CN101258263A - Sputtering target, transparent conductive film, and transparent electrode - Google Patents
Sputtering target, transparent conductive film, and transparent electrode Download PDFInfo
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- CN101258263A CN101258263A CNA2006800322564A CN200680032256A CN101258263A CN 101258263 A CN101258263 A CN 101258263A CN A2006800322564 A CNA2006800322564 A CN A2006800322564A CN 200680032256 A CN200680032256 A CN 200680032256A CN 101258263 A CN101258263 A CN 101258263A
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- 239000011701 zinc Substances 0.000 claims abstract description 264
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- 238000002441 X-ray diffraction Methods 0.000 claims abstract description 61
- 229910052738 indium Inorganic materials 0.000 claims abstract description 57
- APFVFJFRJDLVQX-UHFFFAOYSA-N indium atom Chemical compound [In] APFVFJFRJDLVQX-UHFFFAOYSA-N 0.000 claims abstract description 49
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- 229910052725 zinc Inorganic materials 0.000 claims abstract description 44
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 claims abstract description 35
- 229910052718 tin Inorganic materials 0.000 claims abstract description 35
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- 239000001301 oxygen Substances 0.000 claims abstract description 28
- 229910052760 oxygen Inorganic materials 0.000 claims abstract description 28
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 claims abstract description 27
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- Compositions Of Oxide Ceramics (AREA)
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Abstract
The sputtering target of the present invention is characterized by containing at least indium, tin and zinc, and containing Zn2SnO4A spinel structure compound represented by formula and In2O3A sintered body of an oxide of the represented bixbyite structure compound. A sputtering target comprising indium, tin, zinc and oxygen, wherein substantially only a peak of a bixbyite structure compound is observed by X-ray diffraction (XRD).
Description
Technical field
The manufacture method of the sputtering target that the present invention relates to sintering and make (below, abbreviate sputtering target or target sometimes as), sputtering target.In addition, the present invention relates to nesa coating and the transparency electrode of using sputtering target to obtain.
Background technology
In recent years, the development of display unit is remarkable, liquid crystal indicator (LCD) or, el display device (EL) or field-emitter display (FED) etc. use with display unit as the Controlling System in office equipment such as PC or word processor or the factory.Also have, these display unit all have the sandwich structure that the transparent conductive oxides utilized clips display element.
As such transparent conductive oxides, as record described in the non-patent literature 1, it is leading to utilize the film forming indium tin oxide of sputtering method, ion plating method or vapour deposition method (below, roughly be called ITO sometimes) to occupy.
Described ITO is made of the Indium sesquioxide and the stannic oxide of specified amount, it is characterized in that, except the transparency or electroconductibility are superior, can utilize strong acid to carry out etching and processing, and also superior with the connecting airtight property of substrate.
Though ITO has superior performance as transparent conductive oxides, be scarce resource, and existence have to contain in a large number (about 90 atom %) problem to the deleterious indium of organism.In addition, the reason that the bead when indium self is called sputter (thrust) produces, the bead that produces on this target surface also becomes one of reason of paradoxical discharge.Especially, during as the film forming of the noncrystalline ITO film of purpose, finding that therefore, the indium compound on target surface is reduced owing to import the water or the hydrogen of trace in this sputter cavity, the problem that causes bead to become more being easy to generate with the improvement of etching.Also have, find: if paradoxical discharge takes place, then flying is attached in the film forming or the problem on the transparent conductive oxides after the firm film forming as foreign matter.
Like this, owing to the unstable of supplying with (rare property), the problem of hazardous property, need from ITO, reduce indium.But the maximum solid solubility limit in Indium sesquioxide of stannic oxide is considered to about 10%, thereby if the content of the indium among the ITO will be reduced to below the 90 atom %, then causes stannic oxide to remain in the target to assemble shape.The resistance of stannic oxide is more than 100 times of ITO, therefore, the electric charge accumulation in the target takes place, arcing, and the target surface is destroyed, fine separation of fragments, (non-patent literatures 2) such as problems that bead, particulate produce.Therefore, be difficult to the content of indium is adjusted to below the 90% atom %.
Therefore,, suppress the method for paradoxical discharge, inquired into and contained by In as the generation that prevents bead
2O
3(ZnO)
mThe hexagonal crystal lamellar compound of (wherein, m is 2～20 integer) expression, and make the crystallization particle diameter of this hexagonal crystal lamellar compound be made as the method (patent documentation 1,2) of the following value of 5 μ m.But, in the method, if indium is reduced to below 90～70 atom %, the sintered density or the electroconductibility that then become target reduce, the reason that paradoxical discharge or film forming speed are slack-off, or cause the intensity of target low, break easily, or cause the problem etc. of the air of the nesa coating by the spatter film forming thermotolerance variation under existing.In addition,, need high temperature in order stably to generate the hexagonal crystal lamellar compound, and the problem that also causes industrial cost to uprise.And then, there is not resistance to the etching solution that contains the phosphoric acid that in the etching of metal or alloy, uses, be difficult to carry out the etching of metal or alloy film.
In addition, as the nesa coating of cutting down indium significantly, also having inquired into zinc oxide-stannic oxide is the nesa coating (patent documentation 3) of principal constituent.But the resistance of target is very high, exists to be difficult to carry out sputter, or the problem of paradoxical discharge takes place easily.In addition, also there is not to inquire into the sputtering target that is used to address these problems.
In patent documentation 4, disclose and contained spinel structure compound (Zn
2X
2O
4In the formula, X represents to have the element of the above valence of positive trivalent) xenogenesis element doping zinc oxide sintered compact, but to containing by Zn simultaneously
2SnO
4Expression spinel structure compound and by In
2O
3Effect under the situation of the bixbite structural compounds of expression is without any discussion.
In addition, basically not to by In
2O
3The sintered compact that expression bixbite structural compounds constitutes is that the ITO target is inquired into (patent documentation 5), but in the ITO target, generates Sn easily
3In
4O
12Deng, promptly allowing to make basically under the situation of the sintered compact that constitutes by the bixbite structural compounds, the narrow range of creating conditions is difficult to stably make.In addition, if reduce the content of indium, then be difficult to make the sintered compact that constitutes by the bixbite structural compounds basically.
In addition, that knows has, and in the IZO target that is made of indium and zinc, under the situation in zinc is the scope of 15～20 atom %, generates by In
2O
3(ZnO) the hexagonal crystal lamellar compound (non-patent literature 3) of m (m is 2～20 integer) expression.These crystal types are compared with ZnO, have the resistance that reduces target, improve the effect of relative density.But, if reduce indium amount (increasing the zinc amount) in such target, then exist to cause that the resistance of target uprises, or relative density reduces the trouble of problem such as the film forming speed that the intensity of target reduces is slack-off.
On the other hand, in recent years, the multifunction of liquid crystal indicator makes progress, and becoming with the substrate headed by the electrode base board with semi-transflective reflective type liquid crystal needs to use the electrode base board that has disposed metal or alloy.
In patent documentation 6, the liquid crystal indicator that has transparent region and reflector space on nesa coating is disclosed.And then, in patent documentation 7, put down in writing:, can oversimplify " film forming-etching " operation by adopting " by the not acid etching of corroding metal, but metal is had resistance with etching solution, be difficult to etched (having etching selectivity) " nesa coating.But, in the method for patent documentation 7, exist interpolation to cause the crystallized temperature of nesa coating or the trouble of work function change owing to the lanthanon class.In addition, need add scarce resource in nesa coating in order to regulate etching speed is lanthanide oxide etc.And then the content of the indium in the nesa coating is not cut down substantially.
Patent documentation 1:WO01/038599 handbook
Patent documentation 2: the spy opens flat 06-234565 communique
Patent documentation 3: the spy opens flat 08-171824 communique
Patent documentation 4: the spy opens flat 03-50148 communique
Patent documentation 5: the spy opens the 2002-030429 communique
Patent documentation 6: the spy opens the 2001-272674 communique
Patent documentation 7: the spy opens the 2004-240091 communique
Non-patent literature 1: " technology of nesa coating " ((オ one system) the company's publication of (strain) ohm, JSPS, transparent oxide, photoelectron material the 166th council volume, 1999)
Non-patent literature 2: pottery 37 (2002) No.9p675-678
Non-patent literature 3: American Ceramic Society's magazine, 81 (5) 1310-16 (1998))
Summary of the invention
The object of the present invention is to provide resistance low, theoretical relative density height, the target that intensity is high, the target that has reduced indium content, the paradoxical discharge that takes place when suppressing to use sputtering method and the target that can stably carry out sputter and manufacture method thereof, and the nesa coating that uses this sputtering target to make with the nesa coating film forming.
Another object of the present invention is to provide the nesa coating that can carry out with the selection etching (do not corroded the acid etching of metal or alloy, but metal or alloy is had resistance with etching solution, be difficult to etched) of metal or alloy.
It is few to another object of the present invention is to provide in the thermal treatment under atmospheric pressure resistance to rise, the nesa coating that the distribution of the resistance in big area is few.
Another object of the present invention is to provide transparency electrode and electrode base board by these electrically conducting transparent film productions.
Another object of the present invention is to provide and to use these nesa coatings, make the method for electrode base board simply.
With indium, tin and zinc is temperature history can be by the form of raw material, sintering the time of the oxidesintering target of principal constituent, heat treating method, ratio of components etc., contains with by In
2O
3(ZnO)
mThe hexagonal crystal lamellar compound of (m represents 2～20 integer) expression, the rutile construction compound of representing by SnO2, wurtzite shape compound that ZnO represents, by Zn
2SnO
4The expression the spinel structure compound, by In
2O
3The expression the bixbite structural compounds, by ZnIn
2O
4ZnSnO headed by the spinel structure compound of expression
3, Sn
3In
4O
12Etc. crystalline texture.In addition, think that these crystalline textures can carry out various combinations.
In a plurality of combination of compounds, contain by Zn
2SnO
4The expression the spinel structure compound and by In
2O
3It is low that the compound exhibits of the bixbite structural compounds of expression can become resistance, theoretical relative density height, the target that intensity is high.The reason of this effect do not understand fully, but in being speculated as at specific sintering condition, forming, and the easy solid solution of In is in by Zn
2SnO
4The spinel structure compound of expression, Sn etc. easily solid solution in by In
2O
3The reason of the bixbite structural compounds of expression.That is, be speculated as: under the situation that the Zn of positive divalence exists, the positive easy solid solution of quaternary Sn is in the In that contains just tervalent In
2O
3In, or under the close situation of the Zn of positive divalence and positive quaternary Sn, Zn
2SnO
4In the easy just tervalent In of solid solution.
In addition, be made as the bixbite structure basically, find:, also can show the similar (And of IZO body even indium content is reduced in 60～75 atom % scopes by crystalline texture with target) the etching and processing film properties similar with ITO.
Find: use these targets, the nesa coating that utilizes sputtering film-forming is under the situation of cutting down indium content, and electroconductibility, etching, thermotolerance etc. are also superior, and being fit to the liquid-crystal display is the indicating meter or the various uses such as touch panel, solar cell of representative.
And then, find; Therefore these targets, by regulating filming condition etc., can also be applicable to that with TFT (thin film transistor) be the film forming of the transparent oxide semiconductor of representative owing to can stably carry out sputter.
In addition, inventor waits discovery: tin, zinc are that the nesa coating of specific atomic ratio carries out the selection etching with metal or alloy.
According to the present invention as can be known, provide following sputtering target, its manufacture method, nesa coating and transparency electrode.
1. a sputtering target is characterized in that,
It is to contain indium, tin and zinc at least, and comprises by Zn
2SnO
4The spinel structure compound of expression reaches by In
2O
3The sintered compact of the oxide compound of the bixbite structural compounds of expression.
2. according to 1 described sputtering target, it is characterized in that,
Being the value in 0.25～0.6 the scope by the atomic ratio of In/ (In+Sn+Zn) expression, is the value in 0.15～0.3 the scope by the atomic ratio of Sn/ (In+Sn+Zn) expression, is the value in 0.15～0.5 the scope by the atomic ratio of Zn/ (In+Sn+Zn) expression.
3. according to 1 or 2 described sputtering targets, it is characterized in that,
About the peak in the X-ray diffraction (XRD), by Zn
2SnO
4Maximum peak intensity (I (the Zn of the spinel structure compound of expression
2SnO
4)), with by In
2O
3Maximum peak intensity (I (the In of the bixbite structural compounds of expression
2O
3)) ratio (I (Zn
2SnO
4)/I (In
2O
3)) in 0.05～20 scope.
4. according to each described sputtering target in 1～3, it is characterized in that,
About the peak in the X-ray diffraction (XRD), by SnO
2Maximum peak intensity (I (the SnO of the rutile structure compound of expression
2)), by Zn
2SnO
4Maximum peak intensity (I (the Zn of the spinel structure compound of expression
2SnO
4)) and by In
2O
3Maximum peak intensity (I (the In of the bixbite structural compounds of expression
2O
3)) satisfy following relation,
I(SnO
2)＜I(Zn
2SnO
4)
I(SnO
2)＜I(In
2O
3)
I(SnO
2)＜Max.(I(Zn
2SnO
4)，I(In
2O
3))÷10
[in the above-mentioned relation formula, (Max. (X, Y) any one big side among expression X and the Y].
5. according to each described sputtering target in 1～4, it is characterized in that,
About the peak in the X-ray diffraction (XRD), the maximum peak intensity (I (ZnO)) of the wurtzite shape compound of representing by ZnO, by Zn
2SnO
4Maximum peak intensity (I (the Zn of the spinel structure compound of expression
2SnO
4)) and by In
2O
3Maximum peak intensity (I (the In of the bixbite structural compounds of expression
2O
3)) satisfy following relation,
I(ZnO)＜I(Zn
2SnO
4)
I(ZnO)＜I(In
2O
3)
I(ZnO)＜Max.(I(Zn
2SnO
4)，I(In
2O
3))÷10
[in the above-mentioned relation formula, (Max. (X, Y) any one big side among expression X and the Y].
6. according to each described sputtering target in 1～5, it is characterized in that,
About the peak in the X-ray diffraction (XRD), by In
2O
3(ZnO)
mMaximum peak intensity (I (the In of the hexagonal crystal lamellar compound of (m represents 2～20 integer) expression
2O
3(ZnO)
m)), by Zn
2SnO
4Maximum peak intensity (I (the Zn of the spinel structure compound of expression
2SnO
4)) and by In
2O
3Maximum peak intensity (I (the In of the bixbite structural compounds of expression
2O
3)) satisfy following relation,
I(In
2O
3(ZnO)
m)＜I(Zn
2SnO
4)
I(In
2O
3(ZnO)
m)＜I(In
2O
3)
I(In
2O
3(ZnO)
m)＜Max.(I(Zn
2SnO
4)，I(In
2O
3))÷10
[in the above-mentioned relation formula, (Max. (X, Y) any one big side among expression X and the Y].
7. according to each described sputtering target in 1～6, it is characterized in that,
In the image of electron rays microanalyser (EPMA), part S of rich indium (In) and rich plumbous part S (Zn) constitute island structure, its area than S (Zn)/S (In) in 0.05～100 scope.
8. according to each described sputtering target in 1～7, it is characterized in that,
By In
2O
3The crystallization particle diameter of the bixbite structural compounds of expression is below the 10 μ m.
9. according to each described sputtering target in 1～8, it is characterized in that,
Body resistance is in the scope of 0.3～100m Ω cm.
10. according to each described sputtering target in 1～9, it is characterized in that,
Theoretical relative density is more than 90%.
11. the manufacture method of a sputtering target, this sputtering target are each described sputtering targets in 1～10, wherein, described manufacture method comprises:
Obtain with the powder of the powder of indium compound, zn cpds, and the tin compound powder of the particle diameter little than the particle diameter of these powder with the atomic ratio represented by In/ (In+Sn+Zn) in 0.25～0.6 scope, by the atomic ratio of Sn/ (In+Sn+Zn) expression in 0.15～0.3 scope, the operation of the mixture that cooperates by the ratio of atomic ratio in 0.15～0.5 scope of Zn/ (In+Sn+Zn) expression;
With described mixture press molding, be made into the operation of body;
The operation of the described molding of sintering.
12. a nesa coating, it is to use each described sputtering target in 1～10, utilizes sputtering method to carry out that film forming forms.
13. a transparency electrode, it is that etching 12 described nesa coatings obtain.
14. a sputtering target is characterized in that,
Contain indium, tin, zinc and oxygen, utilize X-ray diffraction (XRD), only observe the peak of bixbite structural compounds basically.
15. according to 14 described sputtering targets, it is characterized in that,
Described bixbite structural compounds is by In
2O
3Expression.
16. according to 14 or 15 described sputtering targets, it is characterized in that,
Atomic ratio by In/ (In+Sn+Zn) expression be greater than 0.6 and less than the value in 0.75 the scope, is 0.11～0.23 the interior value of scope by the atomic ratio of Sn/ (In+Sn+Zn) expression.
17. according to each described sputtering target in 14～16, it is characterized in that,
About the peak in the X-ray diffraction (XRD), the maximum peak position of bixbite structural compounds is with respect to In
2O
3The peak of single crystal powder is shifted to positive dirction (wide-angle side).
18. according to each described sputtering target in 14～17, it is characterized in that,
The mean diameter of the Zn aggregate of being observed by electron rays microanalyser (EPMA) is below the 50 μ m.
19. according to each described sputtering target in 14～18, it is characterized in that,
The content of Cr, Cd is respectively below the 10ppm (quality).
20. according to each described sputtering target in 14～19, it is characterized in that,
The content of Fe, Si, Ti, Cu is respectively below the 10ppm (quality).
21. according to each described sputtering target in 14～20, it is characterized in that,
The crystallization particle diameter of bixbite structural compounds is below the 20 μ m.
22. according to each described sputtering target in 14～21, it is characterized in that,
Body resistance is in the scope of 0.2～100m Ω cm.
23. according to each described sputtering target in 14～22, it is characterized in that,
Theoretical relative density is more than 90%.
24. the manufacture method of a sputtering target is characterized in that, comprising:
Obtain will as the compound of indium, tin and the zinc of the raw material of sputtering target with by the atomic ratio of In/ (In+Sn+Zn) expression greater than 0.6 less than 0.75 scope in, and the operation of the mixture that cooperates by the ratio of atomic ratio in 0.11～0.23 scope of Sn/ (In+Sn+Zn) expression;
With described mixture press molding, be made into the operation of body;
10～1, in 000 ℃/hour the scope, the operation that the temperature of described molding is heated up;
1,100～1, the temperature in 700 ℃ the scope is burnt till described molding, obtains the operation of sintered compact;
10～1, in 000 ℃/hour the scope, cool off the operation of described sintered compact.
25. a nesa coating, it is to utilize sputtering method, each described sputtering target in 14～23 is carried out film forming forms.
26. a transparency electrode, it is that etching 25 described nesa coatings are made.
27. according to 26 described transparency electrodes, it is characterized in that,
The cone angle of electrode tip is 30～89 degree.
28. the making method of a transparency electrode is characterized in that,
With containing 1～10 quality % oxalic acid aqueous solution, under 20～50 ℃ temperature range, etching 25 described nesa coatings.
29. a nesa coating, wherein,
Comprise: the amorphousness oxide compound of indium (In), zinc (Zn), tin (Sn) is 0.20 when following at the atomic ratio with respect to the Sn of In, Zn and Sn, satisfies following atomic ratio 1, surpassing at 0.20 o'clock, satisfies following atomic ratio 2.
Atomic ratio 1
0.50＜In/(In+Zn+Sn)＜0.75
0.11＜Sn/(In+Zn+Sn)≤0.20
0.11＜Zn/(In+Zn+Sn)＜0.34
Atomic ratio 2
0.30＜In/(In+Zn+Sn)＜0.60
0.20＜Sn/(In+Zn+Sn)＜0.25
0.14＜Zn/(In+Zn+Sn)＜0.46
30. according to 29 described nesa coatings, wherein,
The ratio that utilization contains etching speed A that the etching solution of phosphoric acid carries out, contain the etching speed B that the etching solution of oxalic acid carries out with utilization is that B/A is more than 10.
31. a transparency electrode, it comprises: 29 or 30 described nesa coatings, wherein,
The cone angle of described transparency electrode is 30～89 degree
32. an electrode base board, it comprises: the transparency electrode that comprises 29 or 30 described nesa coatings; By metal or alloy constitute the layer.
33. according to 32 described electrode base boards, wherein,
Described metal or alloy comprises: the element that is selected from Al, Ag, Cr, Mo, Ta, W.
34. according to 32 or 33 described electrode base boards, wherein,
Be used for semi-transflective reflective type liquid crystal.
35. according to each described electrode base board in 32～34, wherein,
The described layer that is made of metal or alloy is a supporting electrode.
36. the manufacture method of an electrode base board, it is the manufacture method of each described electrode base board in 32～35, wherein, comprising:
Make the operation of nesa coating;
On at least a portion on the described nesa coating stacked by metal or alloy constitute the layer operation;
With the etching solution etching that contains oxygen acid described by metal or alloy constitute the layer operation;
Operation with the described nesa coating of etching solution etching that contains carboxylic acid.
Description of drawings
Fig. 1 is the figure of chart that is illustrated in the X-ray diffraction of the target that obtains among the embodiment 1.
Fig. 2 is the figure of chart that is illustrated in the X-ray diffraction of the target that obtains among the embodiment 3.
Fig. 3 is the figure of chart that is illustrated in the X-ray diffraction of the target that obtains among the embodiment 4.
Fig. 4 be expression to target of the present invention, when utilizing electron rays microanalyser (EPMA) to carry out the ultimate analysis of target section, rich indium (In) is mutually and the figure of the notion of the island structure that is separated of rich zinc (Zn).
Fig. 5 is the ultimate analysis image that utilizes the target section that electron rays microanalyser (EPMA) carries out of the target that obtains among the embodiment 1.
Fig. 6 is the ultimate analysis image that utilizes the target section that electron rays microanalyser (EPMA) carries out of the target that obtains in the comparative example 1.
Fig. 7 is the figure of chart that is illustrated in the X-ray diffraction of the target that obtains among the embodiment 6.
Fig. 8 (a)～(e) is the figure with the manufacture method that schematically shows the electrode base board among the embodiment 10.
Embodiment
Below, first mode of the present invention is described.
I. sputtering target
The sputtering target of first mode (below, be called the target of first mode) be characterised in that, contain indium, tin and zinc at least, and comprise by Zn
2SnO
4The spinel structure compound of expression reaches by In
2O
3The sintered compact of the oxide compound of the bixbite structural compounds of expression.The target of preferred first mode comprises basically by Zn
2SnO
4The spinel structure compound of expression reaches by In
2O
3The sintered compact of the oxide compound of the bixbite structural compounds of expression.
As mentioned above, by containing by Zn simultaneously
2SnO
4The spinel structure compound of expression reaches by In
2O
3The bixbite structural compounds of expression, it is low to form resistance, theoretical relative density height, the target that intensity is high.
At this, the spinel structure compound is described.
As disclosed in " crystal chemistry " (talk society, emerging works of middle zero diopter, 1973), usually with AB
2X
4Type or A
2BX
4Type is called spinel structure, and the compound that will have such spinel structure is called the spinel structure compound.
Usually, negatively charged ion in spinel structure (being generally oxygen) forms cube the closeest filling, and positively charged ion is present in the part of its tetrahedral interstice and octahedral interstice.
Also have, the spinel structure compound comprises that also atom in the crystalline texture or ion are by the substitutional solid solution of other atomic substitutions of a part, the intrusion type sosoloid that other atoms are added on position between lattice.
Spinel structure compound as the constituent of the target of first mode is by Zn
2SnO
4The spinel structure compound of expression.That is, in X-ray diffraction, show peak pattern or similar (displacement) pattern of the No.24-1470 of JCPDS (Joint Committeeon Powder Diffraction Standards) database.
Secondly, the bixbite structural compounds is described.Bixbite structural compounds (bixbyite) also is called rare-earth oxide C type or Mn
2O
3(I) type oxide compound.As disclosed in " technology of nesa coating " (the company publication of (strain) ohm, JSPS, transparent oxide, photoelectron material the 166th council compile, 1999) etc., stoichiometric ratio is M
2X
3(M is a positively charged ion, and X is a negatively charged ion, is generally oxonium ion), a structure cell is by M
2X
316 molecules, amount to 80 atoms (M is 32, and X is 48) and constitute.As the bixbite structural compounds of the constituent of the target of first mode be wherein by In
2O
3The compound of expression, promptly in X-ray diffraction, show peak pattern or the similar compound of (displacement) pattern of the No.06-0416 of JCPDS (Joint Committee on Powder Diffraction Standards) database.
Also have, the bixbite structural compounds comprises that also atom in the crystalline texture or ion are by the substitutional solid solution of other atomic substitutions of a part, the intrusion type sosoloid that other atoms are added on position between lattice.
The crystalline state of the compound in the target can be judged by utilizing X-ray diffraction method to observe from the test portion of target (sintered compact) sampling.
The atomic ratio that the target of preferred first mode is represented by In/ (In+Sn+Zn) is 0.25～0.6 the interior value of scope, being the value in 0.15～0.3 the scope by the atomic ratio of Sn/ (In+Sn+Zn) expression, is the value in 0.15～0.5 the scope by the atomic ratio of Zn/ (In+Sn+Zn) expression.
At this, the above-mentioned atomic ratio in the target of first mode can be measured by utilizing inductively coupled plasma (ICP) luminescence analysis.
If less than 0.25, then exist the body resistance of target to uprise by the atomic ratio of In/ (In+Sn+Zn) expression, or the trouble of density reductions, existence utilizes the trouble that the resistance of the nesa coating that sputter obtains uprises in addition.If greater than 0.6, then exist to can not get the trouble that indium is cut down effect.
If less than 0.15, then exist the intensity of target to reduce by the atomic ratio of Sn/ (In+Sn+Zn) expression, or the trouble that uprises of body resistance.In addition, exist and to utilize the normal atmosphere thermotolerance down of the nesa coating that sputter obtains to reduce, or the contact electricity resistive is big, or reduce with weather resistance after the contacting of distribution, maybe can not survey the trouble of inspection, if greater than 0.3, then existence is difficult to the trouble of Wet-type etching.
If less than 0.15, then have the trouble that is difficult to carry out Wet-type etching,, then there are the thermotolerance of utilizing the nesa coating that sputter obtains or the trouble of electroconductibility reduction if greater than 0.5 by the atomic ratio of Zn/ (In+Sn+Zn) expression.
In addition,, change sintering condition, can not contain by Zn simultaneously even then exist if the atomic ratio of atom breaks away from above-mentioned scope
2SnO
4The spinel structure compound of expression reaches by In
2O
3The trouble of the bixbite structural compounds of expression.
By the atomic ratio of In/ (In+Sn+Zn) expression more preferably in 0.26～0.59 the scope, and then in preferred 0.26～0.52 the scope, in especially preferred 0.31～0.49 the scope.
In the scope by the atomic ratio preferred 0.17～0.24 of Sn/ (In+Sn+Zn) expression, more preferably in 0.19～0.24 the scope, in especially preferred 0.21～0.24 the scope.
In the scope by the atomic ratio preferred 0.19～0.49 of Zn/ (In+Sn+Zn) expression, more preferably in 0.2～0.49 the scope, in especially preferred 0.21～0.45 the scope.
Preferably in the target of first mode, about the peak in the X-ray diffraction (XRD), by Zn
2SnO
4Maximum peak intensity (I (the Zn of the spinel structure compound of expression
2SnO
4)), with by In
2O
3Maximum peak intensity (I (the In of the bixbite structural compounds of expression
2O
3)) ratio (I (Zn
2SnO
4)/I (In
2O
3)) in 0.05～20 scope.
If the ratio (I (Zn of above-mentioned maximum peak intensity
2SnO
4)/I (In
2O
3)) less than 0.05, then by Zn
2SnO
4The bixbite structural compounds of expression is few, and when not being made as under the pyritous situation, the density refractory that has a target to be rising, or the intensity of target reduces easily, or Sn is to In
2O
3Solid solution become unstable, produce the SnO (isolator) of trace, become the trouble of paradoxical discharge etc. taken place easily.In addition, if the ratio (I (Zn of above-mentioned maximum peak intensity
2SnO
4)/I (In
2O
3)) greater than 20, then by In
2O
3The bixbite structural compounds of expression is few, the trouble that exists the resistance of target to uprise.
Ratio (I (the Zn of above-mentioned maximum peak intensity
2SnO
4)/I (In
2O
3)) more preferably in 0.1～10 the scope, and then in preferred 0.15～7 the scope, in especially preferred 0.2～5 the scope, most preferably in 0.7～4 the scope.
The ratio of above-mentioned maximum peak intensity can be by the chart that utilizes X-ray diffraction (XRD) to obtain, and is calculated by the maximum peak intensity that exists in any range (for example, 2 θ=15～65 ° scope) and obtains.
In addition, especially reduce under the situation of resistance of target the ratio (I (Zn of preferred above-mentioned maximum peak intensity in desire
2SnO
4)/I (In
2O
3)) bigger than 1.In addition, improve under the situation of sintered density of target the ratio (I (Zn of preferred above-mentioned maximum peak intensity in desire
2SnO
4)/I (In
2O
3)) littler than 1.
And then, by Zn
2SnO
4The spinel structure compound of expression reaches by In
2O
3The maximum peak intensity of the bixbite structural compounds of expression is during all greater than the maximum peak intensity of the compound beyond it, and performance contains the effect of the compound of two structures, and is therefore preferred.
Preferably in the target of first mode, about the peak in the X-ray diffraction (XRD), by SnO
2Maximum peak intensity (I (the SnO of the rutile structure compound of expression
2)), by Zn
2SnO
4Maximum peak intensity (I (the Zn of the spinel structure compound of expression
2SnO
4)) and by In
2O
3Maximum peak intensity (I (the In of the bixbite structural compounds of expression
2O
3)) satisfy following relation,
I(SnO
2)＜I(Zn
2SnO
4)
I(SnO
2)＜I(In
2O
3)
I(SnO
2)＜Max.(I(Zn
2SnO
4)，I(In
2O
3))÷10
[in the above-mentioned relation formula, (Max. (X, Y) any one big side among expression X and the Y].
In addition, preferably in the target of first mode, about the peak in the X-ray diffraction (XRD), the maximum peak intensity (I (ZnO)) of the wurtzite shape compound of representing by ZnO, by Zn
2SnO
4Maximum peak intensity (I (the Zn of the spinel structure compound of expression
2SnO
4)) and by In
2O
3Maximum peak intensity (I (the In of the bixbite structural compounds of expression
2O
3)) satisfy following relation,
I(ZnO)＜I(Zn
2SnO
4)
I(ZnO)＜I(In
2O
3)
I(ZnO)＜Max.(I(Zn
2SnO
4)，I(In
2O
3))÷10
[in the above-mentioned relation formula, (Max. (X, Y) any one big side among expression X and the Y].
In the above-mentioned relation formula, represent in the target of first mode by SnO
2The content of the rutile structure compound of expression and/or the wurtzite shape compound represented by ZnO is few, or is substantially devoid of.
At this, the rutile structure compound is meant AX
2The type compound is that chain with regular octahedron of rib is parallel to tetragonal L axle and advances, and positively charged ion forms the compound of the arrangement of B.C.T..In first mode rutile structure compound of indication be wherein by SnO
2The rutile structure compound of expression.
The rutile structure compound is meant the AX type compound that adopts four-coordination, is the compound that adopts six side's filled-types.The rutile structure compound of indication is the wurtzite shape compound of being represented by ZnO wherein in first mode.
And then the target of preferred first mode is substantially devoid of by Sn
3In
4O
12The double oxide of expression.
About by Sn
3In
4O
12The double oxide of expression has open in " the special Leah (ま て り あ) of horse ", the 34th volume, No. 3 (1995), 344-341 etc.
If the target of first mode contains in a large number by SnO
2The rutile structure compound of expression or by the wurtzite shape compound that ZnO represents then exists the body resistance of target to rise, or the trouble of the problem generations such as relative density reduction of target.
In addition, if contain by Sn
3In
4O
12The double oxide of expression is then because Sn
3In
4O
12Sputtering raste slow, therefore exist to become to produce the former of bead and therefore suffer from.
Preferably in the target of first mode, about the peak in the X-ray diffraction (XRD), by In
2O
3(ZnO)
mMaximum peak intensity (I (the In of the hexagonal crystal lamellar compound of (m represents 2～20 integer) expression
2O
3(ZnO)
m)), by Zn
2SnO
4Maximum peak intensity (I (the Zn of the spinel structure compound of expression
2SnO
4)) and by In
2O
3Maximum peak intensity (I (the In of the bixbite structural compounds of expression
2O
3)) satisfy following relation,
I(In
2O
3(ZnO)
m)＜I(Zn
2SnO
4)
I(In
2O
3(ZnO)
m)＜I(In
2O
3)
I(In
2O
3(ZnO)
m)＜Max.(I(Zn
2SnO
4)，I(In
2O
3))÷10
[in the above-mentioned relation formula, (Max. (X, Y) any one big side among expression X and the Y].
The above-mentioned relation formula is represented in the target of first mode by In
2O
3(ZnO)
mThe content of the hexagonal crystal lamellar compound of (m represents 2～20 integer) expression is few, or is substantially devoid of.
At this, the rutile structure compound is meant the al. at L.Dupont et, Journal of Solid StateChemistry 158,119-133 (2001), Toshihiro Moriga et al., J., Am.Ceram Soc., the compound of record among 81 (5) 1310-16 (1998) etc., the rutile structure compound of first mode is meant by In
2O
3(ZnO)
m(m represents 2～20 integer) or Zn
kIn
2O
K+3The compound of (k is an integer) expression.
If the target of first mode contains in a large number by In
2O
3(ZnO)
mThe hexagonal crystal lamellar compound of (m represents 2～20 integer) expression then exists the resistance of target to uprise, or paradoxical discharge takes place, or the intensity of target is insufficient and the trouble broken easily etc.
Preferably in the target of first mode, in the ultimate analysis of the target section that electron rays microanalyser (EPMA) carries out, the part of rich indium (In) and the part of rich zinc (Zn) show island structure (representing synoptic diagram in Fig. 4), the area of area S (In), the S (Zn) that calculates by the image of In and Zn than S (Zn)/S (In) in 0.05～100 scope.Area is more preferred 0.05～20 than S (Zn)/S (In), and more preferably 0.1～10, especially preferred 0.2～5.
Herein, the rich part of analyzing the element density (common more than 1.5～2 times) that is higher than periphery with EPMA that is meant mutually.
If rich indium (In) does not mutually form island structure mutually with rich zinc (Zn), or the area of area S (In), S (Zn) than S (Zn)/S (In) outside 0.05～100 scope, then have the density reduction of target, or body resistance uprises, or the trouble of intensity reduction.Especially, do not forming under the situation of island structure, body resistance uprises easily.This is presumably following reason: if do not constitute island structure, then form the state of a large amount of solid solutions of Zn in just tervalent In compound of positive divalence, form current carrier trap (carrier trap), density reduces, and body resistance uprises.
Preferably in the target of first mode, by In
2O
3The crystallization particle diameter of the bixbite structural compounds of expression is below the 10 μ m, more preferably below the 6 μ m, below the especially preferred 4 μ m.
If by In
2O
3Then there is the trouble that paradoxical discharge or bead take place easily in the crystallization particle diameter of the bixbite structural compounds of expression greater than 10 μ m.
The crystallization particle diameter of each compound can utilize electron rays microanalyser (EPMA) to measure.
The body resistance of the target of preferred first mode is below the 100m Ω cm, and preferred in addition theoretical relative density is more than 90%.
If the body resistance of target uprises, or theoretical relative density is less than 90%, and then existing becomes guiding discharge and hit that disruptive is former therefore suffers from.
The body resistance of the target of preferred first mode is in the scope of 0.3～50m Ω cm, more preferably in the scope of 0.3～10m Ω cm, in the scope of especially preferred 0.4～5m Ω cm, most preferably in the scope of 0.4～3m Ω cm.
At this, the mensuration of the body resistance value of target utilizes four probe method to carry out.
The theoretical relative density of the target of first mode is preferred more than 95%, and is especially preferred more than 98%.If theoretical relative density is less than 90%, then exist the intensity of target to reduce, or film forming speed is slack-off, or the trouble of utilizing the resistance of the film that sputter makes to uprise.
At this, following the obtaining of theoretical relative density of target.
The proportion of ZnO, SnO2, In2O3 is made as 5.66g/cm respectively
3, 6.95g/cm
3, 7.12g/cm
3, than calculating density, calculate and utilize the ratio of the density that Archimedes's method measures by this amount, with it as theoretical relative density.
The preferred 10kg/mm of the fracture resistence force of the target of first mode
2More than, more preferably 11kg/mm
2More than, especially preferred 12kg/mm
2More than.Applying load during owing to the transportation that has target, installation, the trouble of target breakage requires target to have certain above fracture resistence force, if less than 10kg/mm
2, then have the trouble of cannot stand as the use of target.
The fracture resistence force of target can be measured according to JIS R 1601.
II. the manufacture method of sputtering target
The manufacture method of the sputtering target of first mode (below, be sometimes referred to as the manufacture method of first mode), it is characterized in that, comprising:
Obtain with the powder of the powder of indium compound, zn cpds, and the tin compound powder of the particle diameter little than the particle diameter of these powder with the atomic ratio represented by In/ (In+Sn+Zn) in 0.25～0.6 scope, by the atomic ratio of Sn/ (In+Sn+Zn) expression in 0.15～0.3 scope, the operation of the mixture that cooperates by the ratio of atomic ratio in 0.15～0.5 scope of Zn/ (In+Sn+Zn) expression;
With described mixture press molding, be made into the operation of body;
The operation of the described molding of sintering.
Below, according to each operation, the manufacture method of first mode is described.
(1) compounding operation
Compounding operation is the necessary operation of the raw material of sputtering targets such as mixed metal oxide.
As raw material, use powder, and the tin compound powder of the particle diameter littler of powder, the zn cpds of indium compound than the particle diameter of these powder.This be because: if the particle diameter of the powder of the particle diameter of tin compound powder and indium compound, zn cpds is identical or bigger than it, SnO then
2Exist (remaining) in target, body resistance may uprise.
In addition, the particle diameter of preferred tin compound powder is little less than the particle diameter of indium compound powder and zn cpds powder, below 1/2nd of particle diameter of the particle diameter of tin compound powder and then preferred indium compound powder.In addition, the particle diameter of the particle diameter ratio indium compound powder of especially preferred zn cpds powder is little.
Particle diameter as each metallic compound of the raw material of target can utilize the method for record among the JIS R 1619 to measure.
Oxide compound as indium, tin and the zinc of the raw material of target need be in the scope of atomic ratio 0.25～0.6 by In/ (In+Sn+Zn) expression,, in 0.15～0.3 scope, cooperate by the atomic ratio of Sn/ (In+Sn+Zn) expression by the ratio of atomic ratio in 0.15～0.5 scope of Zn/ (In+Sn+Zn) expression.If break away from above-mentioned scope, then can not get having the target of first mode of described effect.
As the compound of indium, for example, can enumerate Indium sesquioxide, indium hydroxide etc.
As the compound of tin, for example, can enumerate stannic oxide, stannic hydroxide etc.
As the compound of zinc, for example, can enumerate zinc oxide, zinc hydroxide etc.
As all cpds, from the remaining difficulty aspect of agglomerating easness, by product, preferred oxides.
In addition, the purity of raw material is generally 2N (99 quality %), more than the preferred 3N (99.9 quality %), more than the especially preferred 4N (99.99 quality %).If purity less than 2N, then contains heavy metals such as Cr, Cd etc. sometimes, if contain these heavy metals etc., then use the weather resistance damage of the nesa coating of this target making sometimes, or product is produced hazardous property.
Preferably the raw material with above-mentioned particle diameter relation that will use in the manufacturing of the target of metal oxide etc. mixes, and uses common mixing pulverizer, for example wet-type ball mill or ball mill or ultrasonic unit, mixes equably, pulverizes.
Under the situation of the manufacturing raw material of targets such as metal oxide being mixed and pulverizing, the particle diameter of the mixture after the pulverizing is generally below the 10 μ m, below the preferred 3 μ m, below the especially preferred 1 μ m.If the particle diameter of metallic compound is excessive, then the density of target may be difficult to improve.
Can utilize the method for putting down in writing among the JIS R1619 to measure as the particle diameter after the pulverizing of the mixture of the metallic compound of the raw material of target.
(2) burn operation temporarily
After burning temporarily operation and be the mixture that obtains as the compound of the raw material of sputtering target, the operation of this mixture being burnt temporarily, be provided with as required.
If burn temporarily, then improve density easily and preferred, but have the trouble of cost rising owing to become.Therefore, more preferably do not burn temporarily and improve density.
Burning in the operation temporarily, under 500～1200 ℃, under 1～100 hour the condition mixture of metal oxide is heat-treated.This be because less than 500 ℃ or less than 1 hour heat-treat condition under, the thermolysis of indium compound or zn cpds, tin compound is insufficient sometimes.On the other hand because in heat-treat condition greater than 1200 ℃ situation or under greater than 100 hours situation, cause thickization of particle sometimes.
Thereby, especially preferably in 800～1200 ℃ temperature range, under 2～50 hours the condition, heat-treat (burning temporarily).
Also have, preferably before following forming process and firing process, pulverize at this temporary burning thing that obtains.Should burn temporarily the pulverizing of thing and use ball mill, roller mill, ball mill, jet mill etc., the particle diameter that makes temporary burning thing is to get final product in the scope of 0.01～1.0 μ m.If the particle diameter that burns thing temporarily is less than 0.01 μ m, then volume density becomes too small, is difficult to operation sometimes, if greater than 1.0 μ m, then is difficult to improve the density of target sometimes.
Burning temporarily thing can utilize among the JIS R 1619 record and method to measure.
(3) forming process
Forming process is with the mixture of metal oxide (being the temporary thing that burns under the situation that temporary burning operation is set) press molding, with its necessary operation as molding.Utilize this operation, be configured as the shape that is fit to as target.Under the situation that temporary burning operation is set, the micropowder of the temporary burning thing that obtains can be carried out granulation, utilize pressure forming to form desirable shape.
Handle as operable shaping in this operation, for example, can enumerate metal pattern shaping, casting forming, sputtering forming etc., but (target 0 is preferably used the shapings such as (CIP) of cold rolling hydrostaticpressure in order to obtain the high sintered compact of sintered density.
Also have, when being shaped processing, use shaping additives such as polyvinyl alcohol or methylcellulose gum, high molecular wax, oleic acid.
(4) firing process
Firing process is the necessary operation of burning till the molding that obtains in the above-mentioned forming process.Burn till and to utilize hot rolling hydrostaticpressure (HIP) to burn till to wait to carry out.
As the firing condition under this situation, add at oxygen atmosphere or oxygen and to depress, usually under 700～1700 ℃, preferably under 1100～1650 ℃, more preferably under 1300～1600 ℃, carried out usually 30 minutes～360 hours, preferred 8～180 hours, more preferably 12～96 hours burn till.If less than 700 ℃, then there is the density that is difficult to improve target in firing temperature, or the trouble of sintering spended time, if greater than 1700 ℃,, exist to form and depart from then owing to the gasification of composition, or the trouble of damage stove.
In addition, if less than 30 minutes, then be difficult to improve the density of target combustion time, if greater than 360 hours, then owing to spend manufacturing time, cost uprises, and therefore, can not adopt in the practicality.
On the other hand,, or under the temperature more than 1700 ℃, burn till, then generate the hexagonal crystal lamellar compound, fully form spinel crystallization (spinel structure compound) sometimes if powdered mixture is burnt till under the atmosphere that does not contain oxygen.Therefore, can not improve the density of the target that obtains sometimes fully, the generation of the paradoxical discharge in the time of can not suppressing sputter fully.
In addition, the heat-up rate when burning till is generally below 20 ℃/minute, and is preferred below 8 ℃/minute, more preferably below 4 ℃/minute, so that preferred below 2 ℃/minute, especially preferred below 0.5 ℃/minute.If than 20 ℃/minute fast, then generate the hexagonal crystal lamellar compound sometimes, can not form spinel crystallization (spinel structure compound) fully.
(5) reduction operation
The reduction operation is to reduce the operation of handling, be provided with as required as all homogenizations of target for the body resistance of the sintered compact that will obtain in the above-mentioned firing process.
As the method for reducing that in this operation, can be suitable for, for example, can enumerate method or vacuum firing that utilizes reducing gas or the reduction that utilizes rare gas element etc.
Under the situation that the reduction that utilizes reducing gas is handled, can use the mixed gas of hydrogen, methane, carbon monoxide or these gas and oxygen etc.
Under the situation that the reduction of burning till in utilizing rare gas element is handled, can use the mixed gas of nitrogen, argon or these gas and oxygen etc.
Also have, the temperature when reduction is handled is generally 100～800 ℃, preferred 200～800 ℃.In addition, the time of reduction processing is generally 0.01～10 hour, preferred 0.05～5 hour.
(6) manufacturing procedure
Manufacturing procedure is to be used for sintered compact that sintering is as described above obtained and then machining for being fit to the shape to the assembling of sputter equipment, assembling such as back up pad is installed in addition with operation anchor clamps, that be provided with as required.
The thickness of target is generally 2～20mm, preferred 3～12mm, especially preferred 4～6mm.In addition, a plurality of targets are installed on a back up pad, also can as a target basically.In addition, preferably utilize 200～10, No. 000 diamond wheel that precision work is carried out on the surface, especially preferably utilize 400～5, No. 000 diamond wheel to carry out precision work.If use littler or greater than 10, No. 000 diamond wheel, the trouble that then exists target to break easily than No. 200.
Preferably in the target of first mode, by In
2O
3The peak position of the bixbite structural compounds of expression is with respect to In
2O
3The X-ray diffraction of powder (XRD) peak position is shifted to positive dirction (wide-angle side).This peak shift is (2 θ) displacement 0.05 degree in the maximum peak position preferably, more preferably more than 0.1 degree, more than especially preferred 0.2 degree.In addition, owing to positive dirction (wide-angle side) displacement, therefore, infer: the positively charged ion solid solution displacement that the ratio of ionic radii indium ion is little, spacing of lattice is from shortening.Also has In
2O
3The X-ray diffraction of powder (XRD) peak position is disclosed among the No.06-0416 of JCPDS (Joint Committee onPowder Diffraction Standards) database.
At this, the displacement angle at peak can be measured by the chart of resolving X-ray diffraction.
If direction of displacement is minus side (a narrow angle side), it is insufficient then to exist current carrier to produce, and the resistance of target uprises displacement.This is speculated as following reason: to In
2O
3In the solid solution capacity (atomicity) of other atoms insufficient, carrier electrons produces fully.
Preferably in the target of first mode, by Zn
2SnO
4The peak position of the spinel structure compound of expression is shifted to negative direction (narrow angle side).This displacement is more than preferred 0.05 degree in the position of maximum peak (2 θ), more preferably more than 0.1 degree, more than especially preferred 0.2 degree.In addition, because to negative direction (narrow angle side) displacement, therefore, be speculated as: spacing of lattice is from elongated.
If direction of displacement is positive side (a wide-angle side), it is insufficient then to exist current carrier to produce, the trouble that the resistance of target uprises.This is speculated as following reason: to Zn
2SnO
4In the solid solution capacity (atomicity) of other atoms insufficient, carrier electrons produces fully.
Also has Zn
2SnO
4The X-ray diffraction of powder (XRD) peak position is disclosed among the No.24-1470 of JCPDS (JointCommittee on Powder Diffraction Standards) database.
In the target of first mode, from viewpoints such as the unstable (rare property) supplied with, hazardous propertyes, the content of preferred indium is below the 69 weight %, more preferably below the 64 weight %, and then below the preferred 50 weight %.
In the target of first mode, the atomic ratio (Zn/Sn) of preferred zinc and tin is in 0.5～10 scope, more preferably in 0.7～7 the scope, more preferably in 1～4 the scope, in especially preferred 1.1～3 the scope.If the atomic ratio (Zn/Sn) of zinc and tin greater than 10, then exists the thermotolerance under the normal atmosphere to reduce, or the trouble of acid resistance reduction.If less than 0.5, then there is spatter film forming and the rate of etch of the nesa coating made became slow, or produces the particulate of stannic oxide in the target, become the former of paradoxical discharge and therefore suffer from.
The atomic ratio of zinc and tin (Zn/Sn) can utilize inductively coupled plasma (ICP) luminescence analysis to measure.
III. nesa coating
The nesa coating of first mode is characterised in that, utilizes the sputtering target of above-mentioned first mode, utilizes sputtering method to carry out film forming.
Sputtering method and the sputtering condition that uses is not particularly limited, but preferred direct current (DC) magnetron method, interchange (AC) magnetron method, high frequency (RF) magnetron method.In liquid-crystal display (LCD) panel use, device maximizes, and therefore, preferred DC magnetron method, AC magnetron method especially preferably can be stablized film forming AC magnetron method.
As sputtering condition, sputtering pressure in the scope of 0.05～2Pa, in the scope of preferred 0.1～1Pa, more preferably in the scope of 0.2～0.8Pa, arrives pressure and is generally 10 usually
-3～10
-7Scope in, preferred 5 * 10
-4～10
-6In the scope of Pa, more preferably 10
-4～10
-5In the scope of Pa, substrate temperature is generally in 25～500 ℃ the scope, in preferred 50～300 ℃ scope, more preferably in 100～250 ℃ the scope.
As importing gas, can use rare gas elementes such as Ne, Ar, Kr, Xe, but wherein, from the fast aspect of film forming speed, preferred Ar.In addition, under the situation of Zn/Sn＜1, contain aerobic 0.01～5% if import gas, then than the easy reduction of resistance, therefore preferred.Under the situation of Zn/Sn＞2, contain hydrogen 0.01～5% if import gas, the resistance of the nesa coating that then obtains reduces easily, and is therefore preferred.
Preferred amorphousness of the nesa coating of first mode or microlitic structure, especially preferred amorphous structure.Can judge whether the nesa coating of first mode is amorphousness by X-ray diffraction method.By making nesa coating is amorphousness, obtains etching and becomes easily, and etched residue is difficult to take place, even also obtain the effect of the film of homogeneous for big area.
The etching speed that utilizes oxalic acid to carry out under 45 ℃ of film forming nesa coating is generally in 20～1000nm/ minute the scope, and in preferred 50～300nm/ minute the scope, more preferably 60～250nm is in the especially preferred 80～200nm/ minute scope.If slower than 20nm/ minute, then not only rhythm of production is slack-off sometimes, and etch residue is residual sometimes.If faster than 1000nm/ minute, then sometimes because too fast and can not the control line width etc., or inequality becomes serious sometimes.
In addition, the nesa coating of first mode preferably has resistance to the PAN as the metal wiring etching solution.If nesa coating has the PAN resistance, then on the nesa coating with the metal wiring material filming after, can under nesa coating dissolved situation, carry out the etching of metal wiring.The etching speed that the PAN resistance is preferably based on PAN is down below 20nm/ minute, more preferably below 10nm/ minute at 50 ℃.
The nesa coating of first mode is below the 1800 μ Ω cm than resistance preferably, more preferably below the 1300 μ Ω cm, below the especially preferred 900 μ Ω cm.
The ratio resistance of nesa coating can utilize four probe method to measure.
In addition, the thickness of the nesa coating of first mode is generally 1～500nm, preferred 10～240nm, and more preferably 20～190nm is in the scope of especially preferred 30～140nm.If thicker than 500nm, then there is partly crystallization, or the trouble that shortens of film formation time, if thinner, then be subjected to the influence of substrate than 1nm, there is the trouble that uprises than resistance.The thickness of nesa coating can utilize tracer method to measure.
IV. transparency electrode
The transparency electrode of first mode is characterised in that, the nesa coating of above-mentioned first mode of etching and obtaining.
Therefore the transparency electrode of first mode, possesses the above-mentioned characteristic of the nesa coating of first mode by the electrically conducting transparent film production of above-mentioned first mode.
Be used to the not restriction especially of engraving method of the transparency electrode of first mode of making, can be according to purpose, situation, etching solution, engraving method, the etching condition selecting to be fit to get final product.
In addition, preferred 35～89 degree of the cone angle of etched end, more preferably 40～87 spend, in the scopes of especially preferred 45～85 degree.If cone angle is less than 35 degree, then wimble fraction excessively enlarges, and aperture opening ratio reduces sometimes, or short circuit sometimes.If greater than 89 degree, then form back taper, weather resistance reduces sometimes, or causes panel can not normally bring into play function sometimes.
The cone angle of electrode tip can utilize electron microscope (SEM) observation section and measure.
According to first mode as can be known, can provide resistance low, theoretical relative density height, the target that intensity is high.
According to first mode as can be known, can provide electroconductibility, etching, thermotolerance etc. superior, nesa coating with PAN (mixing acid of phosphoric acid, acetic acid, nitric acid) resistance.
Below, second mode of the present invention is described.
I. sputtering target
(I-1) structure of sputtering target
The sputtering target of second mode (below, be sometimes referred to as the target of second mode) be characterised in that, contain indium, tin, zinc and oxygen, utilize X-ray diffraction (XRD), only observe the peak of bixbite structural compounds basically.
The bixbite structural compounds is as illustrating in first mode.
" utilize X-ray diffraction (XRD), only observe the peak of bixbite structural compounds basically " to be meant in X-ray diffraction, show the No.06-0416 (In of JCPDS (Joint Committee on PowderDiffraction Standards) database
2O
3Monocrystal) peak pattern or similar (displacement) pattern, the maximum peak of other structures is less than 5% of the maximum peak of bixbite structural compounds, fully little or confirm basically less than.
In addition, preferred by X-ray diffraction method, SnO
2Or Sn
3In
4O
12The peak less than 3% of the maximum peak of bixbite structural compounds, fully little or confirm basically less than.If these compounds exist, then exist the resistance of target to uprise, or when sputter, becoming on the target is easy to generate electric charge (charge), or becomes the reason of paradoxical discharge or bead generation.
The target of second mode be greater than 0.6 and less than the value in 0.75 the scope by the atomic ratio of In/ (In+Sn+Zn) expression preferably, is 0.11～0.23 the interior value of scope by the atomic ratio of Sn/ (In+Sn+Zn) expression.
It is, then as follows by the atomic ratio of In/ (In+Sn+Zn) expression if represent with inequality,
0.6＜In/(In+Sn+Zn)＜0.75
Do not comprise 0.6 and 0.75.
On the other hand, the atomic ratio of being represented by Sn/ (In+Sn+Zn) is expressed as follows,
0.11≤Sn/(In+Sn+Zn)≤0.23
Comprise 0.11 and 0.23.
By In/ (In+Sn+Zn) if the atomic ratio below 0.6 of expression, then exist bixbite structure single layer structure to become unstable, produce the trouble of other crystal type, if more than 0.75, then there is the easy crystallization of making of sputter of film, etching speed is slack-off, or is easy to generate residual trouble after the etching.In addition, the reduction effect of indium becomes insufficient.By the more preferably value in 0.61～0.69 the scope of the atomic ratio of In/ (In+Sn+Zn) expression, and then the value in preferred 0.61～0.65 the scope.
, then exist less than 0.11 as if the atomic ratio of representing by Sn/ (In+Sn+Zn) by In
2O
3(ZnO)
mThe hexagonal crystal lamellar compound or the ZnO of (m represents 2～20 integer) expression generate, and if greater than 0.23, then there is Sn in the trouble of the resistance rising of target
3In
4O
12, SnO
2, generation such as SnO, the resistance of target raises, or the trouble of bead generation.
By the more preferably value in 0.11～0.21 the scope of the atomic ratio of Sn/ (In+Sn+Zn) expression, so the value in preferred 0.11～0.19 the scope, the value in especially preferred 0.12～0.19 the scope.
And then, by the value in the scope of the atom preferred 0.03～0.3 of Zn/ (In+Sn+Zn) expression, the more preferably value in 0.06～0.3 the scope, the value in especially preferred 0.12～0.3 the scope.Less than 0.03, then etch residue is residual sometimes as if the atom of being represented by Zn/ (In+Sn+Zn), if greater than 0.3, then has the thermotolerance variation under the normal atmosphere, or the slack-off trouble of film forming speed.
At this, the above-mentioned atomic ratio in the target of second mode can utilize inductively coupled plasma (ICP) luminescence analysis to measure.
The peak position of the preferred bixbite structural compounds of the target of second mode is with respect to In
2O
3The X-ray diffraction of powder (XRD) peak position is shifted to positive dirction (wide-angle side).Be meant to positive dirction (wide-angle side) displacement: the positively charged ion solid solution displacement that the ratio of ionic radii indium ion is little, spacing of lattice is from shortening.Also has In
2O
3The X-ray diffraction of powder (XRD) peak position (pattern) is disclosed among the No.06-0416 of JCPDS (JointCommittee on Powder Diffraction Standards) database.
If the maximum peak position of bixbite structural compounds is less than 0.1, then other atoms become insufficient to the solid solution of bixbite structural compounds, the trouble that exists other crystal type to separate out.
The displacement of the peak position of bixbite structural compounds is more than 0.05 degree in the position of maximum peak (2 θ) preferably, more preferably more than 0.1 degree, more than especially preferred 0.2 degree.
At this, the displacement angle at peak can be measured by the chart of resolving X-ray diffraction.
Fig. 7 is the chart of the X-ray diffraction of the target of second mode of manufacturing among the embodiment 6 described later, and the displacement that shows the maximum peak position of bixbite structural compounds is 0.4 degree.
It is below the 50 μ m that the target of second mode is preferably used the mean diameter of the Zn cohesion portion of electronics ray microanalyzer (EPMA) observation.
If the mean diameter of Zn cohesion portion greater than 50 μ m, then exists the part upper stress of Zn aggregate to concentrate, intensity reduces, and produces electric charge (charge), and so the trouble that causes paradoxical discharge is not preferred.
The mean diameter of Zn cohesion portion is more preferably below the 30 μ m, and then below the preferred 15 μ m.
In addition, be generally below 10% with respect to the Zn aggregate area ratio of target sectional area, preferred below 5%, more preferably below 1%.
The content of the preferred Cr of the target of second mode, Cd is respectively 10ppm (quality).
Cr, Cd are the impurity in the target of second mode, if its content respectively greater than 10ppm (quality), then becomes other crystal type, have the trouble that is difficult to take the bixbite structural compounds.In addition, in film forming, when being used in liquid crystal indicator, exist weather resistance to reduce, or the trouble of friction burn is taken place easily.
Under the situation of removing above-mentioned Zn cohesion part, preferred In, Sn, Zn all roughly disperse equably.
The content difference of Cr, Cd more preferably below the 5ppm, is especially distinguished below the preferred 1ppm.
The content of the Fe of the target of second mode, Si, Ti, Cu is respectively below the preferred 10ppm (quality).
Fe, Si, Ti, Cu are the impurity of the target of second mode, if its content respectively greater than 10ppm (quality), then exists the crystal type that is easy to generate other, the trouble that is difficult to take the bixbite structure.
The content difference of Fe, Si, Ti, Cu more preferably below the 5ppm, is especially distinguished below the preferred 1ppm.
The content of above-mentioned impurity element can be measured by inductively coupled plasma (ICP) luminescence analysis.
In addition, in the scope of the effect of not sacrificing second mode, contain Mg, B, Ga, improve transmitance, or add Al, improve thermotolerance, or add Zr, improve resistance to chemical reagents and also can.
In the target of second mode, below the preferred 20 μ m of the crystallization particle diameter of bixbite structural compounds.
If the crystallization particle diameter of bixbite structural compounds then exists the grain boundary to become focal point of stress greater than 20 μ m, intensity reduces, or the trouble of the easy damage of the smoothness on target surface.
The crystallization particle diameter of bixbite structural compounds is more preferably below the 8 μ m, below the especially preferred 4 μ m.
The crystallization particle diameter of bixbite structural compounds can be measured by electron rays microanalyser (EPMA).
The target preferred body resistance of second mode is in the scope of 0.2～100m Ω cm.
If body resistance less than 0.2m Ω cm, then exists resistance to become less than film forming film, the film that disperses becomes the former of bead therefore suffers from, if greater than 100m Ω cm, then has the trouble of sputter instability.
The body resistance of the target of second mode is more preferably in the scope of 0.3～10m Ω cm, more preferably in 0.4～6m Ω cm scope, in especially preferred 0.4～4m Ω cm scope.
The preferred theoretical relative density of the target of second mode is more than 90%.Disruptive is former if the theoretical relative density of target less than 90%, then exists guiding discharge to hit therefore suffers from.
The theoretical relative density of the target of second mode is more preferably more than 94%, and then preferred more than 95%, especially more than 98%.
The preferred 10kg/mm of the fracture resistence force of the target of second mode
2More than, more preferably 11kg/mm
2More than, especially preferred 12kg/mm
2More than.The transportation of target, install as described in the explanation in first mode.Owing to there is applying load, therefore the trouble of target breakage, needs target to have certain above fracture resistence force, less than 10kg/mm
2Situation under, have the trouble cannot stand as the use of target.
The measuring method of the body resistance of target, theoretical relative density, fracture resistence force as in first mode explanation as described in.
(I-2) manufacture method of sputtering target
The manufacture method of the sputtering target of second mode (below, be sometimes referred to as the target manufacture method of second mode), obtain will as the compound of indium, tin and the zinc of the raw material of sputtering target with by the atomic ratio of In/ (In+Sn+Zn) expression greater than 0.6 less than 0.75 scope in, and the operation of the mixture that cooperates by the ratio of atomic ratio in 0.11～0.23 scope of Sn/ (In+Sn+Zn) expression;
With described mixture press molding, be made into the operation of body;
10～1, in 000 ℃/hour the scope, the operation that the temperature of described molding is heated up;
1,100～1, the temperature in 700 ℃ the scope is burnt till described molding, obtains the operation of sintered compact;
10～1, in 000 ℃/hour the scope, cool off the operation of described sintered compact.
Below, by each operation, the target manufacture method of second mode is described.
(1) compounding operation
Compounding operation is the necessary operation as the metallic compound of the raw material of sputtering target.
As raw material, preferably use powder, and the tin compound powder of the particle diameter littler of powder, the zn cpds of the following indium compound of particle diameter 6 μ m than the particle diameter of these powder.This be because: if the particle diameter of the powder of the powder of the particle diameter of tin compound powder and indium compound, zn cpds is identical or bigger than it, then have SnO
2Exist (remaining) in target, becoming is difficult to produce the bixbite structure, or the trouble that uprises of the body resistance of target.
In addition, the particle diameter of the tin compound powder preferably particle diameter than indium compound powder and zn cpds powder is little, and the particle diameter of tin compound powder is below 1/2nd of particle diameter of indium compound powder more preferably.In addition, if the particle diameter of zn cpds powder then generates the bixbite structure, so especially preferred easily less than the particle diameter of indium compound powder.
Each metallic compound that is used in the manufacturing raw material of target preferably uses common mixing pulverizer, for example wet-type ball mill or ball mill or ultrasonic unit, mixes equably, pulverizes.
As the compound of indium, tin and the zinc of the raw material of sputtering target need with by the atomic ratio of In/ (In+Sn+Zn) expression greater than 0.6 less than 0.75 scope in, and cooperate by the ratio of atomic ratio in 0.11～0.23 scope of Sn/ (In+Sn+Zn) expression.If break away from above-mentioned scope, then can not get having the target of second mode of described effect.
The compound of indium as in first mode explanation as described in.
Under the situation of pulverizing as the metal oxide of the manufacturing raw material of target, the metal oxide after the pulverizing is generally below the 10 μ m, below the preferred 3 μ m, more preferably below the 1 μ m, and then below the preferred 0.1 μ m.If the particle diameter of metal oxide is excessive, then there be the trouble of the density refractory of target with rising.
Can measure according to JIS R1619 as the particle diameter after the pulverizing of the metallic compound of the raw material of target.
(2) burn operation temporarily
Burn temporarily thus need be obtain indium compound and zn cpds, and the mixture of tin compound after, the operation that the coring that this mixture is burnt temporarily need be provided with.
After obtaining indium compound and zn cpds, reaching the mixture of tin compound, preferably this mixture is burnt temporarily.But under the situation of large-scale targets such as liquid crystal panel purposes, crystal type is unstable sometimes, therefore, in this case, preferably without temporary burning operation.
Burn temporarily thermal treatment in the operation as described in the explanation in first mode.
Also have, preferably be shaped at this temporary burning thing that obtains and also pulverizing before the sintering.Should burn the pulverizing of thing temporarily, as described in explanation in first mode.
(3) forming process
Forming process as in first mode explanation as described in.
(4) firing process
Sintering circuit is after the micropowder that will obtain in above-mentioned forming process carries out granulation, the necessary operation that the molding that utilizes pressure forming to be configured as desirable shape is burnt till.Firing process comprises: 10～1, and in 000 ℃/hour the scope, the operation that the temperature of described molding is heated up; 1,100～1, the temperature in 700 ℃ the scope is burnt till described molding, obtains the operation of sintered compact; 10～1, in 000 ℃/hour the scope, cool off the operation of described sintered compact.
Burn till and to utilize hot rolling hydrostaticpressure (HIP) to burn till etc. to carry out.
Firing condition is usually 1,100～1, in 700 ℃ the scope, in preferred 1,260～1, the 640 ℃ scope, more preferably in 1,310～1,590 ℃ the scope, especially preferred 1, in 360～1,540 ℃ the scope, in 30 minutes～360 hours the scope, in preferred 8～180 hours scope, more preferably burn till in 12～120 hours the scope.
Burn till preferably to add to depress and carry out at oxygen atmosphere or oxygen.If burn till raw material powder mixture in the atmosphere that does not contain oxygen, during then existence was burnt till, gaseous constituents such as oxygen broke away from from raw material, form the trouble of variation.In addition, if burn till under the temperature more than 1,700 ℃, then exist the generation of hexagonal crystal lamellar compound preferential, the bixbite crystalline generates the trouble that becomes insufficient, or has the part gasification of composition, and becoming is difficult to control the trouble of ratio of components.In addition, if less than 1,100 ℃, then have the crystal type that does not generate as purpose, the sintered density of target does not rise, and the resistance of target rises, or the trouble of intensity reduction.In addition, generate the high crystal type of other resistance if sintering temperature less than 1,100 ℃, then exists, or the raw material composition is remaining, or the trouble of the relative density reduction of target.If it is remaining that sintering time less than 30 minutes, then exists raw material to form, or the trouble of the relative density reduction of target.
In addition, the heat-up rate of molding is usually 10～1, in 000 ℃/hour the scope, in preferred 20～600 ℃/hour scope, more preferably in 30～300 ℃/hour the scope.If greater than 1,000 ℃/hour, then generate the hexagonal crystal lamellar compound sometimes, the hexagonal crystal lamellar compound generates deficiently.If less than 10 ℃/hour, then there is spended time, reduce the trouble of productivity.
In addition, the cooling rate of sintered compact is usually 10～1, in 000 ℃/hour the scope, in preferred 15～600 ℃/hour scope, more preferably in 20～300 ℃/hour the scope, in especially preferred 30～100 ℃/hour scope.If greater than 1,000 ℃/hour, then there is output hexagonal crystal lamellar compound, the formation of bixbite structure becomes insufficient, or has the trouble that cracks in the target.If less than 10 ℃/hour, then there is spended time, reduce the trouble of productivity.
And then cooling rate is preferably less than heat-up rate, and is more preferably below 60%, especially preferred below 40%.If cooling rate less than heat-up rate, then can be made the target as purpose in the relatively shorter time.
(5) reduction operation
The reduction operation as in first mode explanation as described in.
(6) manufacturing procedure
Manufacturing procedure is that sintered compact and then machining that sintering is as described above obtained are the shape that is fit to be assemblied in sputter equipment, in addition, is used to install the operation that as required be provided with of assembling such as back up pad with anchor clamps.
The thickness of target is generally 2～20mm, preferred 3～12mm, especially preferred 4～6mm.In addition, a plurality of targets are installed on a back up pad, also can as a target basically.In addition, preferably utilize 80～No. 10000 diamond wheel that precision work is carried out on the surface, more preferably utilize 100～No. 40000 diamond wheels to carry out precision work.Especially preferably carry out precision work with 200～No. 1000 diamond wheel.If use than No. 80 little diamond wheels, the trouble that then exists target to break easily.
In order to make the target of second mode, preferably use the target manufacture method of above-mentioned second mode.As long as raw material with the above-mentioned particle diameter of above-mentioned specific atomic ratio hybrid target, use the sintering condition (degree, cooling rate, sintering temperature, sintering time mutually heat up) in the above-mentioned firing process, just the operation beyond it is not limited especially, for example, can also adopt the spy open 2002-69544 communique, spy open at the bottom of 2004-359984 communique, the Japanese Patent No. 3628554 etc. in disclosed known method or following method.In addition, also can use the manufacture method of a part that has made up these methods.
The manufacture method of industrial sputtering target (1)
(i) with ball mill, ball mill etc. raw material and water, the auxiliary agent of weighing together carried out wet mixing, pulverizing.
(ii) the raw mix that obtains is carried out drying, granulation, make prilling powder with sputter moisture eliminator etc.
(iii), carry out the SIP moulding with the rubber mould with after the prilling powder pressure forming that obtains.
(iv) will obtain formed body add to depress at oxygen and burn till, obtain sintered body.
(v) with the sintered body that obtains with cuttings such as diamond custting machine, water cutting machines, then, with grindings such as diamond wheels.
(vi) apply Yi Dalu indium cerates such as (イ Le イ Application ジ ウ system), with back up pad applying with generations such as copper.
(back up pad that is used for vii) that cerate is handled, oxide compound is removed etc. is ground, the target surface treatment.
The manufacture method of industrial sputtering target (2)
(i) carry out the dry type mixing, pulverize with the raw material of ball mill, make prilling powder weighing.
(ii) the prilling powder that obtains is carried out pressure forming.
(iii) the formed body that obtains is depressed at normal atmosphere and burnt till, obtain sintered body.
The manufacture method of industrial sputtering target (3)
(i) carry out the dry type mixing, pulverize with the raw material of ball mill, make prilling powder weighing.
(ii) the prilling powder that obtains is carried out wet mixing, pulverizing with ball mill, V mixing machine etc., obtain the granulation dispersion liquid.
(iii) obtain formed body with cast molding by the granulation dispersion liquid that obtains.
The formed body that obtains is contacted with air at supporter, make its drying after, depress at normal atmosphere and to burn till, obtain sintered body.
II. nesa coating
(II-1) structure of nesa coating
The nesa coating of second mode is characterised in that, utilizes the sputtering target film forming of sputtering method with above-mentioned second mode.
The nesa coating of preferred amorphousness of the nesa coating of second mode or crystallite, especially preferred amorphous nesa coating.If crystallinity, the etching speed when then having electrically conducting transparent film production described later is slack-off, or residual residue after the etching, or when making transparency electrode, and the cone angle of electrode tip is not the trouble of 30～89 degree.
Preferably etching is the resistance of PAN (nitration mixture of phosphoric acid, acetic acid, nitric acid) to the nesa coating of second mode to metal wiring.If nesa coating has the PAN resistance, then on the nesa coating with the metal wiring film forming after, can be under the situation of not dissolving nesa coating, the etching metal distribution.
(II-2) manufacture method of nesa coating
Be used for the sputtering method of nesa coating of second mode of making and sputtering condition as described in the explanation of first mode.
Even the nesa coating of second mode is cut down indium, electroconductibility, etching, thermotolerance etc. are superior.In addition, the nesa coating of second mode has, and not only can be used as metal or alloy be the etching solution etching with the phosphoric acid of etching solution, also can be with the etched in the lump advantage of metal or alloy.
The nesa coating of second mode preferred its be below the 1200 μ Ω cm than resistance, more preferably below the 900 μ Ω cm, especially preferred 600 μ Ω cm.If greater than 1200 μ Ω cm, then need sometimes to reduce resistance and increase the appropriate situation of thickness than resistance.
The ratio resistance of nesa coating can utilize four probe method to measure.
The thickness of the nesa coating of second mode as in first mode explanation as described in.
III. transparency electrode
(III-1) structure of transparency electrode
The transparency electrode of second mode is characterised in that, makes by the nesa coating of etching second mode.Thereby the transparency electrode of second mode possesses the above-mentioned characteristic of the nesa coating of above-mentioned second mode.
The transparency electrode of second mode is in the scope of 30～89 degree at the cone angle of electrode tip preferably, more preferably in the scope of 35～85 degree, in the scope of especially preferred 40～80 degree.The cone angle of electrode tip can be measured by utilizing electron microscope (SEM) to observe the cross section.
If the cone angle of electrode tip is less than 30 degree, then the distance of electrode edge part is elongated, under the situation that drives liquid crystal panel or organic EL panel, poor contrast occurs sometimes between pixel periphery and inside.In addition,, then exist the electrode cause the edge section to break or peel off, become the former of the defective of alignment films or broken string and therefore suffer from if greater than 89 degree.
In addition, the transparency electrode of second mode is regulated the cone angle of electrode tip easily, therefore, especially is fit to be arranged at the situation on the organic membrane that is difficult to regulate cone angle.
(III-2) making method of transparency electrode
The making method of second mode is characterised in that, with containing 1～10 quality % oxalic acid aqueous solution, and under 20～50 ℃ temperature range, the nesa coating of above-mentioned second mode of etching.More preferably 1～5 quality % of oxalic acid content that contains the aqueous solution of oxalic acid.
In the making method of the transparency electrode of second mode, the cone angle of preferred fabrication electrode tip is the transparency electrodes in the scopes of 30～89 degree.
Utilize etching speed under 35 ℃ the situation of the film forming nesa coating of oxalic acid aqueous solution etching of 5 quality % to be generally in 10～500nm/ minute the scope, in preferred 20～150nm/ minute the scope, especially in 30～100nm/ minute the scope.If less than 10nm/ minute, then exist productive temp slack-off, and the trouble of residual etch residue on the transparency electrode that obtains.If greater than 500nm/ minute, then because too fast, therefore exist can not the control line width etc. trouble.
In addition, if film forming nesa coating has the resistance as the PAN (nitration mixture of phosphoric acid, acetic acid, nitric acid) of metal wiring etching solution, then on the nesa coating with the metal wiring film forming after, can be under the situation of not dissolving nesa coating the etching metal distribution.The etching speed that the PAN resistance is preferably based on PAN is down below 20nm/ minute, more preferably below 10nm/ minute at 50 ℃.
According to second mode as can be known, provide resistance low, theoretical relative density height, the target that intensity is high.
According to second mode as can be known, reduce indium content, also suppress to use sputtering method even provide, and the paradoxical discharge that produces during with the nesa coating film forming, the target that can stably carry out sputter.
According to second mode as can be known, provide and use target of the present invention, with the nesa coating of sputtering film-forming, even it cuts down indium, electroconductibility, etching, thermotolerance etc. are superior, and being fit to the liquid-crystal display is the indicating meter or the various uses such as touch panel, solar cell of representative.
Below, Third Way of the present invention is described.
The nesa coating of Third Way comprises: the amorphousness oxide compound of indium (In), zinc (Zn), tin (Sn).And 0.20 when following, In, Zn and Sn satisfy following atomic ratio with respect to the atomic ratio of In, Zn and Sn.
0.50＜In/(In+Zn+Sn)＜0.75
0.11＜Sn/(In+Zn+Sn)≤0.20
0.11＜Zn/(In+Zn+Sn)＜0.34
The atomic ratio of indium (In/ (In+Sn+Zn)) is preferred 0.54～0.67, and more preferably 0.55～0.66, especially preferred 0.56～0.65.If below 0.5, then cause becoming big than resistance, or during as electrode, the trouble of the weather resistance reduction of TCP (Tape Carrier Package) connection section.If more than 0.75, when then causing being etchant etching with nitric acid, etching speed is slack-off, or residual residue after the etching, or be difficult to carry out the adjusting of cone angle, or reduce the connecting airtight property of metal or alloy, or based on the etching speed A of the etching solution that contains phosphoric acid with based on the trouble of the ratio B/A reduction of the etching speed B of the etching solution that contains oxalic acid.
The atomic ratio of tin (Sn/ (In+Sn+Zn)) is preferred 0.12～0.20, and more preferably 0.13～0.19, especially preferred 0.16～0.19.If below 0.11, then etching speed is too fast sometimes, be difficult to control, or under the situation of heat-treating in the presence of oxygen, rise significantly than resistance sometimes, or the weather resistance of TCp connection section reduces sometimes.
The atomic ratio of zinc (Zn/ (In+Sn+Zn)) is preferred 0.18～0.34, and more preferably 0.20～0.34, especially preferred 0.20～0.30.If below 0.11, then etching speed is slack-off sometimes, or after etching residual residue, or the connecting airtight property reduction of metal or alloy.If more than 0.34, then under the situation of in the presence of oxygen, heat-treating sometimes, rise significantly, or the weather resistance of TCP connection section reduces than resistance.
In addition, the nesa coating of Third Way with respect to the atomic ratio of the Sn of In, Zn and Sn greater than 0.20 o'clock, In, Zn and Sn satisfy following atomic ratio.
0.30＜In/(In+Zn+Sn)＜0.60
0.20＜Sn/(In+Zn+Sn)＜0.25
0.14＜Zn/(In+Zn+Sn)＜0.46
The atomic ratio of indium (In/ (In+Sn+Zn)) is preferred 0.35～0.55, and more preferably 0.40～0.52.If below 0.30, then become big than resistance sometimes, or the weather resistance of TCP connection section reduces.If more than 0.60, then sometimes when being etchant etching with nitric acid, etching speed is slack-off, or residual residue after the etching, or distributes in the face of etching speed and become big.
The atomic ratio of tin (Sn/ (In+Sn+Zn)) is preferred 0.21～0.24, and more preferably 0.21～0.23.If more than 0.25, then sometimes when being etchant etching with nitric acid, etching speed is slack-off, or after etching residual residue, or the connecting airtight property reduction of metal and alloy.
The atomic ratio of zinc (Zn/ (In+Sn+Zn)) preferred 0.15～0.45.If below 0.14, then etching speed is slack-off sometimes, or after etching residual residue, or the connecting airtight property reduction of metal or alloy.If more than 0.46, then under the situation of in the presence of oxygen, heat-treating sometimes, rise significantly, or the weather resistance of TCP connection section reduces than resistance.
In addition, the sputtering target of Third Way except containing indium, tin, zinc, also can contain aluminium, gallium, magnesium, boron, germanium, niobium, molybdenum, tungsten, yttrium, antimony, hafnium, tantalum, calcium, beryllium, strontium, cerium, lanthanum class etc. in the scope of not sacrificing Third Way.
The nesa coating of Third Way preferably when making contains nesa coating and metal alloy layer, is used to the etching solution etching of etching nesa coating easily, is difficult to be used to the etching solution etching of etching metal or alloy layer.Specifically, be preferably based on be used for the etching nesa coating etched etching speed than fast based on the etching speed of the etching solution that is used for etching metal or alloy layer.
Usually,, use the etching solution that contains carboxylic acids such as oxalic acid,, use the etching solution that contains oxygen acid such as phosphoric acid as the etching solution that is used for etching metal or alloy layer as the etching solution that is used for the etching nesa coating.
The ratio that the nesa coating of Third Way preferably utilizes etching speed A that the etching solution that contains phosphoric acid carries out, contain the etching speed B that the etching solution of oxalic acid carries out with utilization is that B/A is more than 10.
B/A is preferred 15～100000, and more preferably 20～10000.If less than 10, then sometimes when the metal or alloy etching, be exposed to the partly attenuation of nesa coating of etching solution, or the surface becomes coarse.
If greater than 100000, the control that then is fit to speed or cone angle sometimes becomes difficult.
As the etching solution that contains phosphoric acid, the nitration mixture of preferred package phosphoric acid, nitric acid, acetic acid, more preferably phosphoric acid is 20～95wt%, nitric acid 0.5～5wt%, the scope of acetic acid 3～50wt%.This etching solution also can and then contain tensio-active agent except containing these acid.Tensio-active agent preferred anionic system or nonionic system, more preferably negatively charged ion is a tensio-active agent.Tensio-active agent preferred anionic system or nonionic system, more preferably negatively charged ion is a tensio-active agent.
Contain the scope of the preferred oxalic acid of etching solution of oxalic acid at 0.5～20wt%.This etching solution contains Witco 1298 Soft Acid, poly-oxyethylene acid esters, poly-sulfoacid compound etc.And, in order to improve wettability, and then contain tensio-active agent and also can each laminar surface that carries out the etched multi-layer film.Tensio-active agent preferred anionic or nonionogenic tenside, more preferably anion surfactant.
As anion surfactant, can enumerate as fluorine and be Fu Tajite 110 (Ni Aise of Co., Ltd.), the EF-104 (Mitsubishi horse special Leah Co., Ltd.) of tensio-active agent, be the Pa Sete SF-T (NOF Corp) etc. of tensio-active agent as non-fluorine.
In addition, as nonionogenic tenside, can enumerate as fluorine and be the EF-122A (Mitsubishi horse special Leah Co., Ltd.) of tensio-active agent, be the Fu Tajite 250 (Ni Aise of Co., Ltd.) etc. of tensio-active agent as non-fluorine.
Preferred 20～50 ℃ of etch temperature.
In addition, based on the preferred 10～1000mm/ of etching speed minute under 35 ℃ of the etching solution that contains oxalic acid, more preferably 20～500nm/ minute, more preferably 25～300nm/ minute, especially preferred 50～200nm/ minute.If less than 10nm/ minute, then production rate is slack-off sometimes, if greater than 1000nm/ minute, then can not control cone angle or line width sometimes.
The nesa coating of Third Way can be used as transparency electrode and uses.This transparency electrode is preferably used preferred 30～89 degree of cone angle of the end of the etching solution etching making that contains oxalic acid.This cone angle is 35～89 degree more preferably, especially preferred 40～85 degree.
Cone angle can utilize etchant concentration or etch temperature control.Preferred 15～55 ℃ of this etch temperature, more preferably 20～50 ℃, especially preferred 25～45 ℃.If be lower than 15 ℃, then etching speed is slack-off sometimes, or the equipment dewfall.If be higher than 55 ℃, moisture evaporation sometimes then, concentration change.
The position that the nesa coating of Third Way and transparency electrode constitute is not limited on the inorganicss such as glass, inorganic insulating membrane, can be arranged on the basically organic or organic membrane such as polyimide, acrylic resin, Resins, epoxy, silicone resin, polycarbonate resin, polystyrene resin.And then the crystallinity inequality does not take place as crystallinity films such as many crystallizations ITO in the nesa coating of Third Way, transparency electrode on organic substrate or organic membrane, preferably as on organic substrate or the nesa coating that uses on the organic membrane, transparency electrode.Therefore, preferably as nesa coating, the transparency electrode used on FSP organic planarization films such as (Field Shield Fixel).
The transparency electrode of Third Way with being connected of outside (terminal) part wait in the connection portion (contact surface element) with other conductors, the atomic ratio of tin and zinc preferred 0.25～0.95, more preferably 0.35～0.9, and then preferred 0.45～0.85, especially preferred 0.55～0.85.If less than 0.25, it is excessive then to connect resistance sometimes, or behind anti-moisture test, connects resistance and uprise.If greater than 0.95, etching instability sometimes then.The atomic ratio of tin and zinc (Sn/Zn) can utilize spectrum analysis (ESCA) to measure.
And then, the transparency electrode of Third Way with the connection portion (contact surface element) of other conductors in, zinc atom is than (Zn/ (In+Sn+Zn)) preferred 0.01～0.35, more preferably 0.01～0.25, and then preferred 0.01～0.15, especially preferred 0.05～0.15.If less than 0.01, then etching speed is slack-off sometimes, if greater than 0.35, then the connection resistance that connects etc. of TCP uprises sometimes.Zinc atom conditioned disjunction target than can be by processing after the film forming or film forming the time is formed and is regulated.As the processing after the film forming, can utilize heat treated or laser wearing and tearing processing etc.The zinc atom ratio can be measured by spectrum analysis (ESCA).
The electrode base board of Third Way preferably includes: transparency electrode that is made of the nesa coating of Third Way and the layer that is made of metal or alloy that engages on this transparency electrode.By metal or alloy constitute the layer as supporting electrode performance function.
The metal or alloy that engages with transparency electrode preferably contains the element of selecting from Al, Ag, Cr, Mo, Ta, W, more preferably Al, Ag, Mo.These metals also can be monomer, also can be for being the alloy of principal constituent with these metals.For example, illustration Ag-Pd-Cu, Ag-Nd, Al-Nd, Al-Nb, Al-Ni, Al-Ti, Al-Ta.
The electrode base board of Third Way is fit to have the display pannel of active matrix structure etc., especially is fit to the TFT liquid crystal panel.Wherein, also can be suitable as semi-transflective reflective type liquid crystal uses with, FFS pattern panel with, ocb mode panel with, IPS pattern panel with, VA pattern panel.In addition, also can be used in TN mode panel usefulness, STN mode panel usefulness no problemly.
The TCP connective stability of the nesa coating of Third Way is preferred: according to ACF (anisotropic conducting film), the increment rate of the resistance before and after the PCT (pressure cooking test) that TCP connects is preferred below 500%, more preferably below 300%, especially preferred below 150%.
If greater than 500%, then in the purposes of the environment for use strictnesses such as indicating meter of mobile telephone, become sometimes and in use produce the reason that shows unequal fault.
In addition, and be not limited to TCP being connected of outside and connect, can use also that COG (chip on Glass) connects, COF (Chip on Film) connects and wait other methods of attachment.
The manufacture method of the electrode base board of Third Way comprises: the operation of making nesa coating; With the operation of nesa coating with etching solution etching nesa coating; On at least a portion on the nesa coating stacked by metal or alloy constitute the layer operation; Be somebody's turn to do the operation of the layer that constitutes by metal or alloy with the etching solution etching with the metal or alloy layer.
As the nesa coating etching solution, can use the etching solution that contains carboxylic acids such as oxalic acid, as metal or alloy layer etching solution, can use the etching solution that contains oxygen acid such as phosphoric acid.
As carboxylic acid, preferred dicarboxylic, especially preferred oxalic acid.As oxygen acid, preferred inorganic oxacid more preferably contains the inorganic oxacid of phosphorus, especially preferably phosphoric acid.
According to Third Way of the present invention as can be known, can provide superior, can be fit to the nesa coating of metal or alloy selectively with the connecting airtight property of metal or alloy.
According to Third Way of the present invention as can be known, it is few to provide in the thermal treatment under atmospheric pressure resistance to rise, the nesa coating that the distribution of the resistance on big area is few.
According to Third Way of the present invention as can be known, can provide transparency electrode and electrode base board by these electrically conducting transparent film productions.
According to Third Way of the present invention as can be known, can provide the method that to use these nesa coatings to make electrode base board simply.
[embodiment]
Below, utilize embodiment, and then specify the present invention, but the invention is not restricted to these embodiment.
Embodiment 1
(1) manufacturing of sputtering target and evaluation
(i) manufacturing of target
Make raw material as target, mix median size 3.4 μ m, the Indium sesquioxide of purity 4N, the zinc oxide of 0.6 μ m, purity 4N, the stannic oxide of 0.5 μ m, purity 4N, make that atomic ratio [In/ (In+Sn+Zn)] is 0.53, atomic ratio [Sn/ (In+Sn+Zn)] is 0.17, atomic ratio [Zn/ (In+Sn+Zn)] is 0.30, it is supplied with to wet-type ball mill, mix and pulverized 72 hours, obtained the raw material micropowder.
After the raw material micropowder that obtains carried out granulation, be the size of diameter 10cm, thickness 5mm, in its firing furnace of packing into, add at oxygen and to depress, under 1400 ℃ condition, burnt till 48 hours, obtain sintered compact (target) its pressure forming.Heat-up rate when burning till is 3 ℃/minute.
The (ii) evaluation of target
To the target that obtains, measure theoretical relative density, body resistance value, X-ray diffraction analysis, crystallization particle diameter and various rerum natura.Obtain the chart of X-ray diffraction be illustrated among Fig. 1.
The theoretical relative density of the target that obtains is 97%, and the body resistance value of utilizing four probe method to measure is 1.3m Ω m.
Through utilizing the ICP luminescence analysis to carry out results of elemental analyses, In/ (In+Sn+Zn)=0.53, Sn/ (In+Sn+Zn)=0.17, Zn/ (In+Sn+Zn)=0.30.
In addition, to the test portion that adopts from this sintered compact, utilize the crystalline state in the X-ray diffraction method observation transparent conductive material, its result in the target that obtains, only confirms by Zn
2SnO
4The spinel structure compound of expression reaches by In
2O
3The bixbite structural compounds of expression.
In addition, as shown in Figure 1, the maximum peak of spinel structure compound to the narrow angle side be shifted 0.3 the degree, the maximum peak of bixbite structural compounds to the wide-angle side be shifted 0.3 the degree.
The condition determination of the X-ray diffraction mensuration (XRD) of target is as described below.
Device: (strain) sharp jacket system (Ultima-III)
X ray: Cu-K α line (wavelength
With the monochromatic photometer monochromatization of graphite)
2 θ-θ reflection method, continuous sweep (1.0 °/minute)
Sample room every: 0.02 °
Clearance D S, SS:2/3 °, RS:0.6mm
And then the sintered compact that embedding obtains in resin after the aluminium oxide particles polishing of its surface with particle diameter 0.05 μ m, utilizes electron rays microanalyser (EPMA) EPMA-2300 (Shimadzu Seisakusho Ltd.'s system), measures under the following conditions.
Acceleration voltage: 15kV
Test portion electric current: 0.05 μ A
Bundle size: 1 μ m
Step-length: 0.2 * 0.2 μ m
The result who utilizes above-mentioned condition to measure, sintered compact as shown in Figure 5, formed rich indium (In) mutually with rich zinc (Zn) island structure clearly mutually, the area of area S (In), the S (Zn) that is calculated by image separately is 0.9 than S (Zn)/S (In).
And then, the sintered compact that embedding obtains in resin, after of the aluminium oxide particles polishing of its surface with particle diameter 0.05 μ m, utilizing electron rays microanalyser (EPMA) is JXA-8621MX (NEC corporate system), after being enlarged into 5000 times, be determined at the maximum diameter of the crystalline particle of the spinel compound of observing in the cubic frame of 30 μ m * 30 μ m.In three place's frames, carry out same mensuration, calculate the mean value of maximum particle dia respectively, confirm this sintered compact by Zn
2SnO
4The spinel structure compound of expression reaches by In
2O
3The crystallization particle diameter of the bixbite structural compounds of expression is 3.0 μ m.
In addition, after the sintered compact machining that obtains in above-mentioned (i), carry out precision work, made the sputtering target of the about 10cm of diameter, the about 5mm of thickness with No. 400 diamond wheels.The result of the fracture resistence force of the target of Zhi Zuoing is 13kg/mm after measured
2The mensuration of fracture resistence force is carried out according to JIS R 1601.
(2) film forming of nesa coating and evaluation
(i) film forming of nesa coating
The sputtering target that above-mentioned (1) is obtained in (i) is installed on the DC magnetic controlled tube sputtering apparatus, at room temperature, on glass substrate with the nesa coating film forming.
Sputtering condition as this moment is as described below: sputtering pressure 1 * 10
-1Pa, arrival pressure 5 * 10
-4Pa, 200 ℃ of substrate temperatures, input power 120W, film formation time 15 minutes, importing gas are argon gas 100%.
Its result obtains on glass substrate, is formed with the transparent conducting glass of thickness for the transparent conductive oxides of about 100nm.
The (ii) evaluation of sputter state
The sputtering target that (1) is obtained in (i) is installed on the DC magnetic controlled tube sputtering apparatus, except using the mixed gas in argon gas, added 3% hydrogen, with above-mentioned (2) (i) under the identical condition, carried out sputter in continuous 240 hours, monitor having or not of paradoxical discharge, but paradoxical discharge does not confirm once yet.
In following table 1, paradoxical discharge have or not be expressed as follows: will not have the information slip of paradoxical discharge to be shown " zero ", will have the information slip of paradoxical discharge to be shown " * ".
(iii) about the evaluation of the generation of bead
The target that uses above-mentioned (1) to obtain in (i) under the condition (ii) identical with above-mentioned (2), carries out 8 hours sputter continuously.Then, the surface of the target after utilizing stereomicroscope with sputter is enlarged into 30 times, with its observation.Be determined at the visual field 900mm that any three points on the target surround respectively
2In the generation number of the above bead of 20 μ m, and obtain mean value.
The (iv) evaluation of the rerum natura of transparent and electrically conductive film
To above-mentioned (2) obtain in (i) transparent conducting glass on the electroconductibility of nesa coating, utilize four probe method to measure than resistance, its result is 4 * 10
-4Ω cm (400 μ Ω cm).
Utilize X-ray diffraction analysis, confirming this nesa coating is amorphousness.
Also have, the condition determination of the X-ray diffraction mensuration (XRD) of nesa coating is as described below.
Device: (strain) sharp jacket system Ultima-III
X ray: Cu-K α line (wavelength
With the monochromatic photometer monochromatization of graphite)
2 θ-θ reflection method, continuous sweep (1.0 °/minute)
Sample room every: 0.02 °
Clearance D S, SS:2/3 °, RS:0.6mm
To the smoothness on film surface, measure P-V value (JISB0601 benchmark), its result is 5nm, it is good to confirm smoothness.
And then to the transparency of this transparent conductive oxides, utilizing the light penetration under the light of wavelength 500nm of spectrophotometric determination is 90%, and the transparency is also superior.
And then, at 45 ℃ of these nesa coatings of following etching, its result, etching speed is 150nm/ minute.
In addition, utilizing as the representative phosphoric acid etching speed that to be metal wiring carry out with the PAN (nitration mixture of nitric acid 3.3 quality %, phosphatase 79 1.4 quality %, acetic acid 10.4 quality %) of etching solution is 20nm/ minute down at 50 ℃, and the PAN resistance is good.Also have, in table 1, being expressed as follows of the evaluation of PAN resistance: 50 ℃, a 20nm/ minute following table are shown " zero ", will be shown " * " greater than the information slip of 50 ℃, 20nm/ minute.
Embodiment 2～5, and comparative example 1～7
The proportioning of the metal oxide of raw material is changed into outside the atomic ratio shown in the table 1, with embodiment 1 in the same manner, make, estimate target, make, estimated nesa coating equally and the results are shown in the table 1.The chart of the X-ray diffraction relevant with the target that obtains in embodiment 3 and 4 is illustrated in Fig. 2 and 3.
In addition, in comparative example 1, obtain sintered compact, electron rays microanalyser (EPMA) image of Ce Dinging is illustrated among Fig. 6 similarly to Example 1.
Also have, to comparative example 2,4 and 5 since in the DC sputter discharge instability sometimes, therefore, carried out the RF sputter.
[table 1]
As can be known from the results of Table 1, together contain by Zn
2SnO
4The spinel structure compound of expression reaches by In
2O
3The theoretical relative density height of the target of the bixbite structural compounds of expression, body resistance is low, and fracture resistence force is big.
In addition we know, use the film forming nesa coating of above-mentioned target that paradoxical discharge does not take place, do not produce bead, lower than resistance, the oxalic acid etching speed with appropriateness has the PAN resistance.
Embodiment 6
(1) manufacturing of sputtering target
As raw material, mix purity 4N, the Indium sesquioxide of median size 2 μ m, the zinc oxide of purity 4N, 0.6 μ m, the stannic oxide of purity 4N, 0.5 μ m, make that atomic ratio [In/ (In+Sn+Zn)] is 0.64, atomic ratio [Sn/ (In+Sn+Zn)] is 0.18, atomic ratio [Zn/ (In+Sn+Zn)] is 0.18, it is supplied with to wet-type ball mill, mix and pulverized 20 hours, obtained the raw material micropowder.
After the raw material micropowder that obtains carried out granulation, be the size of diameter 10cm, thickness 5mm, in its firing furnace of packing into, add at oxygen and to depress, under 1400 ℃, burnt till 48 hours, obtain sintered compact (target) its pressure forming.Heat-up rate when burning till is 180 ℃/minute, and cooling rate is 60 ℃/hour.
The (ii) evaluation of target
To the target that obtains, measure density, body resistance value, X-ray diffraction analysis, crystallization particle diameter and various rerum natura.Its result, theoretical relative density is 96%, the body resistance value of utilizing four probe method to measure is 0.6m Ω m.
In addition, to the test portion that adopts from this sintered compact, utilize the crystalline state in the X-ray diffraction method observation transparent conductive material, its result in the target that obtains, only confirms the bixbite structural compounds.Especially, can not confirm to belong to SnO
2Or Sn
3In
4O
12The peak.The chart of the X-ray diffraction of target shown in Fig. 1.
And then, the sintered compact that embedding obtains in resin, after of the aluminium oxide particles polishing of its surface with particle diameter 0.05 μ m, utilizing electron rays microanalyser (EPMA) is JXA-8621MX (NEC corporate system), after being enlarged into 5000 times, be determined at the maximum diameter of the crystalline particle of observing in the cubic frame of 30 μ m * 30 μ m.Carry out same mensuration in three place's frames, calculate the mean value of maximum particle dia respectively, the crystallization particle diameter that confirms the bixbite structural compounds of this sintered compact is 2.5/ μ m.
Through carrying out the ultimate analysis of target, the content of Cr, Cd is less than 1ppm.
In addition, the sintered compact that obtains in (1) is carried out machining, make the sputtering target of the about 10cm of diameter, the about 5mm of thickness, utilize sputtering method to carry out the film forming of nesa coating.
(3) film forming of transparent conductive oxides (nesa coating)
With embodiment 1 (2) (i) in the same manner, obtain on glass substrate, be formed with the transparent conducting glass of thickness for the transparent conductive oxides of about 100nm.
(4) evaluation of sputter state
(i) the generation number of paradoxical discharge
To the sputtering target that obtains in (1), (ii) monitor having or not of paradoxical discharge in the same manner with embodiment 1 (2), but once also do not confirm.
(ii) bead produces number
With embodiment 1 (2) (iii) in the same manner, measure bead and produce number, obtain mean value.
(5) evaluation of the rerum natura of nesa coating
To the electroconductibility of the nesa coating on the transparent conducting glass that obtains in above-mentioned (3), the result who utilizes four probe method to measure than resistance is 500 μ Ω cm.
In addition, utilize X-ray diffraction analysis to confirm this nesa coating and be amorphousness.On the other hand, the smoothness on film surface is also measured, P-V value (JISB0601 benchmark) is 5nm, and therefore, it is good to confirm smoothness.
And then to the transparency of this nesa coating, utilizing the optical fiber transmitance under the light of the wavelength 500nm that spectrophotometer carries out is 90%, and the transparency is also superior.
And then warp is in the result with 35 ℃ of these nesa coatings of etching of 5 quality % oxalic acid, and etching speed is 80nm/ minute.
In addition, the etching speed that utilizes PAN to carry out in the same manner with embodiment 1 is 20nm/ minute down at 50 ℃, and the PAN resistance is good.
Also have, in table 2, the showing below of the evaluation of PAN resistance: 50 ℃, a 20nm/ minute following table are shown " zero ", with 50 ℃, greater than being expressed as " * " under 20nm/ minute the situation.
Also have, the condition determination that X-ray diffraction is measured (XRD) is (iv) identical with embodiment 1 (2).
Embodiment 7,8 and comparative example 8～10
The ratio of components of raw material is adjusted to atomic ratio in the table 2, in addition, with embodiment 6 in the same manner, make, estimated sputtering target and nesa coating.But, used the RF magnetron sputtering in the comparative example 8.That estimates the results are shown in the table 2.
[table 2]
Embodiment 9
Make the large-scale target that constitutes by the bixbite structural compounds basically of the composition identical, utilize DC magnetron sputtering, and oxalic acid etching, on organic membrane, make the electrode of TV usefulness liquid-crystal display with embodiment 6.The lighting test result of the panel through using this electrode making obtains the performance no less than the panel that uses ITO.
In addition, the friction burn does not take place under 10,000 hours continuous illumination yet.
(1) manufacturing of sputtering target
As raw material, the Indium sesquioxide, zinc oxide, the stannic oxide that mix purity 4N, median size 3 μ m, make that atomic ratio [In/ (In+Sn+Zn)] is 0.54, atomic ratio [Sn/ (In+Sn+Zn)] is 0.18, atomic ratio [Zn/ (In+Sn+Zn)] is 0.28, it is supplied with to wet-type ball mill, mix and pulverized 72 hours, obtained the raw material micropowder.
After the raw material micropowder that obtains carried out granulation, be the size of diameter 10cm, thickness 5mm, in its firing furnace of packing into, add at oxygen and to depress, under 1400 ℃, burnt till 48 hours, obtain sintered compact (target) its pressure forming.
(2) film forming of transparent conductive oxides
The sputtering target that obtains in above-mentioned (1) is assemblied in the DC magnetic controlled tube sputtering apparatus, is being arranged on the glass substrate of universal stage the nesa coating film forming.
Sputtering condition is as follows: sputtering pressure 1 * 10
-1Pa, oxygen partial pressure (O
2/ (O
2+ Ar)) 2%, arrive pressure 5 * 10
-4Pa, 200 ℃ of substrate temperatures, drop between power 120W, target substrate apart from 80mm, film formation time 15 minutes.
Its result obtains being formed with the transparent conductive oxides of thickness for about 100nm on glass substrate.Through utilizing ICP (inductively coupled plasma analysis) method analytical results, [In/ (In+Sn+Zn)] is 0.60 by atomic ratio, and atomic ratio [Sn/ (In+Sn+Zn)] is 0.17, and atomic ratio [Zn/ (In+Sn+Zn)] is 0.23, and the zinc amount is lacked than the target ratio of components.Not exclusively know reason, but be speculated as the contrary sputter of zinc composition.
(3) evaluation of the rerum natura of nesa coating
To the electroconductibility of the nesa coating on the transparent conducting glass that obtains in above-mentioned (2), the result who utilizes four probe method to measure than resistance is 600 μ Ω cm.
Under atmospheric pressure, carry out thermal treatment in 1 hour under 240 ℃ after, the result who measures than resistance is 650 μ Ω cm, does not almost change (initial value 1.1 times), and is also stable under the thermal treatment under atmospheric pressure.And then, the ratio resistance at 20 places in the face of glass substrate is measured, estimated inequality, but the difference of maximum value and minimum value is about 1.1 times, very homogeneous.
In addition, utilize X-ray diffraction analysis to confirm this nesa coating and be amorphousness.
Also have, the condition determination that X-ray diffraction is measured (XRD) is (iv) identical with embodiment 1 (2).
On the other hand, the smoothness on film surface is measured, P-V value (JISB0601 benchmark) is 5nm, therefore, confirms good.And then to the transparency of this transparent conductive oxides, utilizing the light penetration of the light of the wavelength 500nm that spectrophotometer carries out is 90%, and the transparency is also superior.
(4) evaluation of the etching characteristic of transparent and electrically conductive film
The nesa coating that the electrically conducting transparent that obtains in the etching solution that contains oxalic acid (oxalic acid 5wt%, the pure water 95wt%) etching above-mentioned (2) with the etching solution (phosphoric acid 87wt%, nitric acid 3wt%, acetic acid 10wt%) of 45 ℃ phosphoric acid and 35 ℃ is peeled off is measured etching speed.
The etching speed that utilizes the etching solution of phosphoric acid, nitric acid, acetic acid to carry out is 5nm/ minute (A), and the etching speed that utilizes the etching solution that contains oxalic acid to carry out is 100nm/ minute (B), B/A=20.
Behind the etchant etching that contains oxalic acid, observe section with electron microscope (SEM), the result who measures cone angle is 80 degree.In addition, with after containing etching reagent 150% over etching (over etch) of oxalic acid, observe with electron microscope (SEM), confirming etch residue does not almost have.
(5) evaluation of nesa coating and connecting airtight property metal
The result of connecting airtight property through utilizing scraping experiment evaluation and Mo (molybdenum), load up is 17N on the AE signal, the film crackle produces to begin to load and is 17N, and good.
Also have, the condition determination of scraping experiment is as described below.
Scraping experiment machine: CSEM corporate system Micro-Scratch-Tester
Scraping distance: 20mm
Scraping load: 0～30N
Rate of load condensate: 30N/ minute
Scraping speed: 20mm/ minute
Diamond needle shape: 0.2mmR
Detection method: load units and AE transmitter
(6) substrate making and estimating
Use the target of above-mentioned (1), with the film of above-mentioned (2), (Fig. 8 (a)) is with nesa coating 12 film forming (Fig. 8 (b)) of thickness 75nm on glass substrate 10.
Secondly, use by the Ag-Pd-Cu alloy (98.5: 0.5: the 1.0wt%) target of Gou Chenging, on nesa coating 12 with alloy layer film forming (Fig. 8 (c).The thickness of alloy layer 14 is 100nm.
On this alloy layer, apply sensitizer (resist).Upload to install at resist and count line width 40 μ m and the line sheet glass of the mask pattern of 70 μ m at interval, after the resist exposure, develop, after bake and bank up with earth.
Secondly, use the etching solution (phosphoric acid 87wt%, nitric acid 3wt%, acetic acid 10wt%) of phosphoric acid, etching alloy layer 14 is made a plurality of lines (line width 40 μ m, line clearance space 70 μ m) (Fig. 8 (d)) that are made of alloy layer 14.With these backboard substrate 10 washings, drying.
And then, go up coating sensitizer 9 resists at electrode layer (nesa coating 12 and the line that constitutes by alloy layer 14)).On resist, mounting is designed to line width 90 μ m and the line sheet glass of the mask pattern of 20 μ m at interval, after the resist exposure, develop, after bake and bank up with earth.Also have, in the exposure of resist, make a part (side) coupling (with reference to Fig. 8 (e)) at the edge of the line that constitutes by alloy layer 14 and nesa coating 12.
Secondly, use the aqueous solution of oxalic acid 5wt%, the above-mentioned nesa coating that obtains 12 of etching has been made a plurality of lines (line width 90 μ m, line clearance space 20 μ m) (Fig. 8 (e)) of nesa coating 12.
The semi-transflective reflective type electrode base board that obtains like this can be realized low resistance.In addition, through observe the result of substrate surface with scanning electron microscope, do not observe surface coarse of nesa coating 12.The etching solution that this expression contains phosphoric acid is etching nesa coating 12 hardly.In addition, almost do not find to carry out the variation of the edge part of the alloy layer 14 before and after the etching with oxalic acid.
(7) connective stability of TCP (Tape Carrier Package)
Utilize ACF (anisotropic conducting film) to carry out TCP and connect, relatively the TCP resistance before and after PCT (pressure cooking test) test.Being initially 4.7 Ω, is 4.7 Ω after the PCT test, stable.
TCP resistance is by carrying out connection based on TCP (with width 40 * 10
-6The connection of the metal terminal electrode of cm), the resistance value of measuring between any two obtains, and shows mean value that connect based on TCP and 50 of connection portions metal terminal.
Embodiment 11
(1) manufacturing of sputtering target
As raw material, mix purity 4N, median size 3 μ m following Indium sesquioxide, zinc oxide, stannic oxide, make that atomic ratio [In/ (In+Sn+Zn)] is 0.44, atomic ratio [Sn/ (In+Sn+Zn)] is 0.24, atomic ratio [Zn/ (In+Sn+Zn)] is 0.32, it is supplied with to wet-type ball mill, mix and pulverized 72 hours, obtained the raw material micropowder.
After the raw material micropowder that obtains carried out granulation, be the size of diameter 10cm, thickness 5mm, in its firing furnace of packing into, add at oxygen and to depress, under 1400 ℃, burnt till 48 hours, obtain sintered compact (target) its pressure forming.
(2) film forming of transparent conductive oxides
The sputtering target that obtains in above-mentioned (1) is assemblied in the DC magnetic controlled tube sputtering apparatus, is being arranged on the glass substrate of universal stage the nesa coating film forming.
Sputtering condition is as follows: sputtering pressure 2 * 10
-1Pa, oxygen partial pressure (O
2/ (O
2+ Ar)) 2%, arrive pressure 5 * 10
-4Between Pa, 200 ℃ of substrate temperatures, target substrate apart from 80mm, dropped into power 120W, film formation time 15 minutes.
Its result obtains being formed with the transparent conductive oxides of thickness for about 100nm on glass substrate.Through utilizing the result of the film that the analysis of ICP method obtains, [In/ (In+Sn+Zn)] is 0.50 by atomic ratio, and atomic ratio [Sn/ (In+Sn+Zn)] is 0.23, and atomic ratio [Zn/ (In+Sn+Zn)] is 0.27, and the zinc amount is lacked than the target ratio of components.Not exclusively know reason, but be speculated as the contrary sputter of zinc composition.
(3) evaluation of the rerum natura of nesa coating
Estimate in the same manner with embodiment 10 (3).The results are shown in the table 4.
(4) evaluation of the etching characteristic of nesa coating
Estimate in the same manner with embodiment 10 (4).The results are shown in the table 4.
(5) evaluation of nesa coating and connecting airtight property metal
Estimate in the same manner with embodiment 10 (5).The results are shown in the table 4.
(6) substrate making and estimating
Estimate in the same manner with embodiment 10 (6).
The semi-transflective reflective type electrode base board that obtains like this can be realized low resistance.In addition, through observe the result of substrate surface with scanning electron microscope, do not observe surface coarse of nesa coating 12.The etching solution that this expression contains phosphoric acid is etching nesa coating 12 hardly.In addition, almost do not find to carry out the variation of the edge part of the alloy layer 14 before and after the etching with oxalic acid.
(7) connective stability of TCP (Tape Carrier Package)
Estimate in the same manner with embodiment 10 (7).The results are shown in the table 4.
Except the ratio of components with raw material is adjusted to the atomic ratio shown in the table 3, with embodiment 10 in the same manner, make sputtering target and nesa coating, estimated nesa coating.The results are shown in the table 4.
Comparative example 11～13
Except the ratio of components with raw material is adjusted to the atomic ratio shown in the table 3, make sputtering target and nesa coating in the same manner with embodiment 10, estimated nesa coating.The results are shown in the table 4.
Comparative example 14～16
Except the ratio of components with raw material is adjusted to the atomic ratio shown in the table 3, make sputtering target and nesa coating in the same manner with embodiment 11, estimated nesa coating.The results are shown in the table 4.
[table 3]
[table 4]
Claims (36)
1. a sputtering target is characterized in that,
It is to contain indium, tin and zinc at least, and comprises by Zn
2SnO
4The spinel structure compound of expression reaches by In
2O
3The sintered compact of the oxide compound of the bixbite structural compounds of expression.
2. sputtering target according to claim 1 is characterized in that,
Being the value in 0.25～0.6 the scope by the atomic ratio of In/ (In+Sn+Zn) expression, is the value in 0.15～0.3 the scope by the atomic ratio of Sn/ (In+Sn+Zn) expression, is the value in 0.15～0.5 the scope by the atomic ratio of Zn/ (In+Sn+Zn) expression.
3. sputtering target according to claim 1 and 2 is characterized in that,
About the peak in the X-ray diffraction (XRD), by Zn
2SnO
4Maximum peak intensity (I (the Zn of the spinel structure compound of expression
2SnO
4)), with by In
2O
3Maximum peak intensity (I (the In of the bixbite structural compounds of expression
2O
3)) ratio (I (Zn
2SnO
4)/I (In
2O
3)) in 0.05～20 scope.
4. according to each described sputtering target in the claim 1～3, it is characterized in that,
About the peak in the X-ray diffraction (XRD), by SnO
2Maximum peak intensity (I (the SnO of the rutile structure compound of expression
2)), by Zn
2SnO
4Maximum peak intensity (I (the Zn of the spinel structure compound of expression
2SnO
4)) and by In
2O
3Maximum peak intensity (I (the In of the bixbite structural compounds of expression
2O
3)) satisfy following relation,
I(SnO
2)＜I(Zn
2SnO
4)
I(SnO
2)＜I(In
2O
3)
I(SnO
2)＜Max.(I(Zn
2SnO
4)，I(In
2O
3))÷10
[in the above-mentioned relation formula, (Max. (X, Y) any one big side among expression X and the Y].
5. according to each described sputtering target in the claim 1～4, it is characterized in that,
About the peak in the X-ray diffraction (XRD), the maximum peak intensity (I (ZnO)) of the wurtzite shape compound of representing by ZnO, by Zn
2SnO
4Maximum peak intensity (I (the Zn of the spinel structure compound of expression
2SnO
4)) and by In
2O
3Maximum peak intensity (I (the In of the bixbite structural compounds of expression
2O
3)) satisfy following relation,
I(ZnO)＜I(Zn
2SnO
4)
I(ZnO)＜I(In
2O
3)
I(ZnO)＜Max.(I(Zn
2SnO
4)，I(In
2O
3))÷10
[in the above-mentioned relation formula, (Max. (X, Y) any one big side among expression X and the Y].
6. according to each described sputtering target in the claim 1～5, it is characterized in that,
About the peak in the X-ray diffraction (XRD), by In
2O
3(ZnO)
mMaximum peak intensity (I (the In of the hexagonal crystal lamellar compound of (m represents 2～20 integer) expression
2O
3(ZnO)
m)), by Zn
2SnO
4Maximum peak intensity (I (the Zn of the spinel structure compound of expression
2SnO
4)) and by In
2O
3Maximum peak intensity (I (the In of the bixbite structural compounds of expression
2O
3)) satisfy following relation,
I(In
2O
3(ZnO)
m)＜I(Zn
2SnO
4)
I(In
2O
3(ZnO)
m)＜I(In
2O
3)
I(In
2O
3(ZnO)
m)＜Max.(I(Zn
2SnO
4)，I(In
2O
3))÷10
[in the above-mentioned relation formula, (Max. (X, Y) any one big side among expression X and the Y].
7. according to each described sputtering target in the claim 1～6, it is characterized in that,
In the image of electron rays microanalyser (EPMA), part S of rich indium (In) and rich plumbous part S (Zn) constitute island structure, its area than S (Zn)/S (In) in 0.05～100 scope.
8. according to each described sputtering target in the claim 1～7, it is characterized in that,
By In
2O
3The crystallization particle diameter of the bixbite structural compounds of expression is below the 10 μ m.
9. according to each described sputtering target in the claim 1～8, it is characterized in that,
Body resistance is in the scope of 0.3～100m Ω cm.
10. according to each described sputtering target in the claim 1～9, it is characterized in that,
Theoretical relative density is more than 90%.
11. the manufacture method of a sputtering target, this sputtering target are each described sputtering targets in the claim 1～10, wherein, described manufacture method comprises:
Obtain with the powder of the powder of indium compound, zn cpds, and the tin compound powder of the particle diameter little than the particle diameter of these powder with the atomic ratio represented by In/ (In+Sn+Zn) in 0.25～0.6 scope, by the atomic ratio of Sn/ (In+Sn+Zn) expression in 0.15～0.3 scope, the operation of the mixture that cooperates by the ratio of atomic ratio in 0.15～0.5 scope of Zn/ (In+Sn+Zn) expression;
With described mixture press molding, be made into the operation of body;
The operation of the described molding of sintering.
12. a nesa coating, it is to use each described sputtering target in the claim 1～10, utilizes sputtering method to carry out that film forming forms.
13. a transparency electrode, it is that the described nesa coating of etching claim 12 obtains.
14. a sputtering target is characterized in that,
Contain indium, tin, zinc and oxygen, utilize X-ray diffraction (XRD), only observe the peak of bixbite structural compounds basically.
15. sputtering target according to claim 14 is characterized in that,
Described bixbite structural compounds is by In
2O
3Expression.
16. according to claim 14 or 15 described sputtering targets, it is characterized in that,
Atomic ratio by In/ (In+Sn+Zn) expression be greater than 0.6 and less than the value in 0.75 the scope, is 0.11～0.23 the interior value of scope by the atomic ratio of Sn/ (In+Sn+Zn) expression.
17. according to each described sputtering target in the claim 14～16, it is characterized in that,
About the peak in the X-ray diffraction (XRD), the maximum peak position of bixbite structural compounds is with respect to In
2O
3The peak of single crystal powder is shifted to positive dirction (wide-angle side).
18. according to each described sputtering target in the claim 14～17, it is characterized in that,
The mean diameter of the Zn aggregate of being observed by electron rays microanalyser (EPMA) is below the 50 μ m.
19. according to each described sputtering target in the claim 14～18, it is characterized in that,
The content of Cr, Cd is respectively below the 10ppm (quality).
20. according to each described sputtering target in the claim 14～19, it is characterized in that,
The content of Fe, Si, Ti, Cu is respectively below the 10ppm (quality).
21. according to each described sputtering target in the claim 14～20, it is characterized in that,
The crystallization particle diameter of bixbite structural compounds is below the 20 μ m.
22. according to each described sputtering target in the claim 14～21, it is characterized in that,
Body resistance is in the scope of 0.2～100m Ω cm.
23. according to each described sputtering target in the claim 14～22, it is characterized in that,
Theoretical relative density is more than 90%.
24. the manufacture method of a sputtering target is characterized in that, comprising:
Obtain will as the compound of indium, tin and the zinc of the raw material of sputtering target with by the atomic ratio of In/ (In+Sn+Zn) expression greater than 0.6 less than 0.75 scope in, and the operation of the mixture that cooperates by the ratio of atomic ratio in 0.11～0.23 scope of Sn/ (In+Sn+Zn) expression;
With described mixture press molding, be made into the operation of body;
10～1, in 000 ℃/hour the scope, the operation that the temperature of described molding is heated up;
1,100～1, the temperature in 700 ℃ the scope is burnt till described molding, obtains the operation of sintered compact;
10～1, in 000 ℃/hour the scope, cool off the operation of described sintered compact.
25. a nesa coating, it is to utilize sputtering method, each described sputtering target in the claim 14～23 is carried out film forming forms.
26. a transparency electrode, it is that the described nesa coating of etching claim 25 is made.
27. transparency electrode according to claim 26 is characterized in that,
The cone angle of electrode tip is 30～89 degree.
28. the making method of a transparency electrode is characterized in that,
With containing 1～10 quality % oxalic acid aqueous solution, under 20～50 ℃ temperature range, the described nesa coating of etching claim 25.
29. a nesa coating, wherein,
Comprise: the amorphousness oxide compound of indium (In), zinc (Zn), tin (Sn) is 0.20 when following at the atomic ratio with respect to the Sn of In, Zn and Sn, satisfies following atomic ratio 1, surpassing at 0.20 o'clock, satisfies following atomic ratio 2.
Atomic ratio 1
0.50＜In/(In+Zn+Sn)＜0.75
0.11＜Sn/(In+Zn+Sn)≤0.20
0.11＜Zn/(In+Zn+Sn)＜0.34
Atomic ratio 2
0.30＜In/(In+Zn+Sn)＜0.60
0.20＜Sn/(In+Zn+Sn)＜0.25
0.14＜Zn/(In+Zn+Sn)＜0.46
30. nesa coating according to claim 29, wherein,
The ratio that utilization contains etching speed A that the etching solution of phosphoric acid carries out, contain the etching speed B that the etching solution of oxalic acid carries out with utilization is that B/A is more than 10.
31. a transparency electrode, it comprises: claim 29 or 30 described nesa coatings, wherein,
The cone angle of described transparency electrode is 30～89 degree
32. an electrode base board, it comprises: the transparency electrode that comprises claim 29 or 30 described nesa coatings; By metal or alloy constitute the layer.
33. electrode base board according to claim 32, wherein,
Described metal or alloy comprises: the element that is selected from Al, Ag, Cr, Mo, Ta, W.
34. according to claim 32 or 33 described electrode base boards, wherein,
Be used for semi-transflective reflective type liquid crystal.
35. according to each described electrode base board in the claim 32～34, wherein,
The described layer that is made of metal or alloy is a supporting electrode.
36. the manufacture method of an electrode base board, it is the manufacture method of each described electrode base board in the claim 32～35, wherein, comprising:
Make the operation of nesa coating;
On at least a portion on the described nesa coating stacked by metal or alloy constitute the layer operation;
With the etching solution etching that contains oxygen acid described by metal or alloy constitute the layer operation;
Operation with the described nesa coating of etching solution etching that contains carboxylic acid.
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| JP253986/2005 | 2005-09-01 | ||
| JP2005253986A JP4933756B2 (en) | 2005-09-01 | 2005-09-01 | Sputtering target |
| JP2005271665A JP4947942B2 (en) | 2005-09-20 | 2005-09-20 | Sputtering target |
| JP271665/2005 | 2005-09-20 | ||
| JP2005303024A JP4804867B2 (en) | 2005-10-18 | 2005-10-18 | Transparent conductive film, transparent electrode, electrode substrate and manufacturing method thereof |
| JP303024/2005 | 2005-10-18 | ||
| PCT/JP2006/317135 WO2007026783A1 (en) | 2005-09-01 | 2006-08-30 | Sputtering target, transparent conductive film and transparent electrode |
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| CN2011102672334A Division CN102337505A (en) | 2005-09-01 | 2006-08-30 | Sputtering target, transparent conductive film, transparent electrode, electrode substrate, and method for producing same |
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