CN105821377A - Oxide sintered compact, sputtering target and oxide thin film - Google Patents
Oxide sintered compact, sputtering target and oxide thin film Download PDFInfo
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Abstract
The present invention relates to an oxide sintered compact, a sputtering target and an oxide thin film. The oxide sintered body made of zinc (Zn), indium (In), titanium (Ti), tin (Sn), gallium (Ga), germanium (Ge), and oxygen (O). The content of in the oxide sintered body is 40-80 mol% when Zn is converted to ZnO. The content of In in the oxide sintered body is 3-25 mol% when In is converted to In2O3. The content of Ti in the oxide sintered body is 2-15 mol% when Ti is converted to TiO2. The content of Sn in the oxide sintered body is 5-35 mol% when Sn is converted to SnO2. The content of Ga in the oxide sintered body is 0.5-10 mol% when Ga is converted to Ga2O3. Ge content of the oxide sintered body is 0.5-10 mol% when converted to GeO2. The present invention can perform DC sputtering by means of a low bulk resistance rate and form a transparent conductive film with excellent chemical properties as well as desired refraction and transmittance rates.
Description
Technical field
The present invention relates to oxidate sintered body, sputtering target and sull, especially relate to carry out the oxide sputtering target of DC sputtering and possess the thin film of desired characteristic.
Background technology
In the various optics such as organic EL, liquid crystal display, contact panel, in the case of utilizing visible ray, it is transparent for needing the material used, particularly in the whole region of visible region, it is desirable to have high-transmission rate.It addition, in various optics, it some times happens that the light loss caused by the refractivity with the membrane material constituted, the interface of substrate.For such high-transmission rate, minimizing light loss, prevent reflection, the method having introducing optical adjustment layer (film).
As the characteristic required for optical adjustment layer, the most mainly refractive index, extinction coefficient (high-transmission rate), but in recent years for higher performance, in addition to refractive index, extinction coefficient (high-transmission rate), also require coexisting of the multifrequency natures such as electric conductivity, etching (etchable), resistance to water, amorphous film.In order to make such multifrequency nature coexist, it is difficult in the case of single oxidation film, needs to be mixed with the complex oxide film of many oxide.The complex oxide film of the oxide being particularly mixed with more than ternary is effective.
Usually used as transparent and there is the material of electric conductivity, it is known that ITO (indium oxide-tin oxide), IZO (Indium sesquioxide .-zinc oxide), GZO (gallium oxide/zinc oxide), AZO (alumina-silica zinc) etc. (patent documentation 1～3).But, the problem that these materials exist has: have absorption, easy crystallization in short wavelength region, it is impossible to fully control above-mentioned multifrequency nature etc..
Patent documentation 4 is recorded in IZO, has added other element further, thus improved the mobility of film, carrier density.It addition, the resistivity that Patent Document 5 discloses the IGZO (Indium sesquioxide .-gallium oxide-lead oxide) containing bixbyite structure and spinel structure is low and film forming stability is excellent.But, all it is directed primarily to improve electric conductivity, is not to control above-mentioned multifrequency nature simultaneously.
Additionally, Patent Document 6 discloses and pass through design and production method, thus manufacturing the technology of AZO, GZO of densification, patent documentation 7 is the technology invented by the present inventor, discloses for obtaining the oxidate sintered body possessing the nesa coating of good absorbance and conductivity.But, all there is the problem being difficult to simultaneously regulate multifrequency nature in arbitrary technology.
It should be noted that above technology all uses as nesa coating (electrode), purposes with and electrode adjacent configuration and be used for controlling the film (optics regulates film, protecting film) of optical characteristics etc. and also differ.
It addition, carried out relating to comprising zinc (Zn), indium (In), titanium (Ti), gallium (Ga), germanium (Ge), the sputtering target of oxygen (O) and the invention (patent documentation 8) of thin film made by this target before the present inventor.This thin film shows desired optical characteristics, electric conductivity, good etching, weatherability (high-temp resisting high-humidity resisting), but there is problems in that and is soluble in the aqueous slkali (alkali resistance is low) used when being patterned by photoetching.On the other hand, if the ratio of regulation constitution element, then other characteristic of infringement can be there is, it is difficult to the problem simultaneously controlling alkali resistance and other multifrequency nature.
Prior art literature
Patent documentation
Patent documentation 1: Japanese Unexamined Patent Publication 2007-008780 publication
Patent documentation 2: Japanese Unexamined Patent Publication 2009-184876 publication
Patent documentation 3: Japanese Unexamined Patent Publication 2007-238375 publication
Patent documentation 4: Japanese Unexamined Patent Publication 2013-001919 publication
Patent documentation 5: International Publication WO2011/040028 publication
Patent documentation 6: International Publication WO2008/018402 publication
Patent documentation 7: Japanese Patent No. 5550768
Patent documentation 8: Japanese Patent Application 2014-184377
Summary of the invention
Invent problem to be solved
The problem of the present invention is to provide the sintered body of a kind of electroconductive oxide thin film that can obtain possessing desired optical characteristics and electrical characteristics and good chemical characteristic.The absorbance of this thin film is high and has desired refractive index, also has good electric conductivity and etching, alkali resistance etc., is useful as optics thin film particularly optics regulation thin film such as organic EL, liquid crystal display, touch panels.It addition, the problem of the present invention is to provide the sputtering target that a kind of body resistivity is low, can carry out DC sputtering.It is an object of the invention to improve the characteristic of optics, reduce production cost, and greatly improve film forming characteristics.
Means for solving the above
In order to solve above-mentioned problem, present inventor has performed further investigation, found that: by using the material system of following proposition, can obtain possessing desired optical characteristics and electrical characteristics and the thin film of excellent chemical characteristic, it is furthermore possible to sputter stably film forming by DC, and the characteristic of the optics using this thin film can be improved, improve productivity ratio.
The present inventor is based on this discovery, it is provided that following invention.
1) oxide sintered body, it is characterized in that, comprise zinc (Zn), indium (In), titanium (Ti), stannum (Sn), gallium (Ga), germanium (Ge) and oxygen (O), Zn content is scaled 40～80 moles of %, In content by ZnO and presses In2O3It is scaled 3～25 moles of %, Ti content and presses TiO2It is scaled 2～15 moles of %, Sn content and presses SnO2It is scaled 5～35 moles of %, Ga content and presses Ga2O3It is scaled 0.5～10 mole of %, Ge content and presses GeO2It is scaled 0.5～10 mole of %.
2) such as above-mentioned 1) as described in oxidate sintered body, it is characterized in that, the content of In meets relational expression 3.0≤In/Ti≤5.0 relative to the content of Ti in terms of atomic number ratio, the content of Ga meets relational expression 1.2≤Ga/Ge≤3.0 relative to the content of Ge in terms of atomic number ratio, the content of Zn is relative to In, Ti, Sn, the content of Ga and Ge meets relational expression 0.5≤Zn/ (In+Ti+Sn+Ga+Ge)≤3.0 in terms of atomic number ratio, Sn, the content of In and Ti meets relational expression 1.0≤(Sn+In+Ti)/(Ga+Ge) relative to the content of Ga and Ge in terms of atomic number ratio.
3) such as above-mentioned 1) or 2) as described in oxidate sintered body, it is characterised in that relative density is more than 90%.
4) according to above-mentioned 1)～3) according to any one of oxidate sintered body, it is characterised in that bulk resistor is 10 below Ω cm.
5) a kind of sputtering target, it is characterised in that use above-mentioned 1)～4) according to any one of oxidate sintered body.
6) a kind of thin film, it is characterized in that, comprise zinc (Zn), indium (In), titanium (Ti), stannum (Sn), gallium (Ga), germanium (Ge) and oxygen (O), Zn content is scaled 40～80 moles of %, In content by ZnO and presses In2O3It is scaled 3～25 moles of %, Ti content and presses TiO2It is scaled 2～15 moles of %, Sn content and presses SnO2It is scaled 5～35 moles of %, Ga content and presses Ga2O3It is scaled 0.5～10 mole of %, Ge content and presses GeO2It is scaled 0.5～10 mole of %.
7) such as above-mentioned 6) as described in thin film, it is characterized in that, the content of In meets relational expression 3.0≤In/Ti≤5.0 relative to the content of Ti in terms of atomic number ratio, the content of Ga meets relational expression 1.2≤Ga/Ge≤3.0 relative to the content of Ge in terms of atomic number ratio, the content of Zn meets relational expression 0.5≤Zn/ (In+Ti+Sn+Ga+Ge)≤3.0 relative to the content of In, Ti, Sn, Ga and Ge in terms of atomic number ratio, and the content of Sn, In and Ti meets relational expression 1.0≤(Sn+In+Ti)/(Ga+Ge) relative to the content of Ga and Ge in terms of atomic number ratio.
8) such as above-mentioned 6) or 7) as described in thin film, it is characterised in that the refractive index under wavelength 550nm is 1.95～2.10.
9) such as above-mentioned 6)～8) according to any one of thin film, it is characterised in that the extinction coefficient under wavelength 405nm are less than 0.05.
10) such as above-mentioned 6)～9) according to any one of thin film, it is characterised in that specific insulation is 1k below Ω cm.
Invention effect
According to the present invention, by using above-mentioned shown material system, it is possible to regulation resistivity and refractive index, it can be ensured that good optical characteristics and electric conductivity, and it is able to ensure that good chemical characteristic (etching characteristic, weatherability, alkali resistance coexist).It addition, the present invention can sputter stably film forming by DC, it is possible to improve productivity ratio.
Detailed description of the invention
It is a feature of the present invention that, comprise zinc (Zn), indium (In), titanium (Ti), stannum (Sn), gallium (Ga), germanium (Ge) and oxygen (O), Zn content is scaled 40～80 moles of %, In content by ZnO and presses In2O3It is scaled 3～25 moles of %, Ti content and presses TiO2It is scaled 2～15 moles of %, Sn content and presses SnO2It is scaled 5～35 moles of %, Ga content and presses Ga2O3It is scaled 0.5～10 mole of %, Ge content and presses GeO2It is scaled 0.5～10 mole of %.The oxidate sintered body sputtering target of so composition is comprised, it is possible to form desired optical characteristics (refractive index, absorbance) and electrical characteristics and electroconductive oxide thin film that good chemical characteristic (etching, weatherability, alkali resistance) coexists by use.Especially by add Sn, it is possible to increase alkali resistance and do not damage other characteristic.
The present invention is using zinc (Zn), indium (In), titanium (Ti), stannum (Sn), gallium (Ga), germanium (Ge) and oxygen (O) as constitution element, but can also contain inevitable impurity within this material.It addition, part or all of each metal in sintered body is presented in composite oxides.In the present invention, carry out the content of each metal in regulation sintered body with oxide conversion, this is because: regulate the cooperation of raw material with oxide, and be easy to its scope and technical meaning are described.It should be noted that for common analytical equipment, it may be determined that the content (weight %) of each metallic element rather than the content of oxide.Accordingly, it is determined that when respectively forming of target, the amount (mole %) converted with each oxide of supposition determines the content of each metallic element.
In the present invention, Zn content is scaled 40～80 moles of % by ZnO.During beyond this scope, it is impossible to obtain desired optical characteristics, electrical characteristics, the most preferred.Particularly, when Zn content presses ZnO conversion less than 40 moles of %, the resistance of thin film uprises thus damages the function as conducting film, the most preferred.On the other hand, during more than 80 moles of %, the control of the optical characteristics such as refractive index becomes difficulty, and etching, resistance to water, alkali resistance reduce in addition, the most preferred.
In the present invention, In content presses In2O3It is scaled 3～25 moles of %.During beyond this scope, it is impossible to obtain desired optical characteristics, electrical characteristics, the most preferred.Particularly, when In content is less than 3 moles of %, it is impossible to obtain the additive effect for giving electric conductivity (that is, resistance raises, the most preferred).On the other hand, time more than 25 moles of %, it is seen that the absorption of the light in the short wavelength region of light can become big, the most preferred.It addition, In is trivalent metallic element, in the case of being replaced into other iso-valence metal (such as Al, B etc.), the resistivity of thin film raises, or resistance to water reduces, the most preferred.
In the present invention, Ti content presses TiO2It is scaled 2～15 moles of %.During beyond this scope, it is impossible to obtain desired optical characteristics, electrical characteristics, the most preferred.Particularly, when Ti content is less than 2 moles of %, it is impossible to obtain the additive effect for optics regulation.On the other hand, during more than 15 moles of %, the resistance of thin film uprises thus damages the function as conducting film, the most preferred.Additionally, it is known that Ti oxide is as high-index material, in the case of being replaced into other the metal (such as Bi, Fe, Co etc.) with said function, produce the absorption in visible ray short wavelength region, the most preferred.
In the present invention, Sn content presses SnO2It is scaled 5～35 moles of %.During beyond this scope, it is impossible to obtain desired chemical characteristic (particularly alkali resistance), the most preferred.Particularly, when Sn content is less than 5 moles of %, alkali resistance reduces (can be dissolved in alkali).On the other hand, during more than 35 moles of %, other characteristic (particularly etching: the easy degree of etching) can reduce, the most preferred.It addition, in addition to Sn oxide, as the oxide with alkali resistance, having Ti oxide, In oxide, Zr oxide, Ti oxide, In oxide is constituent originally, when increasing addition to improve alkali resistance, difficulty is become with coexisting of other characteristic, the most preferred.About being replaced into Zr oxide, the resistivity of thin film can rise, the most preferred.
In the present invention, Ga content presses Ga2O3It is scaled 0.5～10 mole of %.During beyond this scope, it is impossible to obtain desired optical characteristics, electrical characteristics, the most preferred.Particularly, when Ga content is less than 0.5 mole of %, it is impossible to obtain for optics regulation, the additive effect of imparting electric conductivity.On the other hand, during more than 10 moles of %, sintered body, the resistance of film raise, the most preferred.It addition, Ga is trivalent metallic element, in the case of being replaced into other iso-valence metal (such as Al, B etc.), resistance raises, or resistance to water reduces, the most preferred.
In the present invention, Ge content presses GeO2It is scaled 0.5～10 mole of %.During beyond this scope, it is impossible to obtain desired optical characteristics, electrical characteristics, the most preferred.Particularly, when Ge content is less than 0.5 mole of %, it is impossible to obtain the additive effect for optics regulation.On the other hand, during more than 10 moles of %, sintered body, the resistance of film raise, the most preferred.It addition, Ge is low-refraction and the metallic element constituting network former, in the case of being replaced into other the metal (such as Si, B etc.) constituting network former, resistance raises, or resistance to water reduces, the most preferred.
In the present invention, it is preferred to make the content of In meet relational expression 3.0≤In/Ti≤5.0 in terms of atomic number ratio relative to the content of Ti, and the content of Ga meets relational expression 1.2≤Ga/Ge≤3.0 relative to the content of Ge in terms of atomic number ratio.During beyond this scope, it is difficult to have desired optical characteristics and electrical characteristics concurrently.Furthermore it is preferred that make the content of Zn meet relational expression 0.5≤Zn/ (In+Ti+Sn+Ga+Ge)≤3.0 in terms of atomic number ratio relative to the content of In, Ti, Sn, Ga and Ge.During beyond this scope, it is difficult to obtain desired optical characteristics and electrical characteristics, the coexisting of good chemical characteristic, and during more than 3.0, the additive effect of In, Ti, Sn, Ga and Ge reduces, and damages weatherability (high-temp resisting high-humidity resisting), etching, alkali resistance sometimes.During it addition, be less than 0.5, it is impossible to obtain desired electric conductivity, damage the function as conducting film sometimes.Furthermore it is preferred that make the content of Sn, In and Ti meet relational expression 1.0≤(Sn+In+Ti)/(Ga+Ge) in terms of atomic number ratio relative to the content of Ga and Ge.During beyond this scope, alkali resistance reduces, the most preferred.
In the case of the sintered body of the present invention uses as sputtering target, preferably relative density is more than 90%.The raising of density has the effect that the uniformity that can improve sputtered film, additionally it is possible to the generation of powder during suppression sputtering.Relative density is more than 90% can be realized by the manufacture method of the sintered body of the present invention described later.
It addition, in the case of the sintered body of the present invention uses as sputtering target, preferably bulk resistor is 10 below Ω cm.By reducing bulk resistor, it is possible to realize by DC spatter film forming.DC sputtering is compared with RF sputtering, and faster, sputtering yield is more excellent for film forming speed, it is possible to increase production capacity.
The thin film of the present invention can use above-mentioned sinter sputtering target to carry out film forming.Can confirm that becoming to be grouped into and being substantially the same of obtained thin film and sputtering target (sintered body).It addition, generally for preventing reflection, reducing light loss, need the material with specific refractive index, the refractive index of needs is different according to device architecture (refractive index of the peripheral tier of optics regulation film).In the present invention, thin film refractive index n under wavelength 550nm can be controlled in the range of 1.95≤n≤2.10.It addition, optics regulation film itself is preferably high-transmission rate (low extinction coefficient), in the present invention, it is possible to obtain the extinction coefficient under wavelength 405nm and be less than 0.05 and absorb few film in the short wavelength region of visible ray.Additionally, optical adjustment layer needs have suitable electric conductivity sometimes for the electrode layer of auxiliary abutment, in the present invention it is possible to the specific insulation of thin film is controlled at 1k below Ω cm.Additionally, the thin film of the present invention is characterised by, possess good etching characteristic, excellent weatherability (high-temp resisting high-humidity resisting) and alkali resistance.
The sintered body of the present invention can manufacture in the following way, weigh, mix the material powder of the oxide powder comprising each composition metal, then this mixed-powder is carried out under inert gas atmosphere or vacuum atmosphere pressure sintering (hot pressing), or after compressing for material powder, this formed body is carried out normal pressure-sintered.Now, sintering temperature is preferably set to more than 900 DEG C and less than 1500 DEG C.When being set smaller than 900 DEG C, it is impossible to obtain densely sintered body, on the other hand, when being set as more than 1500 DEG C, produce composition deviation due to the evaporation of material, density reduces, the most preferred.It addition, pressing pressure is preferably set to 150～500kgf/cm2。
Additionally, in order to improve density, effectively after weighing, mixing material powder, this mixed-powder is calcined (synthesis), then by its Crushing of Ultrafine, and the powder after Crushing of Ultrafine is used as sintering powder.By so carrying out pre-synthesis and Crushing of Ultrafine, it is possible to obtain the material powder of fine uniform structure such that it is able to make fine and close sintered body.About the particle diameter after Crushing of Ultrafine, mean diameter be below 5 μm, preferably mean diameter be below 2 μm.It addition, calcining heat is preferably set to more than 800 DEG C and less than 1200 DEG C.By being set as such scope, agglutinating property is good, it is possible to improve density further.
Embodiment
Illustrate below based on embodiment and comparative example.It should be noted that the present embodiment only example, the present invention is not by any restriction of this example.That is, the present invention is the most limited by the claims, comprises the various deformation beyond the embodiment that the present invention is comprised.
Evaluation methodologys in embodiment, comparative example etc. are as described below.
(being grouped into about one-tenth)
Device: the SPS3500DD that SII company manufactures
Method: ICP-OES (high-frequency inductive coupling plasma body luminescence analysis)
(about density measurement)
Dimension measurement (slide gauge), gravimetry
(about relative density)
As described below, use solid density to calculate.
Relative density (%)=apparent density/solid density × 100
Solid density is by the oxide conversion mix calculation of each metallic element.
The ZnO converted weight of Zn is being set to a (weight %), the In of In2O3Converted weight is set to b (weight %), the TiO of Ti2Converted weight is set to c (weight %), the SnO of Sn2Converted weight is set to d (weight %), the Ga of Ga2O3Converted weight is set to e (weight %), the GeO of Ge2When converted weight is set to f (weight %),
Solid density=100/ (a/5.61+b/7.18+c/4.26+d/7.00+e/5.95+f/4.70).
It addition, the oxide reduction density of each metallic element uses following values.
ZnO:5.61g/cm3、In2O3: 7.18g/cm3、
TiO2: 4.26g/cm3、SnO2: 7.00g/cm3、
Ga2O3: 5.95g/cm3、GeO2: 4.70g/cm3
(about bulk resistor, specific insulation)
Device: the determination of resistivity device ∑-5+ that NPS company manufactures
Method: DC four point probe method
(about film build method, condition)
Device: ANELVASPL-500
Substrate: φ 4 inches
Substrate temperature: room temperature
(about refractive index, extinction coefficient)
Device: the spectrophotometer UV-2450 that SHIMADZU company manufactures
Mensuration sample:
Membrane sample and non-film forming glass substrate is become on the glass substrate of more than thickness 500nm
Determination data:
(one-tenth membrane sample): the reflectance (being respectively provided with backside reflection) of the reflectance of pellicular front and absorbance and real estate
(glass substrate): there is the reflectance of backside reflection and absorbance, not there is the reflectance of backside reflection
Computational methods: calculated (little pediment letter work, the rationale of optical thin film, Co., Ltd. オ プ ト ロ ニ Network ス company, (2006), 126-131) based on following data by determination data
(about etching, high-temp resisting high-humidity resisting, alkali resistance)
Etching test: the situation utilizing various acid to etch is judged to zero, by utilize various acid not etch or the situation of excessive dissolution be judged to ×.
High-temp resisting high-humidity resisting (weatherability) is tested: after preserving 48 hours under the conditions of temperature 80 DEG C, humidity 80%, implement optical constant and resistance measurement, before and after high temperature and humidity test, the characteristic difference situation less than 10% is judged to zero, the situation that characteristic difference is more than 10% is judged to ×.
Alkaline resistance test: one-tenth membrane sample impregnated in alkaline solution (3 weight %KOH aqueous solution: pH about 13,35 DEG C) before and after 5 minutes, implement optical constant and resistance measurement, the characteristic difference situation less than 10% is judged to zero, the situation that characteristic difference is more than 10% is judged to ×.
(embodiment 1)
Prepare ZnO powder, In2O3Powder, TiO2Powder, SnO2Powder, Ga2O3Powder, GeO2These powder are deployed into the match ratio described in table 1, and are mixed by powder.It follows that by this mixed-powder in an atmosphere, calcine at temperature 1050 DEG C, then (use ZrO by wet type Crushing of Ultrafine2Microballon) it is crushed to below mean diameter 2 μm, sieve with the sieve of mesh 150 μm after drying.Then, by this micropowder flour in an ar atmosphere, temperature 1100 DEG C, pressure 250kgf/cm2Under conditions of hot pressed sintering.Then, by machining, this sintered body is finish-machined to sputtering target shape.Body resistivity and relative density to the target obtained are measured, and result is as shown in table 1, and relative density reaches 99.3%, and bulk resistor is 0.10 Ω cm, it is possible to carry out stable DC sputtering.It addition, the one-tenth of sputtering target is grouped into the result being analyzed is to confirm identical with the match ratio of material powder.
The target using above-mentioned polish and obtain sputters.Sputtering condition is set as: DC sputtering, sputtering power 500W, ar pressure 0.5Pa containing 0.8 volume % oxygen, film forming is thicknessMeasure into the refractive index (wavelength 550nm) of membrane sample, extinction coefficient (wavelength 405nm), specific insulation.As shown in table 1, the refractive index of the thin film formed by sputtering is 2.00, and extinction coefficient are less than 0.01, and specific insulation is 1 × 103Below Ω cm, has obtained desired optical characteristics and electric conductivity.It addition, etching, high-temp resisting high-humidity resisting (weatherability), these chemical characteristics of alkali resistance are the best.
(embodiment 2～11)
About embodiment 2～11, prepare ZnO powder, In2O3Powder, TiO2Powder, SnO2Powder, Ga2O3Powder, GeO2These powder are deployed into the match ratio described in table 1, and are mixed by powder.It follows that carry out this mixed-powder similarly to Example 1 calcining, pulverize, be dried, sieve, then under conditions of similarly to Example 1, micropowder flour is carried out hot pressed sintering.Then, by machining, this sintered body is finish-machined to sputtering target shape.Bulk resistor and relative density to the target obtained are measured, and result is as shown in table 1, and relative density is more than 90%, and bulk resistor is 10 below Ω cm, it is possible to carry out stable DC sputtering.
Then, the target using above-mentioned polish and obtain sputters.Sputtering condition is set as same as in Example 1.Measure into the refractive index (wavelength 550nm) of membrane sample, extinction coefficient (wavelength 405nm), specific insulation.Result is as shown in table 1, and the refractive index of the thin film formed by sputtering is 1.95～2.10, and extinction coefficient are less than 0.05, and specific insulation is 1 × 103Below Ω cm, has obtained desired optical characteristics and electric conductivity.It addition, etching, high-temp resisting high-humidity resisting (weatherability), these chemical characteristics of alkali resistance are the best.
(comparative example 1)
Comparative example 1 is free from the example of Sn.
Prepare ZnO powder, In2O3Powder, TiO2Powder, Ga2O3Powder, GeO2These powder are deployed into the match ratio described in table 1, and are mixed by powder.It follows that carry out this mixed-powder similarly to Example 1 calcining, pulverize, be dried, sieve, then under conditions of similarly to Example 1, micropowder flour is carried out hot pressed sintering.Then, by machining, this sintered body is finish-machined to sputtering target shape.It follows that the target using above-mentioned polish and obtaining sputters.Sputtering condition is set as same as in Example 1.The result carrying out confirming about the chemical characteristic etc. becoming membrane sample is as shown in table 1, obtains the result of alkali resistance difference.
(comparative example 2)
Comparative example 2 is that the content of Sn is less than the example of the amount of regulation in the present invention.
Prepare ZnO powder, In2O3Powder, TiO2Powder, SnO2Powder, Ga2O3Powder, GeO2These powder are deployed into the match ratio described in table 1, and are mixed by powder.It follows that carry out this mixed-powder similarly to Example 1 calcining, pulverize, be dried, sieve, then under conditions of similarly to Example 1, micropowder flour is carried out hot pressed sintering.Then, by machining, this sintered body is finish-machined to sputtering target shape.It follows that the target using above-mentioned polish and obtaining sputters.Sputtering condition is set as same as in Example 1.The result carrying out confirming about the chemical characteristic etc. becoming membrane sample is as shown in table 1, obtains the result of alkali resistance difference.
(comparative example 3)
Comparative example 3 is that the content of Sn is more than the example of the amount of regulation in the present invention.
Prepare ZnO powder, In2O3Powder, TiO2Powder, SnO2Powder, Ga2O3Powder, GeO2These powder are deployed into the match ratio described in table 1, and are mixed by powder.It follows that carry out this mixed-powder similarly to Example 1 calcining, pulverize, be dried, sieve, then under conditions of similarly to Example 1, micropowder flour is carried out hot pressed sintering.Then, by machining, this sintered body is finish-machined to sputtering target shape.It follows that the target using above-mentioned polish and obtaining sputters.But, the target obtained is as shown in table 1, and bulk resistor is more than 500k Ω cm, it is difficult to carries out DC sputtering, therefore carries out RF sputtering.Sputtering condition is set as: sputtering power 500W, ar pressure 0.5Pa containing 0.8 volume % oxygen, film forming is thickness The result carrying out confirming about the chemical characteristic etc. becoming membrane sample is as shown in table 1, and obtaining film is high resistance, the result of etching difference.
(comparative example 4)
Comparative example 4 is that the content of Zn is more than the example of the amount of regulation in the present invention.
Prepare ZnO powder, In2O3Powder, TiO2Powder, SnO2Powder, Ga2O3Powder, GeO2These powder are deployed into the match ratio described in table 1, and are mixed by powder.It follows that carry out this mixed-powder similarly to Example 1 calcining, pulverize, be dried, sieve, then under conditions of similarly to Example 1, micropowder flour is carried out hot pressed sintering.Then, by machining, this sintered body is finish-machined to sputtering target shape.It follows that the target using above-mentioned polish and obtaining sputters.Sputtering condition is set as same as in Example 1.The result carrying out confirming about the chemical characteristic etc. becoming membrane sample is as shown in table 1, obtains etching (excessive dissolution), weatherability, the result of alkali resistance inequality.
(comparative example 5)
Comparative example 5 is that the content of Ge is more than the example of the amount (Ga/Ge ratio is little) of regulation in the present invention.
Prepare ZnO powder, In2O3Powder, TiO2Powder, SnO2Powder, Ga2O3Powder, GeO2These powder are deployed into the match ratio described in table 1, and are mixed by powder.It follows that carry out this mixed-powder similarly to Example 1 calcining, pulverize, be dried, sieve, then under conditions of similarly to Example 1, micropowder flour is carried out hot pressed sintering.Then, by machining, this sintered body is finish-machined to sputtering target shape.It follows that the target using above-mentioned polish and obtaining sputters.But, the target obtained is as shown in table 1, and bulk resistor is more than 500k Ω cm, it is difficult to carries out DC sputtering, therefore carries out RF sputtering.Sputtering condition is set as identical with comparative example 3.The result carrying out confirming about the chemical characteristic etc. becoming membrane sample is as shown in table 1, and obtaining film is high resistance, the result of alkali resistance difference.
(comparative example 6)
Comparative example 6 is that the content of In is less than the example of the amount (In/Ti ratio is little) of regulation in the present invention.
Prepare ZnO powder, In2O3Powder, TiO2Powder, SnO2Powder, Ga2O3Powder, GeO2These powder are deployed into the match ratio described in table 1, and are mixed by powder.It follows that carry out this mixed-powder similarly to Example 1 calcining, pulverize, be dried, sieve, then under conditions of similarly to Example 1, micropowder flour is carried out hot pressed sintering.Then, by machining, this sintered body is finish-machined to sputtering target shape.It follows that the target using above-mentioned polish and obtaining sputters.Sputtering condition is set as same as in Example 1.The result carrying out confirming about the chemical characteristic etc. becoming membrane sample is as shown in table 1, and obtaining film is high resistance, the result of alkali resistance difference.
(comparative example 7)
Comparative example 7 is that the content of In is more than the example of the amount (In/Ti ratio is big) of regulation in the present invention.
Prepare ZnO powder, In2O3Powder, TiO2Powder, SnO2Powder, Ga2O3Powder, GeO2These powder are deployed into the match ratio described in table 1, and are mixed by powder.It follows that carry out this mixed-powder similarly to Example 1 calcining, pulverize, be dried, sieve, then under conditions of similarly to Example 1, micropowder flour is carried out hot pressed sintering.Then, by machining, this sintered body is finish-machined to sputtering target shape.It follows that the target using above-mentioned polish and obtaining sputters.Sputtering condition is set as same as in Example 1.As shown in table 1 about the result becoming the refractive index (wavelength 550nm) of membrane sample, extinction coefficient (wavelength 405nm) etc. to be measured, extinction coefficient are 0.06, do not obtain desired optical characteristics.
(comparative example 8)
Comparative example 8 is that the content of Zn is less than the example of the amount of regulation in the present invention.
Prepare ZnO powder, In2O3Powder, TiO2Powder, SnO2Powder, Ga2O3Powder, GeO2These powder are deployed into the match ratio described in table 1, and are mixed by powder.It follows that carry out this mixed-powder similarly to Example 1 calcining, pulverize, be dried, sieve, then under conditions of similarly to Example 1, micropowder flour is carried out hot pressed sintering.Then, by machining, this sintered body is finish-machined to sputtering target shape.It follows that the target using above-mentioned polish and obtaining sputters.Sputtering condition is set as same as in Example 1.As shown in table 1 about the result becoming the specific insulation etc. of membrane sample to be measured, specific insulation is more than 1 × 103Ω cm, does not obtains desired electric conductivity.
Industrial applicability
The sintered body of the present invention can make sputtering target; the thin film formed by use sputtering target; as the nesa coating in various display, the protecting film of CD, optics regulation film, have the effect that, at aspects such as absorbance, refractive index, electric conductivity, there is the most excellent characteristic.Additionally, also have the effect that and the chemical characteristics such as good etching, weatherability (resistance to water), alkali resistance can be made to coexist.
It addition, the bulk resistance of the sputtering target of the present invention is low, relative density is more than 90%, and density is high, therefore, it is possible to carry out stable DC sputtering.And, also there is following remarkable result: the controlling of the sputtering of the feature sputtered as this DC can be made to become easy, improve film forming speed, improve sputtering yield.It addition, the powder (dust) produced when can reduce the sputtering when film forming, dross, in the case of quality fluctuations is little, improve production.
Claims (10)
1. an oxide sintered body, it is characterized in that, comprise zinc (Zn), indium (In), titanium (Ti), stannum (Sn), gallium (Ga), germanium (Ge) and oxygen (O), Zn content is scaled 40～80 moles of %, In content by ZnO and presses In2O3It is scaled 3～25 moles of %, Ti content and presses TiO2It is scaled 2～15 moles of %, Sn content and presses SnO2It is scaled 5～35 moles of %, Ga content and presses Ga2O3It is scaled 0.5～10 mole of %, Ge content and presses GeO2It is scaled 0.5～10 mole of %.
2. oxidate sintered body as claimed in claim 1, it is characterized in that, the content of In meets relational expression 3.0≤In/Ti≤5.0 relative to the content of Ti in terms of atomic number ratio, the content of Ga meets relational expression 1.2≤Ga/Ge≤3.0 relative to the content of Ge in terms of atomic number ratio, the content of Zn meets relational expression 0.5≤Zn/ (In+Ti+Sn+Ga+Ge)≤3.0 relative to the content of In, Ti, Sn, Ga and Ge in terms of atomic number ratio, and the content of Sn, In and Ti meets relational expression 1.0≤(Sn+In+Ti)/(Ga+Ge) relative to the content of Ga and Ge in terms of atomic number ratio.
3. oxidate sintered body as claimed in claim 1 or 2, it is characterised in that relative density is more than 90%.
4. the oxidate sintered body as according to any one of claims 1 to 3, it is characterised in that bulk resistor is 10 below Ω cm.
5. a sputtering target, it is characterised in that use the oxidate sintered body according to any one of claim 1～4.
6. a thin film, it is characterized in that, comprise zinc (Zn), indium (In), titanium (Ti), stannum (Sn), gallium (Ga), germanium (Ge) and oxygen (O), Zn content is scaled 40～80 moles of %, In content by ZnO and presses In2O3It is scaled 3～25 moles of %, Ti content and presses TiO2It is scaled 2～15 moles of %, Sn content and presses SnO2It is scaled 5～35 moles of %, Ga content and presses Ga2O3It is scaled 0.5～10 mole of %, Ge content and presses GeO2It is scaled 0.5～10 mole of %.
7. thin film as claimed in claim 6, it is characterized in that, the content of In meets relational expression 3.0≤In/Ti≤5.0 relative to the content of Ti in terms of atomic number ratio, the content of Ga meets relational expression 1.2≤Ga/Ge≤3.0 relative to the content of Ge in terms of atomic number ratio, the content of Zn meets relational expression 0.5≤Zn/ (In+Ti+Sn+Ga+Ge)≤3.0 relative to the content of In, Ti, Sn, Ga and Ge in terms of atomic number ratio, and the content of Sn, In and Ti meets relational expression 1.0≤(Sn+In+Ti)/(Ga+Ge) relative to the content of Ga and Ge in terms of atomic number ratio.
Thin film the most as claimed in claims 6 or 7, it is characterised in that the refractive index under wavelength 550nm is 1.95～2.10.
9. the thin film as according to any one of claim 6～8, it is characterised in that the extinction coefficient under wavelength 405nm are less than 0.05.
10. the thin film as according to any one of claim 6～9, it is characterised in that specific insulation is 1k below Ω cm.
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| JP2015010453A JP5735190B1 (en) | 2015-01-22 | 2015-01-22 | Oxide sintered body, sputtering target, and oxide thin film |
| JP2015-010453 | 2015-01-22 |
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| JP (1) | JP5735190B1 (en) |
| KR (1) | KR101600261B1 (en) |
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| CN110741106A (en) * | 2017-08-08 | 2020-01-31 | 三井金属矿业株式会社 | Oxide sintered body and sputtering target |
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| JP2019163494A (en) * | 2018-03-19 | 2019-09-26 | 住友金属鉱山株式会社 | Transparent oxide film, method of manufacturing transparent oxide film, oxide sintered body and transparent resin substrate |
| CN114008237B (en) | 2019-06-28 | 2024-06-25 | 株式会社爱发科 | Sputtering target and method for producing sputtering target |
| WO2024057672A1 (en) * | 2022-09-16 | 2024-03-21 | 株式会社アルバック | Sputtering target for formation of oxide semiconductor thin film, method for producing sputtering target for formation of oxide semiconductor thin film, oxide semiconductor thin film, thin film semiconductor device and method for producing same |
| WO2024057671A1 (en) * | 2022-09-16 | 2024-03-21 | 株式会社アルバック | Sputtering target for oxide semiconductor thin film formation, method for producing sputtering target for oxide semiconductor thin film formation, oxide semiconductor thin film, and thin film semiconductor device and method for producing same |
| JP7425933B1 (en) | 2022-09-16 | 2024-01-31 | 株式会社アルバック | Sputtering target for forming an oxide semiconductor thin film, method for manufacturing a sputtering target for forming an oxide semiconductor thin film, oxide semiconductor thin film, thin film semiconductor device, and method for manufacturing the same |
Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH0769630A (en) * | 1993-08-31 | 1995-03-14 | Mitsubishi Materials Corp | Zinc oxide powder excellent in dispersibility |
| WO2008018402A1 (en) * | 2006-08-11 | 2008-02-14 | Hitachi Metals, Ltd. | Zinc oxide sinter, process for producing the same, and sputtering target |
| JP2009263709A (en) * | 2008-04-24 | 2009-11-12 | Hitachi Ltd | Sputtering target for depositing zinc oxide thin film, and display device and solar cell having zinc oxide thin film obtained by using the target, |
| JP2010285321A (en) * | 2009-06-12 | 2010-12-24 | Sumitomo Metal Mining Co Ltd | Method for manufacturing zinc oxide-based sintered compact for sputtering target |
| CN102597302A (en) * | 2009-11-19 | 2012-07-18 | 出光兴产株式会社 | In-Ga-Zn-O oxide sintered body sputtering target having excellent stability In long-term film formation |
Family Cites Families (15)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5672427A (en) * | 1993-08-31 | 1997-09-30 | Mitsubishi Materials Corporation | Zinc oxide powder having high dispersibility |
| JPH10306367A (en) * | 1997-05-06 | 1998-11-17 | Sumitomo Metal Mining Co Ltd | Zno-ga2o3 sintered body for sputtering target and its production |
| JP4758697B2 (en) | 2005-07-01 | 2011-08-31 | 出光興産株式会社 | Manufacturing method of IZO sputtering target |
| JP4797712B2 (en) | 2006-03-08 | 2011-10-19 | 東ソー株式会社 | ZnO-Al2O3-based sintered body, sputtering target, and method for producing transparent conductive film |
| JP5369444B2 (en) | 2008-02-06 | 2013-12-18 | 住友金属鉱山株式会社 | GZO sintered body manufacturing method |
| JP5288142B2 (en) * | 2008-06-06 | 2013-09-11 | 出光興産株式会社 | Sputtering target for oxide thin film and manufacturing method thereof |
| US20120184066A1 (en) | 2009-09-30 | 2012-07-19 | Idemitsu Kosan Co., Ltd. | SINTERED In-Ga-Zn-O-TYPE OXIDE |
| JP2011187509A (en) * | 2010-03-04 | 2011-09-22 | Fujifilm Corp | Electronic element substrate and method of manufacturing the same |
| JP5723262B2 (en) * | 2010-12-02 | 2015-05-27 | 株式会社神戸製鋼所 | Thin film transistor and sputtering target |
| CN103534382B (en) * | 2011-05-10 | 2016-01-20 | 出光兴产株式会社 | In2O3-SnO2-ZnO sputtering target |
| JP2013001919A (en) | 2011-06-13 | 2013-01-07 | Idemitsu Kosan Co Ltd | In2O3-ZnO-BASED SPUTTERING TARGET AND OXIDE CONDUCTIVE FILM |
| WO2013179676A1 (en) * | 2012-05-31 | 2013-12-05 | 出光興産株式会社 | Sputtering target |
| JP5550768B1 (en) | 2012-07-03 | 2014-07-16 | Ｊｘ日鉱日石金属株式会社 | Sintered body and amorphous film |
| TW201422835A (en) * | 2012-12-03 | 2014-06-16 | Solar Applied Mat Tech Corp | Sputtering target and conductive metal oxide film |
| JP6098269B2 (en) | 2013-03-22 | 2017-03-22 | 東レ株式会社 | Hollow fiber membrane module, method for producing hollow fiber membrane module, water purifier cartridge and water purifier |
-
2015
- 2015-01-22 JP JP2015010453A patent/JP5735190B1/en active Active
- 2015-07-23 KR KR1020150104463A patent/KR101600261B1/en active IP Right Grant
- 2015-07-27 TW TW104124233A patent/TWI564250B/en active
- 2015-09-06 CN CN201510561233.3A patent/CN105821377B/en active Active
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH0769630A (en) * | 1993-08-31 | 1995-03-14 | Mitsubishi Materials Corp | Zinc oxide powder excellent in dispersibility |
| WO2008018402A1 (en) * | 2006-08-11 | 2008-02-14 | Hitachi Metals, Ltd. | Zinc oxide sinter, process for producing the same, and sputtering target |
| JP2009263709A (en) * | 2008-04-24 | 2009-11-12 | Hitachi Ltd | Sputtering target for depositing zinc oxide thin film, and display device and solar cell having zinc oxide thin film obtained by using the target, |
| JP2010285321A (en) * | 2009-06-12 | 2010-12-24 | Sumitomo Metal Mining Co Ltd | Method for manufacturing zinc oxide-based sintered compact for sputtering target |
| CN102597302A (en) * | 2009-11-19 | 2012-07-18 | 出光兴产株式会社 | In-Ga-Zn-O oxide sintered body sputtering target having excellent stability In long-term film formation |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110741106A (en) * | 2017-08-08 | 2020-01-31 | 三井金属矿业株式会社 | Oxide sintered body and sputtering target |
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| CN105821377B (en) | 2017-03-29 |
| KR101600261B1 (en) | 2016-03-09 |
| TWI564250B (en) | 2017-01-01 |
| JP5735190B1 (en) | 2015-06-17 |
| TW201627226A (en) | 2016-08-01 |
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