CN110357626A - Doped tungsten oxide target and preparation method thereof - Google Patents
Doped tungsten oxide target and preparation method thereof Download PDFInfo
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Abstract
The present invention relates to a kind of doped tungsten oxide target and preparation method thereof, preparation method includes: that tungsten oxide activation and grinding are obtained active oxidation tungsten；By doping oxide activation and grinding, activation doping oxide is obtained, wherein the doping oxide is the oxide of one or more compositions in titanium, nickel, tantalum, rhenium, iridium, molybdenum, niobium, silicon, tin, zinc, zirconium and germanium；The active oxidation tungsten and activation doping oxide are uniformly mixed, suppresses, obtains green body；By the blank sintering, doped tungsten oxide target is obtained；Wherein, the active oxidation tungsten and the fineness ratio of activation doping oxide and the relational expression of molar ratio are as follows:
Description
Technical field
The present invention relates to a kind of targets and preparation method thereof, more particularly to a kind of doped tungsten oxide target and its preparation side
Method.
Background technique
When magnetron sputtering prepares electrochromism film layer, if be easy to produce in target preparation process using metal targets
Split-phase influences to plate film uniformity；Due to using reactive sputtering, plated film rate is slower, can also cause in target surface because of a large amount of logical oxygen
Poison generates abnormal electric arc and dust fall, seriously affects film quality and device yield.And use the ceramic target of metal oxide
Material, it is only necessary to be passed through a small amount of oxygen, not easily cause dust fall, sputter rate can improve 5-10 times, but ceramic target compared to metallic target
Must satisfy: target has certain electric conductivity, is able to use the power supplys such as direct current, intermediate frequency；Target essential component uniformly, consistency
It is high.And the oxide target material addition metal prepared in the prior art, target split-phase is caused, the oxidation tungsten electrode of oxidation state is in addition used
The volatilization for easily causing tungsten oxide influences target consistency, can also damage production equipment, it is prior due to inside and outside target atmosphere it is poor
Different larger and tungsten oxide volatilization causes target inside different from external conductivity, causes technological fluctuation, strong influence
Technology stability.In addition also lack how by control powder granularity obtain the method for the uniform electrochromism target of ingredient.
Summary of the invention
It is a primary object of the present invention to provide a kind of novel doped tungsten oxide target and preparation method thereof, to be solved
Certainly the technical issues of be make its obtain ingredient uniformly, good compactness, conductive doped tungsten oxide target, thus more suitable
In practical.
The object of the invention to solve the technical problems adopts the following technical solutions to realize.It proposes according to the present invention
A kind of doped tungsten oxide target preparation method comprising:
By tungsten oxide activation and grinding, active oxidation tungsten is obtained, the tungsten oxide is WO3-x, 0≤x < 2, the activation oxygen
Change tungsten is WOy, y≤3-x；
By doping oxide activation and grinding, activation doping oxide is obtained, the doping oxide is MOm, 0 < m≤3,
The activation doping oxide is MOn, n≤m, wherein M is in titanium, nickel, tantalum, rhenium, iridium, molybdenum, niobium, silicon, tin, zinc, zirconium and germanium
It is one or more；
The active oxidation tungsten and activation doping oxide are uniformly mixed, suppresses, obtains green body；
By the blank sintering, doped tungsten oxide target is obtained；
Wherein, the active oxidation tungsten and the fineness ratio of activation doping oxide and the relational expression of molar ratio are as follows:
In formula:
RwFor the radius of active oxidation tungsten；
RMFor the radius for activating doping oxide；
nwFor the molal quantity of active oxidation tungsten；
nMFor the molal quantity for activating doping oxide；
MwFor the molal weight of active oxidation tungsten；
MMFor the molal weight for activating doping oxide；
ρwFor the density of active oxidation tungsten；
ρMFor the density for activating doping oxide.
The object of the invention to solve the technical problems also can be used following technical measures and further realize.
Preferably, the preparation method of doped tungsten oxide target above-mentioned, wherein active oxidation tungsten particle in the green body
Fineness ratio with activation doping oxide particle is less than 1.
Preferably, the preparation method of doped tungsten oxide target above-mentioned, wherein the tungsten oxide activation includes: that will aoxidize
Tungsten is mixed with reducing agent, is heated under 800-1100 DEG C of inertia or vacuum environment, then under 200-500 DEG C of oxidation environment
Heating.
Preferably, the preparation method of doped tungsten oxide target above-mentioned, wherein the doping oxide activation include: by
Doping oxide is mixed with reducing agent, is heated under 800-1500 DEG C of inertia or vacuum environment, then in 200-500 DEG C of oxygen
Change and is heated under environment.
Preferably, the preparation method of doped tungsten oxide target above-mentioned, wherein the reducing agent be carbon dust or it is organic also
Former agent.
Preferably, the preparation method of doped tungsten oxide target above-mentioned, wherein the organic reducing agent is polyvinyl alcohol
Or methylcellulose.
Preferably, the preparation method of doped tungsten oxide target above-mentioned, wherein being adulterated in the doped tungsten oxide target
The molar content of metallic element is 0.1-20%.
Preferably, the preparation method of doped tungsten oxide target above-mentioned, wherein the atmosphere of the sintering be reducing atmosphere,
Inert atmosphere or vacuum atmosphere, the sintering temperature are 1100-1500 DEG C.
Preferably, the preparation method of doped tungsten oxide target above-mentioned, wherein the reducing atmosphere be inert gas and
The mixed gas of reducing gas；Wherein the ratio of the inert gas and reducing gas is 8:2-9.99:0.01.
Also the following technical solution is employed for the object of the invention to solve the technical problems to realize.It proposes according to the present invention
A kind of doped tungsten oxide target, be prepared by method above-mentioned；The doped tungsten oxide target is MWO3-x, wherein 0.1
﹤ x ﹤ 1, M are one of titanium, nickel, tantalum, rhenium, iridium, molybdenum, niobium, silicon, tin, zinc, zirconium and germanium or a variety of.
By above-mentioned technical proposal, doped tungsten oxide target of the present invention and preparation method thereof is at least had the advantage that
The present invention makes oxide system be in oxygen debt state by activating respectively to tungsten oxide and doping oxide,
The tungsten oxide particles of multivalent state and the doping oxide particle of multivalent state are obtained, raw material activity is improved, forms negative-ion vacancy,
The characteristic of N-type semiconductor is made it have, and the green body of generation is subjected to reduction sintering, further increases negative-ion vacancy, significantly
Its electric conductivity is promoted, so that the doped tungsten oxide target arrived is conductive, direct current or intermediate frequency power supply can be used；Simultaneously
The addition of oxygen debt type tungsten oxide, moreover it is possible to which the volatilization for reducing tungsten oxide improves the consistency of target.
The present invention is conducive to intergranular sintering reaction, obtains by establishing the relationship of granularity and molar ratio between oxide
The electrochromism doped tungsten oxide target that ingredient is uniform, consistency is high.
The present invention only uses pure tungsten oxide and doping oxide as raw material, and undope any other impurity, obtains
The target of high-purity.
The above description is only an overview of the technical scheme of the present invention, in order to better understand the technical means of the present invention,
And can be implemented in accordance with the contents of the specification, with presently preferred embodiments of the present invention, detailed description is as follows below.
Specific embodiment
It is of the invention to reach the technical means and efficacy that predetermined goal of the invention is taken further to illustrate, below in conjunction with
Preferred embodiment, to doped tungsten oxide target proposed according to the present invention and preparation method thereof its specific embodiment, structure, spy
Sign and its effect, detailed description is as follows.In the following description, what different " embodiment " or " embodiment " referred to is not necessarily same
One embodiment.In addition, the special characteristic, structure or feature in one or more embodiments can be combined by any suitable form.
One embodiment of the present of invention proposes a kind of preparation method of doped tungsten oxide target comprising:
By tungsten oxide activation and grinding, active oxidation tungsten is obtained, the tungsten oxide is WO3-x, 0≤x < 2, the activation oxygen
Change tungsten is WOy, y≤3-x；
By doping oxide activation and grinding, activation doping oxide is obtained, the doping oxide is MOm, 0 < m≤3,
The activation doping oxide is MOn, n≤m, wherein M is in titanium, nickel, tantalum, rhenium, iridium, molybdenum, niobium, silicon, tin, zinc, zirconium and germanium
It is one or more；
The active oxidation tungsten and activation doping oxide are uniformly mixed, suppresses, obtains green body；
By the blank sintering, doped tungsten oxide target is obtained；
Wherein, the active oxidation tungsten and the fineness ratio of activation doping oxide and the relational expression of molar ratio are as follows:
In formula:
RwFor the radius of active oxidation tungsten；
RMFor the radius for activating doping oxide；
nwFor the molal quantity of active oxidation tungsten；
nMFor the molal quantity for activating doping oxide；
MwFor the molal weight of active oxidation tungsten；
MMFor the molal weight for activating doping oxide；
ρwFor the density of active oxidation tungsten；
ρMFor the density for activating doping oxide.
The above-mentioned relation formula of the embodiment of the present invention is derived by by following formula, and specific derivation process is as follows:
4/3 π R of m=nM=X ρ V=X ρ3
In formula: m is quality, and n is molal quantity, and M is molal weight, and X is particle number, and ρ is density, and V is volume, and R is
Grain radius.
XwFor the particle number of active oxidation tungsten；
XMFor the particle number for activating doping oxide；
nwFor the molal quantity of active oxidation tungsten；
nMFor the molal quantity for activating doping oxide；
MwFor the molal weight of active oxidation tungsten；
MMFor the molal weight for activating doping oxide；
ρwFor the density of active oxidation tungsten；
ρMFor the density for activating doping oxide；
RwFor the radius of active oxidation tungsten；
RMFor the radius for activating doping oxide.
The ratio of particle radius is equal to the ratio of particle diameter, and fineness ratio can be indicated with the diameter of particle ratio, i.e.,
Fineness ratio can be equal to the radius ratio of particle.Therefore, the R in above formula can both substitute into radius, can also substitute into diameter
Or granularity.
In the embodiment of the present invention, after activated and grinding, obtained active oxidation tungsten and activation doping oxide is all
Grain.
The embodiment of the present invention is conducive to intergranular sintering reaction, obtains by establishing the relationship between granularity and molar ratio
The electrochromism doped tungsten oxide target uniform to ingredient, consistency is high.
It should be noted that the purpose that the embodiment of the present invention respectively activates tungsten oxide and doping oxide is to make oxygen
Compound system is in oxygen debt state, obtains the tungsten oxide particles of multivalent state and the doping oxide particle of multivalent state, and improve
Raw material activity, forms negative-ion vacancy, makes it have the characteristic of N-type semiconductor, promote its electric conductivity performance, so that arrive
Doped tungsten oxide target is conductive, and direct current or intermediate frequency power supply can be used；The addition of oxygen debt type tungsten oxide simultaneously, moreover it is possible to reduce
The volatilization of tungsten oxide improves the consistency of target.
It realizes the approach of the purpose of above-mentioned activation: the fresh easy reaction of oxide surface being allowed by heating, at this time activation front and back
The oxygen content of oxide is identical；Further, it can allow oxide oxygen loss, form oxygen debt type oxide, make it have N-type
The characteristic of semiconductor promotes its electric conductivity performance, and the oxygen content of activation front and back oxide has suitable reduction at this time.
It is further preferred that tungsten oxide is made to lose part oxygen under high temperature inert or vacuum environment, need to control heating
Temperature and time does not generate tungsten again while so that tungsten oxide is lost part oxygen, obtains the tungsten oxide particles of multivalent state.
Preferably, in the green body active oxidation tungsten and activation doping oxide fineness ratio less than 1.
In the embodiment of the present invention, the fineness ratio of active oxidation tungsten and activation doping oxide is conducive to intergranular less than 1
Sintering reaction forms uniform doped tungsten oxide product, enters doping oxide mutually in tungsten oxide phase, reduces doping oxide
Phase.
The tungsten oxide activation includes: to heat tungsten oxide under 800-1100 DEG C of inertia or vacuum environment.
Preferably, tungsten oxide activation includes: to mix tungsten oxide with reducing agent, in 800-1100
DEG C inertia or vacuum environment under heat, then heated under 200-500 DEG C of oxidation environment.
In the embodiment of the present invention, the preferred nitrogen protection of inert environments or argon gas protection, the preferred 5-1000Pa's of vacuum environment
Vacuum degree, the vacuum degree of more preferable 100-500Pa.
Tungsten oxide is mixed with reducing agent, is heated under 800-1100 DEG C of inertia or vacuum environment, loses tungsten oxide
Tungsten is not generated again while the oxygen of part, obtains the tungsten oxide particles of multivalent state；Then under 200-500 DEG C of oxidation environment
Heating to remove unreacted reducing agent, but will not aoxidize at a temperature of so low the tungsten oxide particles of formation again, make it still
It is maintained at multivalent state.
Contain WO in the tungsten oxide particles of the multivalent state obtained by above-mentioned processing1~3, that is, contain partial oxidation tungsten, dioxy
Change tungsten or a tungsten oxide, the oxide particle that can thus make is in oxygen debt state, forms N-type semiconductor characteristic, i.e. shape
It is conductive at negative-ion vacancy.Furthermore the addition of oxygen debt type tungsten oxide, moreover it is possible to which the volatilization for reducing tungsten oxide improves the densification of target
Degree.
The present invention is not particularly limited reducing agent, as long as can satisfy makes tungsten oxide oxygen loss, in its dosage of control or instead
Under the premise of between seasonable, tungsten is not generated again while tungsten oxide can be made to lose part oxygen, obtains the tungsten oxide of multivalent state
Particle.Itself can be removed by oxidation simultaneously, will not be introduced into new substance into system of the invention.
The doping oxide activation includes: to add doping oxide under 800-1500 DEG C of inertia or vacuum environment
Heat.
Preferably, doping oxide activation includes: to mix doping oxide with reducing agent,
It heats under 800-1500 DEG C of inertia or vacuum environment, is then heated under 200-500 DEG C of oxidation environment.
It is similar to the activation of above-mentioned tungsten oxide, it is equally herein that doping oxide is made to lose portion to the activation of doping oxide
Divide and do not generate corresponding metal again while oxygen, obtains the doping oxide particle of multivalent state.The oxidation that can thus make
Composition granule is in oxygen debt state, forms N-type semiconductor characteristic, that is, forms negative-ion vacancy and conductive.Different doping oxides
Used temperature, environment and reducing agent are also different.
Preferably, the reducing agent is carbon dust or organic reducing agent.
In the embodiment of the present invention, reducing agent can choose powdered carbon, also can choose organic reducing agent, as hydro carbons, aldehydes,
Alcohols etc., the substance containing carbon, hydrogen is ok, and after redox reaction, they will become carbon dioxide and water and are removed,
New substance will not be introduced into system of the invention.
Preferably, the organic reducing agent is polyvinyl alcohol or methylcellulose.
There are two effects for organic reducing agent tool: an effect is reduction, for making oxide become oxygen debt substance, makes its tool
There is conductive characteristic；Another effect is dispersion, and the oxide particle in the present invention is micron order or nanoscale, and high temperature is easily rolled into a ball
Poly-, the addition of organic reducing agent allows it to be not easy adhesion, keeps former granularity.
By respectively activating tungsten oxide and doping oxide, on the one hand tungsten oxide and doping oxide can be become
For reduction-state, increase the electric conductivity of target；On the other hand it can enhance its activity function.
Preferably, the molar content of doped metallic elements is 0.1-20% in doped tungsten oxide target；
The doped metallic elements are one of titanium, nickel, tantalum, rhenium, iridium, molybdenum, niobium, silicon, tin, zinc, zirconium and germanium or more
Kind.
Preferably, the atmosphere of sintering is reducing atmosphere, inert atmosphere or vacuum atmosphere, the sintering temperature
Degree is 1100-1500 DEG C.
In the embodiment of the present invention, the reason of sintering under reducing atmosphere, inert atmosphere or vacuum atmosphere: preventing green body in height
It is oxidized under temperature or a large amount of oxygen loss, causes oxygen debt insufficient or excessive, final electric conductivity can all had an impact.
Preferably, reducing atmosphere is the mixed gas of inert gas and reducing gas；It is lazy described in wherein
Property gas and reducing gas ratio be 8:2-9.99:0.01.Wherein, inert gas is argon gas or nitrogen, and reducing gas is hydrogen
Gas or carbon monoxide.
A kind of doped tungsten oxide target that another embodiment of the present invention proposes, is prepared by method above-mentioned；It is described
Doped tungsten oxide target be MWO3-x, wherein 0.1 ﹤ x ﹤ 1, M are in titanium, nickel, tantalum, rhenium, iridium, molybdenum, niobium, silicon, tin, zinc, zirconium and germanium
It is one or more.
In the promotion of electric conductivity performance, on the one hand by forming oxygen debt oxide, it is conductive to improve raw material activity, target
Property, the volatilization of tungsten oxide under high temperature is on the other hand reduced by the way that the tungsten oxide of oxygen debt type is added, and improves the consistency of target.
The doped tungsten oxide target that the present invention is prepared is conductive.Direct current or intermediate frequency power supply can be used.
In the embodiment of the present invention, doped tungsten oxide target sintering process belongs to solid-phase sintering, has very with the particle of material
Close relationship.Two kinds of materials are to be uniformly mixed, and particle reduces theoretically, are conducive to be uniformly mixed, in addition for content
Low element can be preferably uniformly mixed if granule number is identical as the granule number of tungsten oxide even more, also more advantageous
In the progress of solid-phase sintering.Therefore, in order to by low content dopant uniform doping, by active oxidation tungsten and activation doping oxide
Fineness ratio connected with molar ratio.
Embodiment 1
The present embodiment proposes a kind of preparation method of doped tungsten oxide target comprising:
Tungstic acid is heated under 1100 DEG C of vacuum environment, makes its activation, grinds and cross sieve classification, obtains activation oxygen
Change tungsten (WO2.5) particle, granularity 500nm；
Titanium oxide is made its activation, grind and simultaneously cross sieve classification, obtain in 1500 DEG C, vacuum degree to heat under conditions of 200Pa
To active oxidation titanium (TiO1.5) particle, granularity 200nm；
Obtained active oxidation tungsten particle and active oxidation titanium particle are uniformly mixed, molar ratio 9:1, at 60Mpa
5min is suppressed, green body is obtained；
Obtained green body is obtained into titanium doped oxidation tungsten target material in 1100 DEG C, vacuum degree to be sintered under conditions of 10Pa.
Embodiment 2
The present embodiment proposes a kind of preparation method of doped tungsten oxide target comprising:
By tungsten oxide (WO2.5) mixed with carbon dust, it is heated under 900 DEG C of inert environments, makes its activation, ground and be sieved
Classification, obtains active oxidation tungsten (WO2) particle, granularity 500nm；
Tantalum oxide is mixed with carbon dust, is heated under 1100 DEG C of inert environments, its activation is made, grinds and cross sieve classification,
Obtain active oxidation tantalum (TaO2) particle, granularity 150nm；
Obtained active oxidation tungsten particle and active oxidation tantalum particle are uniformly mixed, molar ratio 9.5:0.5,
5min is suppressed under 10MPa, obtains green body；
Obtained green body is sintered under 1200 DEG C of reducing atmosphere, wherein reducing atmosphere is the gaseous mixture of argon gas and hydrogen
The ratio of body, argon gas and hydrogen is 8:2, obtains tantalum doped tungsten oxide target.
Embodiment 3
The present embodiment proposes a kind of preparation method of doped tungsten oxide target comprising:
By tungsten oxide (WO3) and polyvinyl alcohol, it is heated under 1000 DEG C of inert environments, makes its activation, grinding is simultaneously
Sieve classification is crossed, active oxidation tungsten (WO is obtained3) particle, granularity 2500nm；
It by nickel oxide and polyvinyl alcohol, is heated under 1300 DEG C of inert environments, makes its activation, ground and cross and sieve
Grade, obtains active oxidation nickel (NiO) particle, granularity 800nm；
Obtained active oxidation tungsten particle and active oxidation nickel particle are uniformly mixed, molar ratio 9:1, at 10MPa
6min is suppressed, green body is obtained；
Obtained green body is sintered under 1300 DEG C of reducing atmosphere, wherein reducing atmosphere is the mixed of nitrogen and carbon monoxide
The ratio of conjunction gas, nitrogen and carbon monoxide is 9.99:0.01, obtains nickel doped tungsten oxide target.
Embodiment 4
The present embodiment proposes a kind of preparation method of doped tungsten oxide target comprising:
By tungsten oxide (WO2.5) mixed with methylcellulose, it is heated under 800 DEG C of inert environments, makes its activation, ground
And sieve classification is crossed, obtain active oxidation tungsten (WO2) particle, granularity 1000nm；
Zinc oxide is mixed with methylcellulose, is heated under 800 DEG C of inert environments, its activation is made, grinds and is sieved
Classification, obtains active oxidation zinc (ZnO) particle, granularity 450nm；
Obtained active oxidation tungsten particle and active oxidation zinc particle are uniformly mixed, molar ratio 8:2, are pressed in 40MPa
10min processed, obtains green body；
Obtained green body is sintered under 1500 DEG C of reducing atmosphere, wherein reducing atmosphere is the gaseous mixture of nitrogen and hydrogen
The ratio of body, nitrogen and hydrogen is 9:1, obtains zinc doping oxidation tungsten target material.
Embodiment 5
The present embodiment proposes a kind of preparation method of doped tungsten oxide target comprising:
By tungsten oxide (WO3) heated under 1000 DEG C of vacuum environment, make its activation, grinds and cross sieve classification, lived
Change tungsten oxide (WO2.8) particle, granularity 500nm；
Tin oxide and nickel oxide are heated under 1500 DEG C of vacuum environment, make its activation, grinds and crosses sieve classification, obtain
Active oxidation tin and nickel oxide (SnO2、NiO0.98) particle, granularity 150nm；
Obtained active oxidation tungsten particle and active oxidation tin and nickel oxide particle are uniformly mixed, molar ratio 9.5:
0.2:0.3 suppresses 10min in 120MPa, obtains green body；
Obtained green body is sintered under 1400 DEG C of vacuum atmosphere, obtains tin nickel doped tungsten oxide target.
Comparative example
This comparative example proposes a kind of preparation method of doped tungsten oxide target comprising:
By granularity be 500nm tungstic acid particle and granularity be 500nm titan oxide particles be uniformly mixed, molar ratio is
9:1 suppresses 5min at 60MPa, obtains green body；
Obtained green body is sintered under 1300 DEG C of vacuum atmosphere, obtains titanium doped oxidation tungsten target material.
The doped tungsten oxide target that embodiment 1-5 and comparative example are prepared is detected respectively, specific testing result
It is listed in Table 1.
The performance test results of 1 doped tungsten oxide target of table
As seen from Table 1,1-5 of the embodiment of the present invention is improved by activating respectively to tungsten oxide and doping oxide
Raw material activity, forms negative-ion vacancy, makes it have the characteristic of N-type semiconductor, and the green body of generation is carried out reduction sintering, into
One step increases negative-ion vacancy, greatly promotes its electric conductivity, so that the resistivity of the target generated reduces, consistency increases,
Film defects number reduces.
The above described is only a preferred embodiment of the present invention, be not intended to limit the present invention in any form, according to
According to technical spirit any simple modification, equivalent change and modification to the above embodiments of the invention, this hair is still fallen within
In the range of bright technical solution.
Claims (10)
1. a kind of preparation method of doped tungsten oxide target, characterized in that it comprises:
By tungsten oxide activation and grinding, active oxidation tungsten is obtained；
By doping oxide activation and grinding, obtain activation doping oxide, wherein M be titanium, nickel, tantalum, rhenium, iridium, molybdenum, niobium,
One of silicon, tin, zinc, zirconium and germanium are a variety of；
The active oxidation tungsten and activation doping oxide are uniformly mixed, suppresses, obtains green body；
By the blank sintering, doped tungsten oxide target is obtained；
Wherein, the active oxidation tungsten and the fineness ratio of activation doping oxide and the relational expression of molar ratio are as follows:
In formula:
RwFor the radius of active oxidation tungsten；
RMFor the radius for activating doping oxide；
nwFor the molal quantity of active oxidation tungsten；
nMFor the molal quantity for activating doping oxide；
MwFor the molal weight of active oxidation tungsten；
MMFor the molal weight for activating doping oxide；
ρwFor the density of active oxidation tungsten；
ρMFor the density for activating doping oxide.
2. the preparation method of doped tungsten oxide target according to claim 1, which is characterized in that activated in the green body
The granule number ratio of tungsten oxide and activation doping oxide is less than 1.
3. the preparation method of doped tungsten oxide target according to claim 1, which is characterized in that the tungsten oxide activation
Include: to mix tungsten oxide with reducing agent, is heated under 800-1100 DEG C of inertia or vacuum environment, then at 200-500 DEG C
Oxidation environment under heat.
4. the preparation method of doped tungsten oxide target according to claim 1, which is characterized in that the doping oxide
Activation includes: to mix doping oxide with reducing agent, heats under 800-1500 DEG C of inertia or vacuum environment, then exists
It is heated under 200-500 DEG C of oxidation environment.
5. the preparation method of doped tungsten oxide target according to claim 3 or 4, which is characterized in that the reducing agent
For carbon dust or organic reducing agent.
6. the preparation method of doped tungsten oxide target according to claim 5, which is characterized in that the organic reducing agent
For polyvinyl alcohol or methylcellulose.
7. the preparation method of doped tungsten oxide target according to claim 1, which is characterized in that the doped tungsten oxide
The molar content of doped metallic elements is 0.1-20% in target.
8. the preparation method of doped tungsten oxide target according to claim 1, which is characterized in that the atmosphere of the sintering
For reducing atmosphere, inert atmosphere or vacuum atmosphere, the temperature of the sintering is 1100-1500 DEG C.
9. the preparation method of doped tungsten oxide target according to claim 8, which is characterized in that the reducing atmosphere is
The mixed gas of inert gas and reducing gas；Wherein the ratio of the inert gas and reducing gas is 8:2-9.99:
0.01。
10. a kind of doped tungsten oxide target, which is characterized in that be prepared by method of any of claims 1-9；
The doped tungsten oxide target is WMO3-x, wherein 0.1 ﹤ x ﹤ 1, M are titanium, nickel, tantalum, rhenium, iridium, molybdenum, niobium, silicon, tin, zinc, zirconium
With one of germanium or a variety of.
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Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN112358294A (en) * | 2020-11-13 | 2021-02-12 | 北京航大微纳科技有限公司 | Hot-pressing sintering preparation method of tungsten oxide-based ceramic target material |
| CN112374887A (en) * | 2020-11-13 | 2021-02-19 | 北京航大微纳科技有限公司 | Gel injection molding preparation method of tungsten oxide-based ceramic target material |
| CN112374542A (en) * | 2020-11-13 | 2021-02-19 | 北京航大微纳科技有限公司 | Submicron-grade doped tungsten oxide-based powder and preparation method and application thereof |
| CN112457009A (en) * | 2020-11-13 | 2021-03-09 | 北京航大微纳科技有限公司 | Hot isostatic pressing sintering preparation method of tungsten oxide-based ceramic target material |
| CN112479707A (en) * | 2020-11-13 | 2021-03-12 | 北京航大微纳科技有限公司 | Cold isostatic pressing preparation method of tungsten oxide-based ceramic target material |
| CN112501566A (en) * | 2020-11-13 | 2021-03-16 | 北京航空航天大学宁波创新研究院 | Tungsten oxide-based ceramic target material, thin film and thin film preparation process |
Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH03150357A (en) * | 1989-11-06 | 1991-06-26 | Nippon Tungsten Co Ltd | Target and production thereof |
| CN102409214A (en) * | 2011-12-01 | 2012-04-11 | 西安理工大学 | Method for preparing W-10Ti alloy from WO3-TiH2 powder |
| CN103572236A (en) * | 2013-11-06 | 2014-02-12 | 河北东同光电科技有限公司 | High-performance niobium oxide target material and preparation method thereof |
| CN104508176A (en) * | 2012-11-02 | 2015-04-08 | 吉坤日矿日石金属株式会社 | Tungsten sintered body sputtering target and tungsten film formed using said target |
| CN106513684A (en) * | 2016-11-10 | 2017-03-22 | 洛阳科威钨钼有限公司 | Production method for tungsten molybdenum alloy rotary target |
| CN108658472A (en) * | 2017-03-31 | 2018-10-16 | 深圳市景创科技电子有限公司 | A kind of preparation method of intelligent glass cathodic electrochromic layer Coating Materials |
-
2019
- 2019-07-26 CN CN201910683562.3A patent/CN110357626B/en active Active
Patent Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH03150357A (en) * | 1989-11-06 | 1991-06-26 | Nippon Tungsten Co Ltd | Target and production thereof |
| CN102409214A (en) * | 2011-12-01 | 2012-04-11 | 西安理工大学 | Method for preparing W-10Ti alloy from WO3-TiH2 powder |
| CN104508176A (en) * | 2012-11-02 | 2015-04-08 | 吉坤日矿日石金属株式会社 | Tungsten sintered body sputtering target and tungsten film formed using said target |
| CN103572236A (en) * | 2013-11-06 | 2014-02-12 | 河北东同光电科技有限公司 | High-performance niobium oxide target material and preparation method thereof |
| CN106513684A (en) * | 2016-11-10 | 2017-03-22 | 洛阳科威钨钼有限公司 | Production method for tungsten molybdenum alloy rotary target |
| CN108658472A (en) * | 2017-03-31 | 2018-10-16 | 深圳市景创科技电子有限公司 | A kind of preparation method of intelligent glass cathodic electrochromic layer Coating Materials |
Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN112358294A (en) * | 2020-11-13 | 2021-02-12 | 北京航大微纳科技有限公司 | Hot-pressing sintering preparation method of tungsten oxide-based ceramic target material |
| CN112374887A (en) * | 2020-11-13 | 2021-02-19 | 北京航大微纳科技有限公司 | Gel injection molding preparation method of tungsten oxide-based ceramic target material |
| CN112374542A (en) * | 2020-11-13 | 2021-02-19 | 北京航大微纳科技有限公司 | Submicron-grade doped tungsten oxide-based powder and preparation method and application thereof |
| CN112457009A (en) * | 2020-11-13 | 2021-03-09 | 北京航大微纳科技有限公司 | Hot isostatic pressing sintering preparation method of tungsten oxide-based ceramic target material |
| CN112479707A (en) * | 2020-11-13 | 2021-03-12 | 北京航大微纳科技有限公司 | Cold isostatic pressing preparation method of tungsten oxide-based ceramic target material |
| CN112501566A (en) * | 2020-11-13 | 2021-03-16 | 北京航空航天大学宁波创新研究院 | Tungsten oxide-based ceramic target material, thin film and thin film preparation process |
| CN112374542B (en) * | 2020-11-13 | 2023-01-24 | 北京航大微纳科技有限公司 | Submicron-grade doped tungsten oxide-based powder and preparation method and application thereof |
| CN112501566B (en) * | 2020-11-13 | 2023-03-14 | 北京航空航天大学宁波创新研究院 | Tungsten oxide-based ceramic target material, thin film and thin film preparation process |
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