CN104291806A - Method for studying optimal sintering process and optimal doping concentration of gallium-doped zinc oxide ceramic - Google Patents

Method for studying optimal sintering process and optimal doping concentration of gallium-doped zinc oxide ceramic Download PDF

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CN104291806A
CN104291806A CN201410484494.5A CN201410484494A CN104291806A CN 104291806 A CN104291806 A CN 104291806A CN 201410484494 A CN201410484494 A CN 201410484494A CN 104291806 A CN104291806 A CN 104291806A
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sintering
optimal
zinc oxide
optimum
doped zinc
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王越
梅晓平
蒋毅坚
马云峰
曾勇
陈龙
张春萍
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Beijing University of Technology
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Beijing University of Technology
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    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
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    • 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
    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
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    • 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

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Abstract

The invention discloses a method for studying an optimal sintering process and an optimal doping concentration of gallium-doped zinc oxide ceramic and belongs to the field of preparation of conductive ceramic. The method comprises the following steps of blending ZnO and Ga2O3 powder according to a chemical formula of Ga<x>Zn<1-x>O, wherein x is a certain value in the range of 0-1; carrying out ball milling and drying, and carrying out differential thermal analysis on the powder material so as to determine the optimal pre-sintering temperature; determining the optimal sintering temperature by adopting a certain time as sintering time; based on the determined optimal sintering temperature, changing different sintering time and sintering a series of samples; processing the sintered samples, testing the density and electrical properties and determining the optimal sintering time; under the condition of previously determined optimal sintering process, sintering a series of ceramic Ga<x>Zn<1-x>O with different components; processing the sintered samples, carrying out XRD and electrical properties test and determining the optimal concentration of gallium-doped zinc oxide ceramic. The invention provides a process of high-density and low-resistivity GZO ceramic in a conventional sintering manner, which has the advantages of short period and low energy consumption.

Description

A kind of method studying doped zinc oxide gallium pottery optimum sintering process and optimum doping concentration
Technical field
The invention belongs to Ga xzn 1-xthe preparation field of O (being called for short GZO) conductivity ceramics.
Background technology
GZO pottery due to its excellent performance, and is widely used in scintillation material, conductivity ceramics, sputtering target material etc.The ceramic the most general application of current doped zinc oxide gallium is exactly the sputtering target material for the preparation of transparent conductive film, the GZO film prepared with it has larger energy gap (about 3.3eV), there is the electrical and optical properties compared favourably with ito thin film, therefore can be widely used in the fields such as solar cell, piezoelectric device, liquid-crystal display; And the abundant raw material of making ZnO, cheap, preparation cost is lower, nontoxic to environment, and thermostability and chemical stability are all relatively good, and its Application Areas at material is constantly expanded, and is therefore one of material of a kind of replacement ITO of most potentiality.The quality of GZO pottery, as purity, density, resistivity, grain size and distribution etc., will be directly connected to the quality of doped zinc oxide gallium film performance.The preparation of GZO ceramic target is the same with ITO target, and technical difficulty is large, and core technology rests in U.S., Deng developed country substantially.Domesticly be in laboratory development at this field Yet-have at present, GZO ceramic target substantially still dependence on import needed for industrial production, therefore determine that the optimum sintering process of GZO pottery is to serve scientific research and industrial production is extremely urgent.In addition, determine that the best mixes the zinc oxide ceramics of gallium concentration, the performance study for material very has reference value, but also little about the report of this respect.In the last few years, the article about GZO class was delivered more, mainly concentrated on thin-film material, and wherein the article of ceramic-like is delivered less, and the performance study for GZO pottery is relatively less.
Document 1: 2012 year, the people such as the Wu Muying Ga-doped zinc oxide conductivity ceramics that utilized high-temperature solid phase reaction method to prepare.They draw, the Optimal technique process of GZO conductivity ceramics is, calcined temperature 700 DEG C, sintering temperature 1300 DEG C, doping content are mol ratio 2%.But report in article, lowest resistivity 0.1 Ω ㎝ conductive effect is not good, according to 5 component proportions, select optimum doping concentration, systematicness is not strong.(Wu Muying, Liu Minxia, Li Hongtao, Yang Lei, Zhang Weifeng, preparation condition affects the transparent conductivity of Ga-doped zinc oxide film, Journal of Henan University (natural science edition), 2012,42 (6): 707-711)
2009, the Ga-doped zinc oxide pottery (0.2at%, 0.5at%, 1at%) of the people such as J.P.Wiff three components that utilized high-temperature solid phase reaction method to sinter, sintering process was 1400 DEG C, 10h.In literary composition, the sintering process of pottery is more numerous and diverse, and sintering temperature is higher, and do not study the optimum sintering process of pottery, mainly doped zinc oxide aluminium and doped zinc oxide gallium ceramic performance contrast.(J.P.Wiff,Y.Kinemuchi,K.Watari，Hall mobilities of Al-and Ga-doped ZnO polycrystals，Materials Letters 63(2009)2470–2472)
2009, the Ga-doped zinc oxide pottery (0.0at%, 0.1at%, 0.5at%, 1.0at%, 2.0at%, 3.0at%) of the people such as M.S.Jang six components that utilized high-temperature solid phase reaction method to sinter, sintering process was 1300 DEG C, 10h.They find that pottery has lowest resistivity, and numerical value is approximately 1.0 Ω ㎝ when gallium doping mol ratio is 0.5at%.Although reporting optimum doping concentration in literary composition is 0.5at%, ceramic resistor rate is too large, and the component of configuration is meticulous not.(M.S.Jang,M.K.Ryu,M.H.Yoon,S.H.Lee,H.K.Kim,A.Onodera,S.Kojima，A study on the Raman spectra of Al-doped and Ga-doped ZnO ceramics，Current Applied Physics 9(2009)651–657)
Summary of the invention
The object of the present invention is to provide under a kind of conventional sintering mode, the cycle is short, it is low to consume energy, the optimum sintering process of GZO pottery of high compactness and low-resistivity and the preparation technology of optimum doping concentration.
The present invention is achieved by the following scheme
(1) by ZnO, Ga 2o 3chemical formula Ga pressed by powder xzn 1-xo wherein x value is certain certain value within the scope of 0-1, prepares burden, and through ball milling with after drying, gets powder and carries out differential thermal analysis, determine best calcined temperature;
(2) using certain certain hour as sintering time, different sintering temperatures is changed, sintering series of samples; Processed by sample after sintering, line density of going forward side by side and electrical performance testing, determine optimal sintering temperature;
(3) on the optimal sintering temperature basis determined, different sintering times is changed, sintering series of samples; Processed by sample after sintering, line density of going forward side by side and electrical performance testing, determine best sintering time;
(4), in the optimum sintering process situation determined above, the ceramic Ga of a series of different components is sintered xzn 1-xo; Sample after sintering is processed, and carries out XRD and electrical performance testing, determine Ga-doped zinc oxide pottery optimum concn.
Study a method for doped zinc oxide gallium pottery optimum sintering process and optimum doping concentration, it is characterized in that:
(1) by ZnO, Ga 2o 3chemical formula Ga pressed by powder 0.005zn 0.995o prepares burden, and through ball milling with after drying, gets powder and carries out differential thermal analysis, determines that best calcined temperature be 1150 DEG C of burn-in time is 9h;
(2) using 10h as sintering time, different sintering temperatures is changed, sintering series of samples; Processed by sample after sintering, line density of going forward side by side and electrical performance testing, determine that optimal sintering temperature is 1325 DEG C;
(3) on the optimal sintering temperature basis determined, different sintering times is changed, sintering series of samples; Processed by sample after sintering, line density of going forward side by side and electrical performance testing, determine that best sintering time is 4h;
(4), in the optimum sintering process situation determined above, the ceramic Ga of a series of different components is sintered xzn 1-xo; Sample after sintering is processed, and carries out XRD and electrical performance testing, determine that Ga-doped zinc oxide pottery optimum concn is 0.5at%.
The preparation method of doped zinc oxide gallium stupalith, is characterized in that:
By ZnO and Ga 2o 3ga pressed by powder 0.005zn 0.995after O proportioning weighs, pre-burning 9h at the temperature of 1150 DEG C; After pre-burning, powder will be made ceramic body; With 100 DEG C/h of temperature rise rates, in 550 DEG C of binder removal 3h, afterwards temperature is elevated to 1325 DEG C of insulation 4h, by once sintered for sample one-tenth porcelain.
Compared with the prior art, the obvious advantage of present invention process
(1) adopting solid state sintering mode, by systematically testing, determining the processing parameter such as optimal sintering temperature and best sintering time, for the suitability for industrialized production of GZO pottery provides reference
(2) tested by a series of different components, determine gallium doping optimum concn, for the GZO transparent conductive film of production performance the best provides reference.
(3) this technique is relative to existing technique, has once sintered one-tenth porcelain, the feature that preparation cycle is short, also has that sintering temperature is relatively low, soaking time is short, consume energy low feature.This advantage is suitable for suitability for industrialized production.
Accompanying drawing explanation
When Fig. 1 sintering time is 10h, the Ga under different sintering temperature 0.005zn 0.995o powder XRD figure is composed
When Fig. 2 sintering temperature is 1325 DEG C, the Ga under different sintering time 0.005zn 0.995o powder XRD figure is composed
Under Fig. 3 optimum sintering process, part mixes the ceramic powder XRD figure spectrum of gallium concentration
Embodiment
(1) by ZnO (99.99%) and Ga 2o 3(99.99%) Ga pressed by powder 0.005zn 0.995after O proportioning weighs, be placed in and ZrO is housed 2in the nylon tank that mill is situated between, take dehydrated alcohol as disperse means ball milling 24h, after oven dry, then get powder and carry out differential thermal analysis, determine that calcined temperature is 1150 DEG C;
(2) after determining calcined temperature, powder is placed in Al 2o 3close in crucible, with silicon-carbon stove pre-burning 9h at the temperature of 1150 DEG C; By after pre-burning by powder after 24h ball milling, dry, cross 180 mesh sieve 3 times, add polyvinyl alcohol (PVA) sticky agent that mass concentration is 6%, with powder Homogeneous phase mixing, under 80MPa pressure, make ceramic body;
(4) with 100 DEG C/h of temperature rise rates, in 550 DEG C of binder removal 3h, afterwards sample is elevated to respectively top temperature (1250 DEG C, 1275 DEG C, 1300 DEG C, 1325 DEG C, 1350 DEG C), insulation 10h, by once sintered for sample one-tenth porcelain;
(5) get part ceramic material and carry out XRD test, again ceramics sample is carried out density measurement, ceramics sample being cut into the length of side is carry out wear down process after the square of 0.5cm, surface is after polishing, ultrasonic cleaning, indium gallium alloy is put at ceramic plate four angles, carry out Hall effect test afterwards, determine optimal sintering temperature with this;
(6) operational path of reference step 4 and step 5, on the optimal sintering temperature basis determined, changes different sintering times (1h, 4h, 7h, 10h, 13h), sintering series of samples.Sample after sintering is processed, and carries out XRD, density and electrical performance testing, determine best sintering time;
(7), in the optimum sintering process situation determined above, the ceramic Ga of a series of different components is sintered xzn 1-xo (x=0.000,0.001,0.003,0.0035,0.004,0.0045,0.005,0.0055,0.006,0.007,0.008,0.009,0.01,0.015,0.02,0.03).Sample after sintering is processed, and carries out XRD and electrical performance testing, determine Ga-doped zinc oxide pottery optimum concn;
Conclusion: the optimum sintering process of doped zinc oxide gallium pottery is sintering temperature 1325 DEG C, sintering time 4h; It is 0.5at% that zinc oxide ceramics the best mixes gallium concentration, and under this component, the electric property of pottery is best.
Table 1 determines optimum sintering process with the pottery of the mol ratio 0.5at% that adulterates
ρ unit: g/cm 3γ unit: 10 -3Ω ㎝
N unit :-10 19cm -3μ unit: cm 2v -1s -1
The ceramic resistor rate of the different gallium doping content of table 2
γ unit: 10 -3Ω cm.

Claims (2)

1. study a method for doped zinc oxide gallium pottery optimum sintering process and optimum doping concentration, it is characterized in that:
(1) by ZnO, Ga 2o 3chemical formula Ga pressed by powder xzn 1-xo wherein x value is certain certain value within the scope of 0-1, prepares burden, and through ball milling with after drying, gets powder and carries out differential thermal analysis, determine best calcined temperature;
(2) using certain certain hour as sintering time, different sintering temperatures is changed, sintering series of samples; Processed by sample after sintering, line density of going forward side by side and electrical performance testing, determine optimal sintering temperature;
(3) on the optimal sintering temperature basis determined, different sintering times is changed, sintering series of samples; Processed by sample after sintering, line density of going forward side by side and electrical performance testing, determine best sintering time;
(4), in the optimum sintering process situation determined above, the ceramic Ga of a series of different components is sintered xzn 1-xo; Sample after sintering is processed, and carries out XRD and electrical performance testing, determine Ga-doped zinc oxide pottery optimum concn.
2. a kind of method studying doped zinc oxide gallium pottery optimum sintering process and optimum doping concentration according to claim 1, is characterized in that:
(1) by ZnO, Ga 2o 3chemical formula Ga pressed by powder 0.005zn 0.995o prepares burden, and through ball milling with after drying, gets powder and carries out differential thermal analysis, determines that best calcined temperature be 1150 DEG C of burn-in time is 9h;
(2) using 10h as sintering time, different sintering temperatures is changed, sintering series of samples; Processed by sample after sintering, line density of going forward side by side and electrical performance testing, determine that optimal sintering temperature is 1325 DEG C;
(3) on the optimal sintering temperature basis determined, different sintering times is changed, sintering series of samples; Processed by sample after sintering, line density of going forward side by side and electrical performance testing, determine that best sintering time is 4h;
(4), in the optimum sintering process situation determined above, the ceramic Ga of a series of different components is sintered xzn 1-xo; Sample after sintering is processed, and carries out XRD and electrical performance testing, determine that Ga-doped zinc oxide pottery optimum concn is 0.5at%.
CN201410484494.5A 2014-09-21 2014-09-21 Method for studying optimal sintering process and optimal doping concentration of gallium-doped zinc oxide ceramic Pending CN104291806A (en)

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Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN105669182A (en) * 2016-01-05 2016-06-15 北京工业大学 Method for studying optimum sintering process of gallium-doped zinc oxide ceramic by spark plasma sintering

Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN102534498A (en) * 2010-12-23 2012-07-04 海洋王照明科技股份有限公司 Gallium-doped zinc oxide transparent conducting film, and preparation method and application thereof
CN102691037A (en) * 2011-03-21 2012-09-26 海洋王照明科技股份有限公司 Gallium-doped zinc oxide film, and preparation method and application thereof
CN102912307A (en) * 2012-10-25 2013-02-06 东莞理工学院 Method for manufacturing Ga-doped ZnO transparent conducting thin film

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN102534498A (en) * 2010-12-23 2012-07-04 海洋王照明科技股份有限公司 Gallium-doped zinc oxide transparent conducting film, and preparation method and application thereof
CN102691037A (en) * 2011-03-21 2012-09-26 海洋王照明科技股份有限公司 Gallium-doped zinc oxide film, and preparation method and application thereof
CN102912307A (en) * 2012-10-25 2013-02-06 东莞理工学院 Method for manufacturing Ga-doped ZnO transparent conducting thin film

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN105669182A (en) * 2016-01-05 2016-06-15 北京工业大学 Method for studying optimum sintering process of gallium-doped zinc oxide ceramic by spark plasma sintering

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Application publication date: 20150121