CN101208453B - Gallium oxide-zinc oxide sputtering target, method of forming transparent conductive film and transparent conductive film - Google Patents
Gallium oxide-zinc oxide sputtering target, method of forming transparent conductive film and transparent conductive film Download PDFInfo
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Abstract
Provided is a high density gallium oxide-zinc oxide series sintered body sputtering target for forming a transparent conductive film containing 20 to 500 mass ppm of aluminum oxide. In a gallium oxide(Ga 2 O 3 )-zinc oxide (ZnO) series sputtering target (GZO series target) for forming a transparent conductive film, trace amounts of specific elements are added to obtain a target capable of improving the conductivity and the bulk density of the target; in other words, capable of improving the component composition to increase the sintered density, inhibit the formation of nodules, and prevent the generation of an abnormal electrical discharge and particles. Also provided are a method for forming a transparent conductive film using such a target, and a transparent conductive film formed thereby.
Description
Technical field
The present invention relates to a kind of gallium oxide (Ga that can obtain to keep the nesa coating of good visible light transmissivity and electroconductibility
2O
3)-zinc oxide (ZnO) base sputtering target (GZO is a target) and the nesa coating that uses this target to form the method for nesa coating and form thus.
Background technology
All the time, as ITO (doped tin in Indium sesquioxide) the film transparent and electrically conductive excellence of nesa coating, be used for the purposes of broad scopes such as the transparency electrode (film) of display equipments such as liquid-crystal display, electroluminescent display or solar cell.But the problem that this ITO exists is, owing to cost an arm and a leg as the indium of main component, therefore is in a disadvantageous position aspect manufacturing cost.
According to this present situation, have and use of the motion of GZO film as the substitute of ITO.Because this GZO is with gallium oxide (Ga
2O
3)-zinc oxide (ZnO) is the zinc oxide mesentery of main component, therefore has cheap advantage.Known GZO film is because of the damaged phenomenon that has electroconductibility to increase of oxygen as the ZnO of main component, as long as the membrane property of its electroconductibility and photopermeability and so on is near ITO, its utilization ratio just might increase.
As the method that forms this GZO film, mainly be to utilize sputtering method to form this GZO film, especially consider from the stable aspect of operability and film, can utilize direct current (DC) sputter or high frequency (RF) sputter or magnetron sputtering system to form this GZO film.
Utilizing sputtering method to form film is undertaken by following operation, promptly, make positive ion physical impacts such as Ar ion be arranged at the target of negative electrode, the material that utilizes its impact energy to make to constitute target discharges, will be with target material roughly with the film lamination of forming on the substrate of opposed anode side.
And, utilize the lining method of this sputtering method to be characterised in that, by adjusting treatment time, supply capability etc., the film that can with the dust be unit with stable film forming speed formation is to the thick film of tens of μ m.
The nesa coating that has many motions to relate to be used to form the sinter sputtering target of such GZO film or form thus.
For example, motion is in patent documentation 1, and its part has Ga as not producing paradoxical discharge, can forming the Zinc oxide sintered body target with stable film in its a part of target material
2O
3-ZnO target sintered compact, and optionally be added with 1～5 weight % titanium oxide, germanium oxide, aluminum oxide, magnesium oxide, Indium sesquioxide, stannic oxide be the target of main component with zinc oxide.
Motion is in patent documentation 2, as not producing paradoxical discharge, can form the GZO sinter sputtering target of film with stability, while with zinc oxide and gallium oxide powder make particle diameter fine to 1 μ m powder, sintering temperature is adjusted into 1300～1550 ℃, imports that oxygen carries out sintering and the technology that improves its density.
Motion is in patent documentation 3, during as life-time service paradoxical discharge take place less, transmitance height and the low GZO sinter sputtering target of resistance value, be added with the ZnO class sintered compact that is selected from the 3rd element among Al, B, In, Ge, Si, Sn, the Ti of Ga, 0.3～3 atom % of 3～7 atom %.
Motion is in patent documentation 4, in order to prevent the reaction of zinc oxide and water electrical characteristic, optical characteristics is changed, and carries out the technology of sputter in the atmosphere that is formed by hydrogen and rare gas element.
Generally speaking, debatablely especially when forming the GZO film be, erosion portion along with sputter on the target surface produces the micro crowning thing that is called as tuberculosis (nodule), and paradoxical discharge or splash meeting that this tuberculosis causes cause thick particle (particle) to float in sputtering chamber, and these particles are attached on the film of formation and cause its quality to descend.In addition, above-mentioned paradoxical discharge causes the plasma discharge state labile, also can produce and can't stablize film forming problem.
Thereby, when on substrate, forming conducting film, must regularly remove the tuberculosis that produces on the sputtering target, so can cause production efficiency significantly to reduce, therefore, expect that the target of paradoxical discharge phenomenon takes place less, not take place a kind of tuberculosis.
Especially recently the trend that has indicating meter to maximize requires the big area film forming, therefore, needs especially to stablize film forming target.
Above-mentioned patent documentation has been pointed out the problem of paradoxical discharge, as the countermeasure that reduces paradoxical discharge, what propose in the aforesaid patent documentation 1 is titanium oxide, germanium oxide, aluminum oxide, magnesium oxide, Indium sesquioxide, the stannic oxide that optionally adds 1～5 weight %, and what propose in patent documentation 3 is the 3rd element among Al, B, In, Ge, Si, Sn, the Ti of being selected from that adds 0.3～3 atom %.
These countermeasures all are to prevent paradoxical discharge by the emptying aperture in the density that improves sintered compact, the minimizing sintered compact.But,, yet exist sintered density fully not rise and the high problem of volume (bulk) resistance value even utilize such interpolation material.
In addition, also have the improvement of the manufacturing process of target, complicated manufacturing process is the major cause that causes cost to raise, and improvement sintering method or device and when density was risen, existence need make the problem of equipment enlarging, at the industrial effective means of can not saying so.
In general, be grouped into by the one-tenth that adds trace element, promptly changes the GZO sintered compact, for the density that improves target, to prevent to form tuberculosis, suppress the paradoxical discharge phenomenon and produce for the particle be simple effective method, but the change that becomes to be grouped into makes the volume resistance value variation of target sometimes, and sintered density also differs and improves surely, therefore the sufficient countermeasure of can't saying so of the example shown in the above-mentioned patent documentation.
Patent documentation 1: Japanese kokai publication hei 10-306367 communique
Patent documentation 2: Japanese kokai publication hei 10-297964 communique
Patent documentation 3: Japanese kokai publication hei 11-256320 communique
Patent documentation 4: TOHKEMY 2002-363732 communique
Summary of the invention
In view of above-mentioned prior art problems, gallium oxide (Ga of the present invention
2O
3)-zinc oxide (ZnO) base sputtering target (GZO is a target), add the regulation element of trace, can improve its electroconductibility and density, promptly improve and become to be grouped into, can improve sintered density, suppress the formation of tuberculosis, prevent that paradoxical discharge and particulate from taking place, when obtaining such target, also provide a kind of nesa coating that uses this target to form the method for nesa coating and form thus.
In sum, the invention provides:
1) a kind of high-density gallium oxide-zinc oxide sinter sputtering target is characterized in that it contains the aluminum oxide of 20～500 quality ppm.
2) as above-mentioned 1) described gallium oxide-zinc oxide sinter sputtering target, it is characterized in that it contains the gallium oxide of 0.1～10 quality %.
3) as above-mentioned 1) or 2) described high-density gallium oxide-zinc oxide sinter sputtering target, it is characterized in that its sintered density is 5.55g/cm
3More than.
4) as above-mentioned 1)～3) in each described high-density gallium oxide-zinc oxide sinter sputtering target, it is characterized in that the volume resistance value of described target is below the 3.0m Ω cm.
5) a kind of formation method of nesa coating, it is characterized in that, use contains the gallium oxide-zinc oxide target of the aluminum oxide of 20～500 quality ppm, utilizes sputtering method to form the film that the gallium oxide/zinc oxide by the aluminum oxide that contains 20～500 quality ppm constitutes on substrate.
6) as above-mentioned 5) the formation method of described nesa coating, it is characterized in that, contain the gallium oxide of 0.1～10 quality % in the described nesa coating.
7) a kind of nesa coating of the excellent electric conductivity that is made of gallium oxide-zinc oxide is characterized in that it is to utilize sputter to be formed at the nesa coating of the aluminum oxide that contains 20～500 quality ppm on the substrate.
8) as above-mentioned 7) nesa coating of described excellent electric conductivity, it is characterized in that, contain the gallium oxide of 0.1～10 quality % in the described nesa coating.
Gallium oxide (Ga of the present invention
2O
3)-zinc oxide (ZnO) base sputtering target (GZO is a target) has following excellent effect,, contains the aluminum oxide (Al of 20～500 quality ppm by making it that is
2O
3), the target that can obtain having following feature, that is, when significantly improving target density, it is constant suppressing the volume resistance value, suppresses the formation along with these tuberculosis that produce when the spatter film forming, the life-time service paradoxical discharge is few, and can prevent that particulate from taking place.
And, also have following unusual effect, that is, use this target can form transmitance height, nesa coating that resistance value is low, a kind of nesa coating that forms thus can be provided.
Description of drawings
Fig. 1 is that expression the application's the embodiment and the GZO of comparative example are target aluminum oxide (Al when 1400 ℃ of sintering
2O
3) figure of relation of addition and sintered density and volume resistance value.
Fig. 2 is that expression the application's the embodiment and the GZO of comparative example are target aluminum oxide (Al when 1450 ℃ of sintering
2O
3) figure of relation of addition and sintered density and volume resistance value.
Fig. 3 is that expression the application's the embodiment and the GZO of comparative example are target aluminum oxide (Al when 1500 ℃ of sintering
2O
3) figure of relation of addition and sintered density and volume resistance value.
Embodiment
Generally speaking, the electroconductibility of nesa coating is represented with area resistance (Ω/mouth).Usually require it to have area resistance about 5 Ω/mouths.When being applied to aforesaid LCD picture, when requiring the liquid crystal panel height to become more meticulous, also require its area resistance low.The area resistance value representation that obtains divided by the thickness of nesa coating than resistance.
The area electric conductivity of nesa coating is represented with the electric conductivity (than the inverse of resistance) and the product of thickness, this conductivity (Ω
-1Cm
-1) the electric charge e (coulomb) and the carrier degree of excursion μ (cm that hold with the carrier (emptying aperture or electronics) that film comprised
2/ Vsec) and carrier concn n (cm
-3) product represent (σ (Ω
-1Cm
-1)=e μ n).
Thereby, for the electric conductivity that improves nesa coating, reduce than resistance (being also referred to as resistivity) and area resistance, as long as increase carrier degree of excursion μ (cm
2/ Vsec) and carrier concn n (cm
-3) any one party or both sides get final product.
The gallium oxide-zinc oxide sinter sputtering target of the present application is excellent as the target for transparent electroconductive film that formation has such membrane property.The content of gallium oxide is preferably the scope of 0.1～10 quality %.Preferred scope is 2～7 quality %.
The principal element of membrane property about during as sputter can exemplify the density of aforesaid target, and target density is high more, and the tuberculosis of formation is few more, can obtain generation that can the long term inhibition paradoxical discharge and the good film with stable sputter characteristic that particulate takes place.
On the other hand, the volume resistance value of target directly is reflected in the inefficient aspect of nesa coating, therefore, must suppress the increase of volume resistance value as far as possible.
As the doping agent of the gallium oxide-zinc oxide sinter sputtering target realization densification that can make the present application, the aluminum oxide (Al of known 20～500 quality ppm
2O
3) be very effective.This aluminum oxide solid solution also has the characteristic that can keep low volume resistance value as described later in GZO.Adding this aluminum oxide is the most important of the present invention.
When the amount of aluminum oxide is lower than 20 quality ppm, can't realize the densification of target, so its content is set at more than the 20 quality ppm.On the other hand, when the amount of aluminum oxide surpassed 500 quality ppm, sintered density descended rapidly, and the trend that its volume resistance value is increased is arranged.In addition, the excessive interpolation of aluminum oxide also exists meeting that target disruptive problem takes place.Thereby, must set below the 500 quality ppm.
In addition, by suitable selection sintering condition, can make the sintered density of the high-density gallium oxide-zinc oxide sinter sputtering target of the present application is 5.55g/cm
3More than so be 5.6g/cm
3More than.
And the volume resistance value of the high-density gallium oxide-zinc oxide sinter sputtering target of the present application can reach below the 3.0m Ω cm.In existing gallium oxide-zinc oxide sinter sputtering target, can not realize simultaneously that sintered density is 5.6g/cm
3More than and the volume resistance value be below the 3.0m Ω cm.
The volume resistance value of target directly is reflected in the inefficient aspect of nesa coating, can obtain containing the electroconductibility of gallium oxide-zinc oxide of gallium oxide of 0.1～10 quality % and the nesa coating of photopermeability excellence.
Manufacture method as GZO target of the present invention is not particularly limited, and prepares the gallium oxide (Ga of specified amount (0.1～10 quality %)
2O
3) powder, the trace aluminum oxide (Al
2O
3) zinc oxide (ZnO) powder of 20～500 quality ppm powder and residual content.
Generally speaking, in order to improve target density, we can say that the powder before being shaped is thin more good more.Usually use the container of zirconium oxide bead or zirconium white liner to pulverize.This crushing medium itself can not become special source of pollution (being infected with the source).The great advantage of bringing thus is, can improve crushing level, obtains than more high purity, highdensity sputtering target in the past.
With dynamic crushing and classification machine (atritor) mix, micro mist is broken, can obtain mean pore sizes is the mixed powder raw material of 0.8 μ m.These raw material are carried out granulation, obtain globular granulation powder.And then can carry out impact briquetting to this granulation powder, carry out CIP (cold isostatic compaction) again.Then, this molding sintering temperature about 1000～1600 ℃ in the oxygen atmosphere was obtained sintered compact about 1～5 hour.
Need to prove that sintering condition can be changed arbitrarily, and manufacturing method of power also can change to the method beyond above-mentioned, be not particularly limited.Can make sintered density reach 5.55g/cm by above operation
3More than so be 5.6g/cm
3More than.
This sintered compact is carried out grinding, cutting, be processed into the sputtering target of regulation shape, obtain containing the gallium oxide-zinc oxide sinter sputtering target of the gallium oxide of 0.1～10 quality %.
Then, use these sinter sputtering targets, utilize DC sputter, RF sputter, magnetron sputtering etc. on glass substrate etc., to form ELD.Substrate uses the glass of photopermeability usually, but will be appreciated that and be not particularly limited in glass.
Because the gallium oxide-zinc oxide sintered body target has electroconductibility, therefore utilize DC sputter film forming easily.Thereby preferred use DC sputter equipment simple, that reliability is high, the most stable carries out film forming.The typical example of DC sputtering condition is as follows.This sputtering condition also can be changed arbitrarily.
Sputter gas: Ar:90～100%, O
2: 10～0%
Sputter gas pressure: 0.1～5Pa
Electric energy: 0.2～6W/cm
2
Film forming speed: approximately
Substrate temperature: room temperature～300 ℃
Embodiment
Below, embodiments of the invention are described.Need to prove that present embodiment is an example after all, is not subjected to the restriction of this example.That is, in technological thought scope of the present invention, comprise embodiment all modes or change in addition.
(embodiment 1～embodiment 4)
Median size after weighing utilizes zirconia media to pulverize respectively is the following Al of 1 μ m
2O
3Powder and Ga
2O
3Powder, zinc oxide (ZnO) are so that Al
2O
3Powder is respectively 20 quality ppm (embodiment 1), 50 quality ppm (embodiment 2), 200 quality ppm (embodiment 3), 500 quality ppm (embodiment 4), and Ga
2O
3Be 5 quality %, residual content is ZnO, then, uses zirconium white (ZrO
2) ball or pearl be as crushing medium, with dynamic crushing and classification machine to its mix, micro mist is broken, obtaining mean pore sizes is the mixed powder raw material of 0.8 μ m.
These raw material are carried out granulation, obtain globular granulation powder.And then this granulation powder carried out impact briquetting, carry out CIP (cold isostatic compaction) again.Then this molding sintering temperature of 1500 ℃ in the oxygen atmosphere was obtained sintered compact about 4 hours.This sintered compact is carried out grinding, cutting, be processed into the sputtering target of regulation shape.
Then, measure the density and the volume resistance value of the sintered body target that obtains thus.It is the results are shown in table 1～table 3.In addition, with it with being illustrated in Fig. 1.
Need to prove the aluminum oxide (Al that contains in the target
2O
3) be to measure the amount of aluminium and then the Al of the relative target total amount obtained with ICP (inductively coupled plasma method)
2O
3The conversion amount.The Al that contains in the target
2O
3The preceding addition of amount and sintering equates substantially.
Target density utilizes Archimedes's method to measure.In addition, the measuring method of volume resistance value is, determines at random to locate in 5 positions through the roughly All Ranges of the target of mirror ultrafinish, in the target section position dark apart from surperficial 2mm, measures with four probe method, adopts its mean value.
Table 1
Table 2
Table 3
Table 1 and Fig. 1 are illustrated in 1400 ℃ and carry out the agglomerating situation, and table 2 and Fig. 2 are illustrated in 1450 ℃ and carry out the agglomerating situation, and table 3 and Fig. 3 are illustrated in 1500 ℃ and carry out the agglomerating situation.As table 1～table 3 and Fig. 1～shown in Figure 3, have following trend: sintering temperature is from 1400 ℃ to 1500 ℃, and along with temperature raises, density raises, and the volume resistance value reduces.
But the evaporation (volatilization) of meeting generating material when sintering temperature raises because steam output is different different because of the composition that constitutes target, therefore might make composition change.Particularly in the temperature more than 1400 ℃, a part of zinc oxide is from the evaporation on target surface, and temperature is high more obvious more.Must remove to form by cutting the layer that changes has taken place, when the layer that at high temperature causes surface composition to change because of sintering increases, have the problem that its cutting output increases, qualification rate descends.
Also have power loss because of high temperature sintering simultaneously, therefore must suppress it as far as possible and form variation.In this sense, wish as far as possible below 1400 ℃ or near it.
Thereby, more preferably low-temperature sintering, but owing to tend to the direction of low densityization and high volume resistanceization this moment, therefore, wish to adjust this balance, the density of target as requested and volume resistance condition are suitably selected.
Table 1 and Fig. 1 are illustrated in 1400 ℃ and carry out the agglomerating situation, added 20～500 quality ppm aluminum oxide present embodiment high-density gallium oxide-zinc oxide sinter sputtering target with do not add Al
2O
3The gallium oxide-zinc oxide sinter sputtering target of (comparative example 1 described later) is compared, density and volume resistance value all be improved significantly.
That is, has 5.29～5.47g/cm
3Density, the volume resistance value is 3.18～12.0m Ω cm, obtains preferred high-density and low volume resistance value as can be known.
Table 2 and Fig. 2 are illustrated in 1450 ℃ and carry out the agglomerating situation, added 20～500 quality ppm aluminum oxide present embodiment high-density gallium oxide-zinc oxide sinter sputtering target with do not add Al
2O
3The gallium oxide-zinc oxide sinter sputtering target of (comparative example 1 described later) is compared, density be improved significantly.The volume resistance value also improves.That is, has 5.48～5.60g/cm
3Density, the volume resistance value is 2.60～3.14m Ω cm, obtains preferred high-density and low volume resistance value as can be known.
Table 3 and Fig. 3 are illustrated in 1500 ℃ and carry out the agglomerating situation, added 20～500 quality ppm aluminum oxide present embodiment high-density gallium oxide-zinc oxide sinter sputtering target with do not add Al
2O
3The gallium oxide-zinc oxide sinter sputtering target of (comparative example 1 described later) is compared, and density and volume resistance value are equal substantially.That is, has 5.59～5.60g/cm
3Density, the volume resistance value is 2.11～2.49m Ω cm.
The foregoing description shows, add aluminum oxide and compare with not adding aluminum oxide, at a lower temperature sintering, promptly 1400 ℃, 1450 ℃, 1500 ℃ any occasions of agglomerating, can obtain excellent high-density and low volume resistance value.
Then, use this sputtering target, on glass substrate, carry out the DC sputter under the following conditions, measure and observe the generation (lining rate) and the paradoxical discharge of tuberculosis.The generation of tuberculosis (lining rate) is to measure by surface observation after sputter begins 1 hour, and paradoxical discharge is that the paradoxical discharge of sputter after 5 hours measured.
Sputter gas: Ar:100%
Sputter gas pressure: 0.6Pa
Electric energy: 1500W
Film forming speed:
Its result, tuberculosis lining rate is low, in the sputter of sputter after 5 hours, does not almost observe the generation of paradoxical discharge.And, shown in table 1～3, even the frequency of its paradoxical discharge is also considerably less after 10 hours.
In addition, study above-mentioned film formingly, demonstrate with the ITO film of standard and compare not a halfpenny the worse good visible light transmissivity and high conductivity than resistance (Ω cm) and at the membrane property of the transmitance % of 550nm.In the above-described embodiments, to Ga
2O
3Addition be that the gallium oxide-zinc oxide sinter sputtering target of 5 quality % is illustrated, as long as the addition of gallium oxide just can obtain same result in the scope of 0.1～10 quality %.
(comparative example 1～comparative example 4)
Do not add Al
2O
3Situation of powder (comparative example 1) and the median size after weighing utilizes zirconia media to pulverize respectively are the following Al of 1 μ m
2O
3Powder and Ga
2O
3Powder, zinc oxide (ZnO) are so that Al
2O
3Powder is respectively 1000 quality ppm (comparative example 2), 2000 quality ppm (comparative example 3), 5000 quality ppm (comparative example 4), Ga
2O
3Be 5 quality %, residual content is ZnO.
Then, use zirconium white (ZrO
2) ball (or pearl) is as crushing medium, with dynamic crushing and classification machine to its mix, micro mist is broken, obtaining mean pore sizes is the mixed powder raw material of 0.8 μ m.These raw material are carried out granulation, obtain globular granulation powder.
And then this granulation powder carried out impact briquetting, carry out CIP (cold isostatic compaction) again.With this molding sintering temperature 5 hours of 1400 ℃, 1450 ℃, 1500 ℃ in air atmosphere respectively, obtain sintered compact then.These sintered compacies are carried out grinding, cutting, be processed into the sputtering target of regulation shape.
Then, measure the density and the volume resistance value of the sintered body target that obtains thus.Its result is shown in table 1, table 2, table 3 equally.In addition, with it with being illustrated in Fig. 1, Fig. 2, Fig. 3.Need to prove the aluminum oxide (Al that contains in the target
2O
3), target density and volume resistance value with and the same method of embodiment measure.
As table 1 and shown in Figure 1, do not adding Al
2O
3The comparative example 1 of gallium oxide-zinc oxide sinter sputtering target in, carry out under the agglomerating situation at 1400 ℃, its sintered density is low to moderate 5.23g/cm
3, the volume resistance value is unusual high to 2.09 * 10
5M Ω cm (2.09E+05m Ω cm).
Carry out under the agglomerating situation at 1450 ℃, its sintered density is 5.39g/cm
3, the volume resistance value is 3.17m Ω cm, compares with the target under the same sintering condition of embodiment, it is worth variation.
In addition, carry out under the agglomerating situation at 1500 ℃, its sintered density is 5.2g/cm
3, all lower than any embodiment, the volume resistance value is also high to 3.00m Ω cm.
According to these situations as can be known, under the sintering condition of low temperature more, compare with any embodiment, its density is low, volume resistance value height, is not suitable as the gallium oxide-zinc oxide sinter sputtering target.
Shown in comparative example 2, at the Al that contains 1000 quality ppm
2O
3The gallium oxide-zinc oxide sinter sputtering target in, carry out under the agglomerating situation at 1400 ℃, carry out under the agglomerating situation, carry out under the agglomerating situation at 1500 ℃ at 1450 ℃, its density all sharply descends, and compares with embodiment, its density is obviously low.In addition, for the volume resistance value, carry out under the agglomerating situation high unusually at 1400 ℃.In addition, carry out under the agglomerating situation at 1450 ℃, carry out under the agglomerating situation at 1500 ℃, the volume resistance value has slowly trend of rising.Its any situation all is not suitable as target as can be known.
Then, with the same condition of embodiment under, use these sintered body targets, utilize the DC sputter on glass substrate, to form ELD under the following conditions.
Same with embodiment, the generation of tuberculosis (lining rate) is to measure by surface observation after sputter begins 1 hour, and paradoxical discharge is that the paradoxical discharge of sputter after 5 hours measured.It is the results are shown in table 1.
With the interpolation of not adding aluminum oxide, comparative example 2 of comparative example 1 aluminum oxide of 1000 quality ppm, comparative example 3 interpolation the aluminum oxide of 2000 quality ppm, comparative example 4 interpolation the gallium oxide-zinc oxide sinter sputtering target of 5000 quality ppm carry out under the agglomerating situation at 1400 ℃, its volume resistance is too high, can not carry out the DC sputter.In addition, carry out under the agglomerating situation at 1450 ℃, the volume resistance of gallium oxide-zinc oxide sinter sputtering target that has added 5000 quality ppm is also too high, can not carry out the DC sputter.
In addition, though can carry out the DC sputter at 1450 ℃ and 1500 ℃ of agglomerating targets, tuberculosis lining rate and paradoxical discharge are often, and be bad.
On the other hand, in the gallium oxide-zinc oxide sinter sputtering target that contains aluminum oxide shown in comparative example 2, comparative example 3, comparative example 4, carry out carrying out under the agglomerating situation under the agglomerating situation Yu at 1500 ℃ at 1450 ℃, all than the tuberculosis lining rate height of present embodiment and paradoxical discharge often, bad.But also be full of cracks has taken place in the target of observing the aluminum oxide that contains 5000 quality ppm.
By as mentioned above as can be known, by adding appropriate amount of alumina, can suppress the lining rate of sputter characteristic, particularly tuberculosis, suppress the paradoxical discharge that causes by this tuberculosis and splash and the particulate that causes produces, the quality that effectively suppresses conducting film descends.
But, this effect not when the addition of aluminum oxide is lower than 20 quality ppm, and when the addition of aluminum oxide surpasses 500 quality ppm, exist its volume resistance value to increase and do not see the raising of sintered density and the disruptive problem takes place, therefore, to be set at the scope of 20 quality ppm～500 quality ppm suitable for the addition of aluminum oxide.
The possibility of using on the industry
To gallium oxide (Ga2O
3)-zinc oxide (ZnO) base sputtering target (GZO is target) contains the aluminium oxide (Al of 20～500 quality ppm by making it2O
3), when significantly improving target density, it is constant can suppressing the volume resistance value. And can suppress formation along with these tuberculosis that produce when the spatter film forming, use for a long time paradoxical discharge few, and can prevent the generation of particle. Can obtain thus keeping good visible light transmissivity and the ELD of electric conductivity.
Thereby, can be effective to the purposes of the broad scopes such as the transparency electrode (film) of the display devices such as liquid crystal display, electroluminescent display or solar cell.
Claims (7)
1. a high-density gallium oxide-zinc oxide sinter sputtering target is characterized in that, contains the aluminum oxide of 20～500 quality ppm, and sintered density is 5.55g/cm
3More than.
2. gallium oxide-zinc oxide sinter sputtering target as claimed in claim 1 is characterized in that, contains the gallium oxide of 0.1～10 quality %.
3. high-density gallium oxide-zinc oxide sinter sputtering target as claimed in claim 1 is characterized in that, the volume resistance value of described target is below the 3.0m Ω cm.
4. the formation method of a nesa coating, it is characterized in that, use contains the gallium oxide-zinc oxide target of the aluminum oxide of 20～500 quality ppm, utilizes sputtering method to form the film that the gallium oxide/zinc oxide by the aluminum oxide that contains 20～500 quality ppm constitutes on substrate.
5. the formation method of nesa coating as claimed in claim 4 is characterized in that, contains the gallium oxide of 0.1～10 quality % in the described nesa coating.
6. the nesa coating of an excellent electric conductivity that is made of gallium oxide-zinc oxide is characterized in that it is to utilize sputter to be formed at the nesa coating of the aluminum oxide that contains 20～500 quality ppm on the substrate.
7. the nesa coating of excellent electric conductivity as claimed in claim 6 is characterized in that, contains the gallium oxide of 0.1～10 quality % in the described nesa coating.
Applications Claiming Priority (5)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP187554/2005 | 2005-06-28 | ||
| JP2005187554 | 2005-06-28 | ||
| JP2005313219 | 2005-10-27 | ||
| JP313219/2005 | 2005-10-27 | ||
| PCT/JP2006/310734 WO2007000867A1 (en) | 2005-06-28 | 2006-05-30 | Gallium oxide-zinc oxide sputtering target, method of forming transparent conductive film and transparent conductive film |
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| JP5879427B2 (en) * | 2011-03-25 | 2016-03-08 | ▲海▼洋王照明科技股▲ふん▼有限公司 | Fabrication method of multi-element doped zinc oxide thin film |
| CN102787294B (en) * | 2011-05-19 | 2014-08-27 | 海洋王照明科技股份有限公司 | Preparation method and use of titanium-doped zinc-magnesium aluminate film |
| CN102534496B (en) * | 2012-03-13 | 2013-08-21 | 大连理工大学 | High-thermostability transparent conductive film and preparation method and application thereof |
| JP5888599B2 (en) * | 2012-03-13 | 2016-03-22 | 三菱マテリアル株式会社 | Sputtering target and high resistance transparent film manufacturing method |
| KR101625773B1 (en) * | 2012-10-02 | 2016-05-31 | 제이엑스금속주식회사 | Zinc oxide-based sintered compact, zinc oxide-based sputtering target consisting of this sintered compact, and zinc oxide-based thin film obtained by sputtering this target |
| CN103305793B (en) * | 2013-04-24 | 2016-07-06 | 研创应用材料（赣州）股份有限公司 | A kind of method preparing buffer layer oxides target and sull thereof |
| CN103408062B (en) * | 2013-08-02 | 2016-02-03 | 北京航空航天大学 | Gallium aluminium mixes the preparation method of zinc oxide nano powder and high-density high conductance sputtering coating target thereof altogether |
| CN108385062B (en) * | 2018-03-09 | 2020-05-26 | 哈尔滨工业大学 | (Al)xGa1-x)2O3Preparation method of alloy film |
| CN113637941B (en) * | 2021-07-15 | 2023-03-28 | 安徽锦华氧化锌有限公司 | Preparation method of zinc-gallium oxide magnetron sputtering target material |
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