (SEM) photograph of indium gallium zinc target in Fig. 3 embodiment 1.
Specific embodiment
Dedicated word " embodiment " herein, should not necessarily be construed as being better than as any embodiment illustrated by " exemplary " or
It is better than other embodiments.Testing performance index in this law embodiment, unless stated otherwise, using this field conventional methods.
It should be understood that it is to describe special embodiment that heretofore described term, which is only, it is not intended to limit disclosed by the invention
Content.
Unless otherwise stated, technical and scientific terms used herein has the common of the technical field of the invention
The normally understood identical meanings of technical staff；As other not specifically specified raw material, the reagent, test method in the present invention
The usually used raw material and reagent of those skilled in the art, and the experiment side generallyd use are referred both to technological means
Method and technological means；The chronomere that h is indicated is hour, and the chronomere that min is indicated is minute, the speed unit that RPM table shows
For rev/min, the content of dispersing agent, binder and ball-milling medium refers to the mass ratio of the component and mixed powder, such as
0.1~1% dispersing agent, the mass ratio of the quality and mixed powder that refer to dispersing agent are 0.1~1:100.
Term used in the disclosure " basic " and " about " are for describing small fluctuation.It is less than for example, they can refer to
Or be equal to ± 5%, such as less than or equal to ± 2%, such as less than or equal to ± 1%, such as less than or equal to ± 0.5%, such as less than or
Equal to ± 0.2%, such as less than or equal to ± 0.1%, such as less than or equal to ± 0.05%.Concentration, amount and other numeric datas exist
It can indicate or present with range format herein.Such range format only uses for convenience and for the sake of brief, therefore Ying Ling
Work is construed to not only include the numerical value clearly enumerated as the boundary of the range, further includes include all independent within the scope of this
Numerical value or subrange.For example, the numberical range of " 1% to 5% " should be construed to include 1% to 5% clearly enumerating
Value, further includes independent values in the range shown and subrange.It therefore, include independent values in this numberical range, such as 2%,
3.5% and 4% and subrange, such as 1%~3%, 2%~4% and 3%~5%.This principle is equally applicable to only enumerate
The range of one numerical value.In addition, width or the feature regardless of the range, such explanation is all suitable for.
In the disclosure, including claims, all conjunctions, as "comprising", " comprising ", " having ", " having ",
" containing ", " being related to ", " receiving " etc. are understood to be open, that is, refer to " including but not limited to ".Only conjunction
" by ... constitute " and " consist of " be closing conjunction.
Below in conjunction with the controllable IGZO target preparation method flow chart of specific embodiment and phase composition disclosed by the invention,
See Fig. 1, preparation method disclosed by the invention is further illustrated, so as to those skilled in the art's implementation.
In some embodiments, the preparation method of the controllable IGZO target of phase composition is carried out according to following process flow:
(a) indium oxide powder, gallium oxide powder, Zinc oxide powder are mixed according to the molar ratio of setting, obtain mixed powder
End；As some embodiments, indium oxide powder, gallium oxide powder, Zinc oxide powder molar ratio be set as 1:1:m, wherein m
It is 1~8；As other embodiment, the partial size of indium oxide powder is set as 50~200nm, and the partial size of gallium oxide powder is set
It is set to 2~10 μm, the partial size of Zinc oxide powder is set as 80~200nm；
(b) mixed-powder is mixed with the dispersing agent of set amount, binder, ball-milling medium, carries out ball milling using ball-milling device
Mixing, obtains mixed material；In some embodiments, the amount of dispersing agent is set as 0.3~2.0%, and the amount of binder is set as
0.1~1%, the amount of ball-milling medium is set as 50~60%；In some embodiments, ball milling mixing process specifically includes following step
Suddenly, (b1) mixes mixed-powder, 0.1~1% dispersing agent, 50~60% ball-milling medium, in ball milling T1 on ball mill
Between, such as T1 is set as 24 hours；(b2) 0.1~0.3% dispersing agent is added again, continues the ball milling T2 time, such as
T2 is set as 24 hours；(b3) dispersing agent of remainder is added, continues the ball milling T3 time, such as to be set as 1~3 small by T3
When；(b4) binder is added, carries out the ball milling T4 time, such as T4 is set as 1~3 hour；
(c) mixed material carries out mist projection granulating on pelletizer；For example, during mist projection granulating, prilling temperature setting
It is 180~210 DEG C, charging rate is set as 5~15RPM；
(d) the product compression molding that mist projection granulating obtains, obtains target biscuit；In some embodiments, compression molding tool
Body includes: that the product of (d1) mist projection granulating is molded under hydraulic press, and molding pressure is set as 25~100MPa, dwell time setting
For 2~10min；(d2) it demoulds, biscuit is coated with flexible die, is further suppressed in isostatic pressing machine, pressing pressure setting
For 230~300MPa；
(e) target biscuit is sintered, and obtains the controllable IGZO target of phase composition, in some embodiments, target sintering
Process specifically includes: target biscuit is put into sintering furnace by (e1), with the heating rate of 0.5~1 DEG C/min, is warming up to degreasing temperature
600 DEG C of degree, makes the complete degreasing of biscuit；(e2) with the heating rate of 2~5 DEG C/min, 1300~1500 DEG C of sintering temperature are warming up to,
It is passed through oxygen in temperature-rise period, keeps the temperature 6 hours at a sintering temperature；(e3) stop heating, with the rate of temperature fall of 1~3 DEG C/min,
Room temperature is cooled to get the IGZO target controllable to phase composition.
In some embodiments of the present invention, drum's speed of rotation is set as 200~250r/min；It is ground used in mechanical milling process
Ball is respectivelyWithThe mass ratio of three bulbs is 1:1:1；Ratio of grinding media to material is 4:1, and maximum charge is no more than ball grinder
3/4ths of volume.
In some embodiments of the present invention, using ammonium polyacrylate as dispersing agent, using polyvinyl alcohol as binder,
Using water as ball-milling medium, preferably, using pure water as ball-milling medium, such as deionized water.Mechanical milling process can have
Effect refinement and dispersion powder, and the activity of powder is improved, the forming process of reaction and single object phase to subsequent object phase has directly
Influence.
In skimming processes, degreasing heating rate is too fast, it is easy to cause the volatilization of component fierceness, expansion in biscuit to overflow, make
Subsequent sintering process, sintered density can be seriously affected at the fracture of biscuit body or underbead crack, the fracture of formation or underbead crack
Meeting degradation, and sintering crack and contraction phenomenon of rupture are difficult to avoid；However degreasing heating rate can extend sintering slowly excessively
Period reduces sintering efficiency, improves manufacturing cost.In some embodiments, degreasing heating rate can be selected in 0.5~1 DEG C/min
Between；As more preferred embodiment, degreasing heating rate is arranged between 0.6~0.8 DEG C/min.
In sintering process, sintering temperature and soaking time become apparent the influence of the performance of target.Sintering temperature is to sintering
The density and microstructure of body are very sensitive, and sintering temperature raising can be such that sintered density increases, but can accelerate sintered body
Volatilization, because IGZO belongs to the material of highly volatile, and high-temperature will cause metallic zinc and be precipitated again, seriously affect IGZO target
Internal organizational structure, then sintered body target to subsequent magnetron sputtering membrane process generation seriously affect；Temperature is relatively low, i.e., can
Underburnt is caused, sintered density is small, and porosity is high, also there are detrimental effects to subsequent sputter coating.As optional embodiment, root
According to the ratio of material composition, sintering temperature can be selected between 1300 DEG C~1500 DEG C.Soaking time has similar influence, heat preservation
Time, the too short sintered density that will lead to did not reached requirement；Soaking time is too long, is easy to produce burning, leads to coarse grains, target
Material embrittlement is serious, and subsequent back target welding connects and is easy to appear target phenomenon of rupture during sputter coating.As optional embodiment,
The sintered heat insulating time can be selected between 4~8 hours, and more preferably in embodiment, the setting of sintered heat insulating time is small 5~7
When between；In further preferred embodiment, the sintered heat insulating time was arranged between 6~7 hours.
In sintering process, sintering heating rate be can choose between 2~5 DEG C/min, more preferably in 3~4 DEG C/min
Between.
In some embodiments of the present invention, the condition of the temperature-fall period of the preparation method of indium gallium zinc target is, with 1~
3 DEG C/min rate of temperature fall is cooled to room temperature, obtains indium gallium zinc sintered body.
Content in order to better illustrate the present invention gives concrete details in specific embodiment below.This field
It will be appreciated by the skilled person that without certain details, the present invention equally be can be implemented.In embodiment, for this field skill
Certain methods known to art personnel, means, instrument, equipment, raw material composition, molecular structure etc. are not described in detail, in order to convex
Show purport of the invention.
Embodiment 1
In the present embodiment 1, the preparation method of phase composition controllable IGZO (indium gallium zinc) target, comprising:
By the high-purity indium oxide powder of nanoscale, gallium oxide powder, three kinds of components of Zinc oxide powder according to 1:1:1 molar ratio
Example mixing chooses 0.5% ammonium polyacrylate as dispersing agent, chooses 0.8% polyvinyl alcohol as binder, selection 50%
Pure water as ball-milling medium；
The mixture of powders that indium oxide powder, gallium oxide powder, Zinc oxide powder are formed, with ammonium acrylate, pure water, three
The zirconium oxide balls of kind specification are packed into the zirconia ball grinding jar of 1L, carry out mixing and ball milling, ball to mixed material on ball mill
0.1% dispersing agent is added in mill again after 24 hours, 0.2% dispersing agent is added for the last time after continuing ball milling 24 hours, again ball
Mill 1 hour；Binder is added to continue ball milling 1 hour, ball milling terminates；Wherein, drum's speed of rotation 250r/min, in mechanical milling process
The zirconium oxide balls diameter used is respectivelyWithThe mass ratio of three kinds of abrading-balls is 1:1:1；Ratio of grinding media to material is 4:1, dress
Doses is about 3/5ths of tank volume；
The mixed material obtained after ball milling is poured out from ball grinder, and mist projection granulating is carried out on pelletizer, and prilling temperature is
200 DEG C, charging rate 10RPM；
The powder material that the granulation of certain mass obtains is weighed, is placed inIn steel die, it is molded under hydraulic press
Type, briquetting pressure 50MPa, pressure maintaining 5min obtain target biscuit；Target biscuit is coated with flexible die after demoulding, is being waited
It is further suppressed in static pressure machine, pressure 250MPa；
Target biscuit is put into sintering furnace, air is passed through, air mass flow 15L/min is being warming up to 600 DEG C of process
In slowly heat up, keep biscuit degreasing complete, heating rate be 1 DEG C/min；Heating rate is improved at 600 DEG C or more, and will
Air is converted to oxygen, and oxygen flow 12L/min, heating rate is 3 DEG C/min, until being warming up to 1500 DEG C；In the temperature
Then lower heat preservation 6h stops heating and slow cooling to room temperature, rate of temperature fall is 1 DEG C/min, by oxygen when being down to 800 DEG C or less
It closes.Corresponding IGZO ceramic target can be obtained.
It carries out XRD object to IGZO target prepared by the present embodiment 1 mutually to detect, such as Fig. 2, XRD IGZO target as the result is shown
In only single object phase In2Ga2ZnO7, without the generation of other object phases, this uses In with raw material2O3:Ga2O3: ZnO=1:1:
Object phase result after the complete reaction of 1 mol ratio is completely the same, illustrates in this example through the control to technical process,
Obtain the IGZO target that object is mutually single and object is mutually controllable.Fig. 3 is the stereoscan photograph of 1 gained IGZO target of the present embodiment,
From microstructure morphology it can be seen that crystal grain is regular polygon, each intercrystalline combines densification, and intercrystalline and inside are not present two
Secondary phase constitution.
Embodiment 2
In the present embodiment 2, the preparation method of the controllable indium gallium zinc target of phase composition, comprising:
By the high-purity indium oxide powder of nanoscale, gallium oxide powder, three kinds of components of Zinc oxide powder according to 1:1:2 molar ratio
Example mixing chooses 0.4% ammonium polyacrylate as dispersing agent, chooses 0.8% polyvinyl alcohol as binder, selection 55%
Pure water as ball-milling medium；
The mixture of powders that indium oxide powder, gallium oxide powder, Zinc oxide powder are formed, with ammonium acrylate, pure water, three
The zirconium oxide balls of kind specification are packed into the zirconia ball grinding jar of 1L, carry out mixing and ball milling, ball to mixed material on ball mill
0.2% dispersing agent is added in mill again after 24 hours, 0.2% dispersing agent is added for the last time after continuing ball milling 24 hours, again ball
Mill 1 hour；Binder is added to continue ball milling 1 hour, ball milling terminates；Wherein, drum's speed of rotation 230r/min, in mechanical milling process
The ball radius used is respectivelyWithThe mass ratio of three kinds of abrading-balls is 1:1:1；Ratio of grinding media to material is 4:1, and charge is about
It is 3/4ths of tank volume；
The mixed material obtained after ball milling is poured out from ball grinder, and mist projection granulating is carried out on pelletizer, and prilling temperature is
200 DEG C, charging rate 15RPM；
The powder material that the granulation of certain mass obtains is weighed, is placed inIn steel die, it is molded under hydraulic press
Type, briquetting pressure 50MPa, pressure maintaining 5min obtain target biscuit；Target biscuit is coated with flexible die after demoulding, is being waited
It is further suppressed in static pressure machine, pressure 270MPa；
Target biscuit is put into sintering furnace, air is passed through, air mass flow 15L/min is being warming up to 600 DEG C of process
In slowly heat up, keep biscuit degreasing complete, heating rate be 1 DEG C/min；Heating rate is improved at 600 DEG C or more, and will
Air is converted to oxygen, and oxygen flow 12L/min, heating rate is 3 DEG C/min, until being warming up to 1350 DEG C；In the temperature
Then lower heat preservation 6h stops heating and slow cooling to room temperature, rate of temperature fall is 2 DEG C/min, by oxygen when being down to 800 DEG C or less
It closes.Corresponding IGZO ceramic target can be obtained.
It carries out XRD object to IGZO target prepared by the present embodiment 2 mutually to detect, XRD is the results show that obtained IGZO target
In only single object phase InGaZnO4, without the generation of other object phases, this uses In with raw material2O3:Ga2O3: ZnO=1:1:2
Mol ratio complete reaction after object phase result it is completely the same, illustrate in this example by techniques such as molar ratio of material
The control of parametric procedure obtains the mutually single and controllable IGZO target of object.The SEM of gained IGZO target in through this embodiment
Detection, it can be seen that crystal grain combines densification, and only a little crackle generates, and consistency is higher, and crystal grain is regular polygon, crystallite dimension
Bigger than the crystal grain that molar ratio in embodiment 1 is 1:1:1 target, secondary phase constitution is not present in intercrystalline and inside.
Embodiment 3
In the present embodiment 3, the preparation method of the controllable indium gallium zinc target of phase composition, comprising:
By the high-purity indium oxide powder of nanoscale, gallium oxide powder, three kinds of components of Zinc oxide powder according to 1:1:8 molar ratio
Example mixing chooses 0.3% ammonium polyacrylate as dispersing agent, chooses 0.9% polyvinyl alcohol as binder, selection 60%
Pure water as ball-milling medium；
The mixture of powders that indium oxide powder, gallium oxide powder, Zinc oxide powder are formed, with ammonium acrylate, pure water, three
The zirconium oxide balls of kind specification are packed into the zirconia ball grinding jar of 1L, carry out mixing and ball milling, ball to mixed material on ball mill
0.2% dispersing agent is added in mill again after 24 hours, 0.3% dispersing agent is added for the last time after continuing ball milling 24 hours, again ball
Mill 1 hour；Binder is added to continue ball milling 1 hour, ball milling terminates；Wherein, drum's speed of rotation 240r/min, in mechanical milling process
The ball radius used is respectivelyWithThe mass ratio of three kinds of abrading-balls is 1:1:1；Ratio of grinding media to material is 4:1, and charge is about
It is 3/4ths of tank volume；
The mixed material obtained after ball milling is poured out from ball grinder, and mist projection granulating is carried out on pelletizer, and prilling temperature is
200 DEG C, charging rate 10RPM；
The powder material that the granulation of certain mass obtains is weighed, is placed inIn steel die, it is molded under hydraulic press
Type, briquetting pressure 50MPa, pressure maintaining 5min obtain target biscuit；Target biscuit is coated with flexible die after demoulding, is being waited
It is further suppressed in static pressure machine, pressure 250MPa；
Target biscuit is put into sintering furnace, air is passed through, air mass flow 15L/min is being warming up to 600 DEG C of process
In slowly heat up, keep biscuit degreasing complete, heating rate be 1 DEG C/min；Heating rate is improved at 600 DEG C or more, and will
Air is converted to oxygen, and oxygen flow 12L/min, heating rate is 3 DEG C/min, until being warming up to 1450 DEG C；In the temperature
Then lower heat preservation 6h stops heating and slow cooling to room temperature, rate of temperature fall is 2 DEG C/min, by oxygen when being down to 800 DEG C or less
It closes.Corresponding IGZO ceramic target can be obtained.
XRD object is carried out to IGZO target prepared by the present embodiment 3 mutually to detect, it is found that its XRD result is single-phase
InGaZn4O7, without the generation of other object phases, this uses In with raw material2O3:Ga2O3: the mol ratio of ZnO=1:1:8 it is complete
Object phase result after reaction is completely the same, illustrates in this example through the accurate control to technological parameters such as material molar ratios,
Obtain single object phase one, controllable IGZO target.The SEM detection of gained IGZO target in through this embodiment, it is known that crystal grain is
Regular polygon, each intercrystalline combine densification, and secondary phase constitution is not present in intercrystalline and inside.
Using the preparation method of the controllable IGZO target of phase composition ingredient disclosed by the embodiments of the present invention, by preparing
Effective control of technological parameter in journey can obtain single-phase and mutually controllable object high-quality IGZO target according to material molar ratio,
Other miscellaneous phase ingredients are not contained in target, secondary phase constitution is not present in intercrystalline and inside, and intercrystalline combines densification, and target causes
Density is high, value of industrial utilization with higher.
Technical detail disclosed in technical solution and embodiment disclosed by the invention, is merely illustrative structure of the invention
Think, and does not constitute a limitation of the invention, it is all not have a creative change to what technical detail disclosed by the invention was made, it is right
Presently disclosed techniques scheme is applied in combination, all with present invention inventive concept having the same, all in the claims in the present invention
Protection scope within.
Claims (10)
1. the preparation method of the controllable indium gallium zinc target of phase composition, which is characterized in that the preparation method includes:
(a) indium oxide powder, gallium oxide powder, Zinc oxide powder are mixed according to the molar ratio of setting, obtain mixed-powder；
(b) dispersing agent of mixed-powder and set amount, binder, ball-milling medium carry out ball milling mixing using ball-milling device, obtain
Mixed material；
(c) mixed material carries out mist projection granulating on pelletizer；
(d) the product compression molding that mist projection granulating obtains, obtains target biscuit；
(e) target biscuit is sintered, and obtains the controllable indium gallium zinc target of phase composition.
2. the preparation method of the controllable indium gallium zinc target of phase composition according to claim 1, which is characterized in that described
Indium oxide powder, gallium oxide powder, Zinc oxide powder molar ratio be set as 1:1:m, wherein m be 1~8.
3. the preparation method of the controllable indium gallium zinc target of phase composition according to claim 1, which is characterized in that described
The partial size of indium oxide powder is set as 50~200nm, and the partial size of the gallium oxide powder is set as 2~10 μm, the zinc oxide
The partial size of powder is set as 80~200nm.
4. the preparation method of the controllable indium gallium zinc target of phase composition according to claim 1, which is characterized in that described
The amount of dispersing agent is set as 0.3~2.0%, and the amount of the binder is set as 0.1~1%, the amount setting of the ball-milling medium
It is 50~60%.
5. the preparation method of the controllable indium gallium zinc target of phase composition according to claim 1, which is characterized in that described
The process of ball milling mixing includes:
(b1) mixed-powder, part dispersing agent ball-milling medium are mixed, the time T1 that ball milling is set on ball mill；
(b2) part dispersing agent is added again, continues the time T2 of ball milling setting；
(b3) dispersing agent of remainder is added, continues the time T3 of ball milling setting；
(b4) binder is added, carries out the time T4 of ball milling setting.
6. the preparation method of the controllable indium gallium zinc target of phase composition according to claim 5, which is characterized in that described
The process of ball milling mixing specifically includes:
(b1) by mixed-powder, 0.1~1% dispersing agent, 50~60% ball-milling medium mix, on ball mill ball milling when
Between T1 be set as 24 hours；
(b2) 0.1~0.3% dispersing agent is added again, the time T2 for continuing ball milling is set as 24 hours；
(b3) dispersing agent of remainder is added, the time T3 for continuing ball milling is set as 1~3 hour；
(b4) binder is added, the time T4 for carrying out ball milling is set as 1~3 hour.
7. the preparation method of the controllable indium gallium zinc target of phase composition according to claim 1, which is characterized in that described
During mist projection granulating, prilling temperature is set as 180~210 DEG C, and charging rate is set as 5~15RPM.
8. the preparation method of the controllable indium gallium zinc target of phase composition according to claim 1, which is characterized in that described
Compression molding specifically includes:
(d1) product of mist projection granulating is molded under hydraulic press, and molding pressure is set as 25~100MPa, and the dwell time is set as 2
~10min；
(d2) it demoulding, biscuit is coated with flexible die, is further suppressed in isostatic pressing machine, pressing pressure is set as 230~
300MPa。
9. the preparation method of the controllable indium gallium zinc target of phase composition according to claim 1, which is characterized in that described
Target sintering specifically includes:
(e1) target biscuit is put into sintering furnace, with the heating rate of 0.5~1 DEG C/min, is warming up to 600 DEG C of skimming temp,
Make the complete degreasing of biscuit；
(e2) with the heating rate of 2~5 DEG C/min, 1300~1500 DEG C of sintering temperature is warming up to, oxygen is passed through in temperature-rise period,
6 hours are kept the temperature under the sintering temperature；
(e3) stop heating, with the rate of temperature fall of 1~3 DEG C/min, be cooled to room temperature to get the indium gallium controllable to phase composition
Zinc target.
10. the controllable indium gallium zinc target of phase composition, which is characterized in that the target is by according to any one of claims 1 to 9
The preparation method of the controllable indium gallium zinc target of phase composition obtains.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201910156692.1A CN109665834B (en) | 2019-03-01 | 2019-03-01 | Phase-composition-controllable indium gallium zinc oxide target and preparation method thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201910156692.1A CN109665834B (en) | 2019-03-01 | 2019-03-01 | Phase-composition-controllable indium gallium zinc oxide target and preparation method thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN109665834A true CN109665834A (en) | 2019-04-23 |
| CN109665834B CN109665834B (en) | 2021-08-03 |
Family
ID=66151536
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201910156692.1A Active CN109665834B (en) | 2019-03-01 | 2019-03-01 | Phase-composition-controllable indium gallium zinc oxide target and preparation method thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN109665834B (en) |
Cited By (15)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110002853A (en) * | 2019-04-28 | 2019-07-12 | 郑州大学 | The method that twice sintering process prepares IGZO ceramic target |
| CN110128699A (en) * | 2019-06-03 | 2019-08-16 | 江苏极易新材料有限公司 | A kind of method of composite antioxidant granulating |
| CN111018515A (en) * | 2019-12-26 | 2020-04-17 | 广州市尤特新材料有限公司 | Method for manufacturing target material and target material |
| CN111574217A (en) * | 2020-05-20 | 2020-08-25 | 先导薄膜材料（广东）有限公司 | Rare earth doped indium gallium zinc oxide powder and preparation method and application thereof |
| CN112341159A (en) * | 2020-10-20 | 2021-02-09 | 先导薄膜材料（广东）有限公司 | Preparation method of indium gallium zinc oxide target material |
| CN112390622A (en) * | 2020-11-23 | 2021-02-23 | 先导薄膜材料（广东）有限公司 | Preparation method of EIGZO target material |
| CN112509974A (en) * | 2020-12-01 | 2021-03-16 | 绵阳惠科光电科技有限公司 | Preparation method of IGZO array substrate |
| CN112723875A (en) * | 2021-02-03 | 2021-04-30 | 郑州大学 | Gallium oxide doped tin oxide ceramic target material and preparation method thereof |
| CN113233888A (en) * | 2021-04-27 | 2021-08-10 | 先导薄膜材料（广东）有限公司 | Method for preparing IGZO target material by recycling IGZO waste biscuit |
| CN114790106A (en) * | 2022-04-14 | 2022-07-26 | 株洲火炬安泰新材料有限公司 | IGZO target material, preparation method thereof and detection system |
| CN115894010A (en) * | 2022-11-28 | 2023-04-04 | 郑州大学 | Tubular indium gallium zinc (In) oxide 2 Ga 2 ZnO 7 ) Preparation method of fine-grain high-density crack-free target material |
| CN116199496A (en) * | 2022-12-15 | 2023-06-02 | 先导薄膜材料（广东）有限公司 | Indium zinc oxide doped rare earth metal target material and preparation method thereof |
| CN116253556A (en) * | 2023-02-07 | 2023-06-13 | 郑州大学 | Indium tin zinc oxide target material and preparation method thereof |
| CN116655372A (en) * | 2023-06-25 | 2023-08-29 | 深圳众诚达应用材料股份有限公司 | Tin oxide-based target material and preparation method thereof |
| CN117051369A (en) * | 2023-10-11 | 2023-11-14 | 北京航空航天大学宁波创新研究院 | Preparation method of strontium niobate-doped target, target and magnetron sputtering film |
Citations (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101930805A (en) * | 2009-06-22 | 2010-12-29 | 富士胶片株式会社 | IGZO base oxide material and the method for preparing the IGZO base oxide material |
| CN102153352A (en) * | 2010-12-17 | 2011-08-17 | 西北稀有金属材料研究院 | Composite adhesive and application thereof in preparation of sintering target |
| CN102320838A (en) * | 2011-05-10 | 2012-01-18 | 孔伟华 | Flexible transparent conducting film is with metal oxide semiconductor material and preparation method thereof |
| JP2012116718A (en) * | 2010-12-02 | 2012-06-21 | Taiheiyo Cement Corp | Igzo sintered compact and method for producing the same |
| CN105985102A (en) * | 2015-01-30 | 2016-10-05 | 上海光线新材料科技有限公司 | Microwave dielectric ceramic material and preparation method thereof |
| CN106966700A (en) * | 2017-03-09 | 2017-07-21 | 郑州大学 | A kind of short route preparation technology of tin indium oxide sintered body |
| CN107814564A (en) * | 2016-09-13 | 2018-03-20 | 上海硅酸盐研究所中试基地 | Method prepared by a kind of phosphoric acid titanium compound batch of inexpensive carbon coating |
| CN108623287A (en) * | 2018-06-21 | 2018-10-09 | 郑州大学 | A kind of short flow process of indium gallium zinc sintered body |
| CN108623298A (en) * | 2018-07-04 | 2018-10-09 | 郑州大学 | A kind of degreasing sintered integral preparation method of high density tin indium oxide tubular target |
| CN108706965A (en) * | 2018-06-21 | 2018-10-26 | 郑州大学 | A kind of short flow process of indium gallium zinc tubular target |
-
2019
- 2019-03-01 CN CN201910156692.1A patent/CN109665834B/en active Active
Patent Citations (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101930805A (en) * | 2009-06-22 | 2010-12-29 | 富士胶片株式会社 | IGZO base oxide material and the method for preparing the IGZO base oxide material |
| JP2012116718A (en) * | 2010-12-02 | 2012-06-21 | Taiheiyo Cement Corp | Igzo sintered compact and method for producing the same |
| CN102153352A (en) * | 2010-12-17 | 2011-08-17 | 西北稀有金属材料研究院 | Composite adhesive and application thereof in preparation of sintering target |
| CN102320838A (en) * | 2011-05-10 | 2012-01-18 | 孔伟华 | Flexible transparent conducting film is with metal oxide semiconductor material and preparation method thereof |
| CN105985102A (en) * | 2015-01-30 | 2016-10-05 | 上海光线新材料科技有限公司 | Microwave dielectric ceramic material and preparation method thereof |
| CN107814564A (en) * | 2016-09-13 | 2018-03-20 | 上海硅酸盐研究所中试基地 | Method prepared by a kind of phosphoric acid titanium compound batch of inexpensive carbon coating |
| CN106966700A (en) * | 2017-03-09 | 2017-07-21 | 郑州大学 | A kind of short route preparation technology of tin indium oxide sintered body |
| CN108623287A (en) * | 2018-06-21 | 2018-10-09 | 郑州大学 | A kind of short flow process of indium gallium zinc sintered body |
| CN108706965A (en) * | 2018-06-21 | 2018-10-26 | 郑州大学 | A kind of short flow process of indium gallium zinc tubular target |
| CN108623298A (en) * | 2018-07-04 | 2018-10-09 | 郑州大学 | A kind of degreasing sintered integral preparation method of high density tin indium oxide tubular target |
Non-Patent Citations (2)
| Title |
|---|
| 厉衡隆等编: "《铝冶炼生产技术手册》", 31 July 2011, 冶金工业出版社 * |
| 陈杰: "金属源漏多晶硅TFT及非晶IGZO TFT的特性研究", 《中国优秀硕士学位论文全文数据库 信息科技辑》 * |
Cited By (18)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110002853A (en) * | 2019-04-28 | 2019-07-12 | 郑州大学 | The method that twice sintering process prepares IGZO ceramic target |
| CN110128699A (en) * | 2019-06-03 | 2019-08-16 | 江苏极易新材料有限公司 | A kind of method of composite antioxidant granulating |
| CN110128699B (en) * | 2019-06-03 | 2021-03-16 | 江苏极易新材料有限公司 | Method for granulating composite antioxidant |
| CN111018515A (en) * | 2019-12-26 | 2020-04-17 | 广州市尤特新材料有限公司 | Method for manufacturing target material and target material |
| CN111574217A (en) * | 2020-05-20 | 2020-08-25 | 先导薄膜材料（广东）有限公司 | Rare earth doped indium gallium zinc oxide powder and preparation method and application thereof |
| CN112341159A (en) * | 2020-10-20 | 2021-02-09 | 先导薄膜材料（广东）有限公司 | Preparation method of indium gallium zinc oxide target material |
| CN112390622A (en) * | 2020-11-23 | 2021-02-23 | 先导薄膜材料（广东）有限公司 | Preparation method of EIGZO target material |
| CN112509974A (en) * | 2020-12-01 | 2021-03-16 | 绵阳惠科光电科技有限公司 | Preparation method of IGZO array substrate |
| CN112723875A (en) * | 2021-02-03 | 2021-04-30 | 郑州大学 | Gallium oxide doped tin oxide ceramic target material and preparation method thereof |
| CN113233888A (en) * | 2021-04-27 | 2021-08-10 | 先导薄膜材料（广东）有限公司 | Method for preparing IGZO target material by recycling IGZO waste biscuit |
| CN114790106A (en) * | 2022-04-14 | 2022-07-26 | 株洲火炬安泰新材料有限公司 | IGZO target material, preparation method thereof and detection system |
| CN115894010A (en) * | 2022-11-28 | 2023-04-04 | 郑州大学 | Tubular indium gallium zinc (In) oxide 2 Ga 2 ZnO 7 ) Preparation method of fine-grain high-density crack-free target material |
| CN116199496A (en) * | 2022-12-15 | 2023-06-02 | 先导薄膜材料（广东）有限公司 | Indium zinc oxide doped rare earth metal target material and preparation method thereof |
| CN116253556A (en) * | 2023-02-07 | 2023-06-13 | 郑州大学 | Indium tin zinc oxide target material and preparation method thereof |
| CN116655372A (en) * | 2023-06-25 | 2023-08-29 | 深圳众诚达应用材料股份有限公司 | Tin oxide-based target material and preparation method thereof |
| CN116655372B (en) * | 2023-06-25 | 2024-01-26 | 深圳众诚达应用材料股份有限公司 | Tin oxide-based target material and preparation method thereof |
| CN117051369A (en) * | 2023-10-11 | 2023-11-14 | 北京航空航天大学宁波创新研究院 | Preparation method of strontium niobate-doped target, target and magnetron sputtering film |
| CN117051369B (en) * | 2023-10-11 | 2024-01-05 | 北京航空航天大学宁波创新研究院 | Preparation method of strontium niobate-doped target, target and magnetron sputtering film |
Also Published As
| Publication number | Publication date |
|---|---|
| CN109665834B (en) | 2021-08-03 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN109665834A (en) | The controllable indium gallium zinc target and preparation method thereof of phase composition | |
| CN108706965B (en) | A kind of short flow process of indium gallium zinc tubular target | |
| JP3746094B2 (en) | Target and manufacturing method thereof | |
| JP6438588B2 (en) | Translucent rare earth aluminum garnet ceramics | |
| CN107555989A (en) | A kind of black zirconia ceramics and preparation method thereof | |
| CN108623298A (en) | A kind of degreasing sintered integral preparation method of high density tin indium oxide tubular target | |
| CN108623287A (en) | A kind of short flow process of indium gallium zinc sintered body | |
| CN101835920A (en) | Sputtering target for magnetic recording film and method for manufacturing such sputtering target | |
| Yavetskiy et al. | Phase formation and densification peculiarities of Y3Al5O12: Nd3+ during reactive sintering | |
| CN105906338A (en) | Production method of high-density IGZO rotating target material | |
| CN110002853A (en) | The method that twice sintering process prepares IGZO ceramic target | |
| WO2022062293A1 (en) | High-performance energy-saving magnesium-based raw material and preparation method therefor | |
| JP5809605B2 (en) | Method for producing indium gallium zinc oxide composition | |
| NL2030121B1 (en) | Method for preparing large-size high-quality potassium tantalum niobate ceramic target material | |
| CN109437890A (en) | A kind of zirconia ceramics sintering aid and its preparation method and application | |
| JPWO2017110909A1 (en) | Oxide sintered body sputtering target and manufacturing method thereof | |
| Duan et al. | Effect of MgO doping on densification and grain growth behavior of Gd 2 Zr 2 O 7 ceramics by microwave sintering process | |
| CN113548891B (en) | Two-phase cobalt tantalate ceramic block and preparation method thereof | |
| US5106794A (en) | Zirconium oxide sinter for forming thin film thereof and method for production of the same | |
| CN112194482A (en) | Ultralow-loss wide-temperature-power MnZn ferrite, preparation method and application thereof in 5G communication field | |
| CN106187151A (en) | A kind of aluminum doped yttrium zinc oxide ceramic target and preparation method thereof | |
| JP2000353530A (en) | MANUFACTURE OF NiO AND/OR Ni/YSZ COMPOSITE POWDER AND MANUFACTURE OF SOLID ELECTROLYTE FUEL CELL USING THEREOF | |
| CN116253556A (en) | Indium tin zinc oxide target material and preparation method thereof | |
| CN115745573A (en) | Preparation method of fine-grain IZO target material | |
| CN109844167A (en) | Magnetic material sputtering target and its manufacturing method |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |