CN104212997B - The film build method of Cu Mn alloy films and Cu Mn alloy sputtering targets and Cu Mn alloy films - Google Patents
The film build method of Cu Mn alloy films and Cu Mn alloy sputtering targets and Cu Mn alloy films Download PDFInfo
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- CN104212997B CN104212997B CN201410239491.5A CN201410239491A CN104212997B CN 104212997 B CN104212997 B CN 104212997B CN 201410239491 A CN201410239491 A CN 201410239491A CN 104212997 B CN104212997 B CN 104212997B
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- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C14/00—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material
- C23C14/06—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material characterised by the coating material
- C23C14/14—Metallic material, boron or silicon
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- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22C—ALLOYS
- C22C9/00—Alloys based on copper
- C22C9/05—Alloys based on copper with manganese as the next major constituent
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- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C14/00—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material
- C23C14/22—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material characterised by the process of coating
- C23C14/34—Sputtering
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Abstract
The present invention provide cope with it is needed for the display quality for making the flat display of high-resolution is lifted, in electrode film or wiring membrane the Cu Mn alloy films of the new demand of low reflection and for formed it Cu Mn alloy sputtering targets and Cu Mn alloy films film build method.The Cu Mn alloy films are as follows：When metal ingredient is totally considered as into 100 atom %, metal ingredient contains the Mn of 32~45 atom %, surplus and is made up of Cu and inevitable impurity, the visible reflectance of the Cu Mn alloy films is less than 30%, is suitably for the electrode film or wiring membrane of flat display.
Description
Technical field
The present invention relates to require what antiradar reflectivity, such as flat display electrode film or wiring membrane were used
Cu-Mn alloy films and for formed it Cu-Mn alloy sputtering targets and Cu-Mn alloy films film build method.
Background technology
With above transparent glass substrate etc. formed thin-film device liquid crystal display (hereinafter referred to as " LCD "),
Flat display apparatus (the Flat of the electrophoresis escopes for being utilized such as plasma display (hereinafter referred to as " PDP "), Electronic Paper etc.
Panel Display, hereinafter referred to as " FPD ") big picture, high-resolution, quick response, it is desirable to its wiring membrane low resistance
Change.Additionally, adding the touch panel of operability in developing FPD in recent years or using resin substrate or very thin glass substrate
Flexible FPD etc. new product.
In addition, the touch panel substrate picture that directly operability is assigned while the picture of viewing FPD is also being advanced
The product that touch panel operation is carried out in maximization, smart mobile phone, panel computer and desktop computer etc. is also being popularized.Touch
The position detecting electrode of panel is generally used as the indium tin oxide (hereinafter referred to as " ITO ") of nesa coating.
In addition, in recent years, the custom for being configured with quadrangle ito film is developed into the capacitive touch panels that can be detected with multiple spot
Claim rhombus configuration, metal film is used as the electrode film of connection quadrangle ito film or the diaphragm of wiring membrane, the metal film is used
It is readily obtained Mo the or Mo alloys with the contact of ito film.
Additionally, the flexible FPD of resin film substrate or very thin glass substrate beyond having used glass substrate etc., using
The product of touch panel is just energetically developed.
However, when forming the metal film and curved substrate of above-mentioned Mo or Mo alloys in these purposes, it is known that produce sometimes
Following problem：Easily cracked in Mo films or Mo alloy films, it is impossible to ensure the adaptation with substrate, it is impossible to fully tie up
Hold the effect of protection wiring membrane Cu films.Method accordingly, as Mo or Mo alloys are not used, Cu alloys attract attention and carry again
Go out by it to ensure the above-mentioned adaptation with substrate.(with reference to 1~patent document of patent document 3)
Prior art literature
Patent document
Patent document 1：Japanese Unexamined Patent Publication 2012-211378 publications
Patent document 2：Japanese Unexamined Patent Publication 2012-212811 publications
Patent document 3：Japanese Unexamined Patent Publication 2013-67857 publications
The content of the invention
Problems to be solved by the invention
On the Cu alloy films proposed in patent document 1 and patent document 2, in order to obtain with low-resistance wiring membrane
Propose at least one element to be formed and contained in the group for being selected from and being made up of Ag, Au, C, W, Ca, Mg, Al, Sn, B and Ni in Cu
Cu-Mn-X alloy films as Cu films basilar memebrane, for ensuring that Cu alloy films are closely sealed with substrate, dielectric film or semiconductor film
Property.
In addition, in order to ensure for the semiconductor film (hereinafter referred to as " IGZO being made up of indium-gallium-zinc-oxygen in patent document 3
Film ") shielding, it is proposed that formed by comprising concentration being more than 8 atom % and the Mn of below 30 atom % and inevitable
Impurity Cu-Mn alloys formed Cu alloy films method.
On the other hand, used in nearest main flow is with 4 times of large-scale 4K-TV of the more high-resolution of full HD pixel
The lower Cu of resistance increases as the method for main wiring material compared with Al.In addition, for left away from eyes several tens cm
The small high-definition for but realizing full HD display of picture though the smart mobile phone of right super close distance operating display frame has expanded.With
The high-definition, incident light makes the problem of display quality reduction gradually significantly change by Metal film reflector.Therefore, metal film has
The requirement of this new features of antiradar reflectivity (being otherwise referred to as below " low reflection ") rapidly increases.
In addition, in the manufacturing process of flat display, touch panel, pattern is carried out after electrode film/wiring membrane is formed
In the heating treatment step of photoresist during change, due to carrying out 230 DEG C or so of heating in air atmosphere, therefore
If the metal film for obtaining low reflection preferably below the temperature, when may be heated at 200 DEG C.
Now, the Al films used by the wiring membrane of flat display apparatus midplane display element are have in visible region
The metal film of more than 90% high reflectance.In addition, be equally flat display wiring membrane used by Cu films in visible ray
Region has 70% reflectivity, has equal with Ag films more than 95% high reflection in the long wavelength region of more than 600nm
Rate.On the other hand, the Mo films or Mo alloy films being laminated to protect these wiring membranes have 60% or so reflectivity.These
Even if metal film is by the manufacturing process of flat display, reflectivity also hardly changes, thus metal film reflection especially
It is to turn into make the principal element of display quality reduction in the display device of high-resolution.
Therefore, in the display device of high-resolution, it is desirable to the electricity of the lower reflection of less than the 30% of half of Mo etc. or so
Pole film/wiring membrane.
As described above, various Cu alloy films are developed so far, but these patent documents are conceived to wiring membrane, screened film and carry out
Research, on should to the display device of high-resolution from now on needed for this new features of low reflection do not carry out any research.
It is an object of the invention to provide cope with make the flat display of high-resolution display quality lifting needed for
, Cu-Mn alloy films of the new demand of low reflection and for forming its Cu-Mn alloy sputtering targets in electrode film or wiring membrane
And the film build method of Cu-Mn alloy films.
The scheme for solving problem
The present inventor is in view of the above problems, low anti-in order to be obtained in flat display, the manufacturing process of touch panel
The characteristic penetrated, takes with Cu as main component, optimizes addition element and addition.As a result, being added in finding Cu specific
The Cu-Mn alloy films of the Mn of amount can obtain the characteristic of low reflection, it is achieved thereby that of the invention.
That is, the present invention relates to Cu-Mn alloy films, wherein, when metal ingredient is totally considered as into 100 atom %, metal ingredient
Mn, surplus containing 32~45 atom % are made up of Cu and inevitable impurity, the visible reflectance of the Cu-Mn alloy films
Rate is less than 30%.
In addition, Cu-Mn alloy films of the invention contain metal ingredient and oxygen, metal ingredient is totally considered as 100 atom %
When, aforementioned metal composition contains the Mn of 32~45 atom %, surplus and is made up of Cu and inevitable impurity, and oxygen is relative to foregoing
The ratio of the summation of metal ingredient and foregoing oxygen with atomic ratio measuring be 0.3~0.6.
In addition, Cu-Mn alloy films of the invention are suitably for the electrode film or wiring membrane of flat display.
In addition, the Cu-Mn that the present invention is the Mn containing 32~45 atom %, surplus to be made up of Cu and inevitable impurity
Alloy sputtering target.
Recrystallized structure is contained in the Cu-Mn alloy sputtering targets of the invention preferably crystal boundary with Cu-Mn alloyed powders
Tissue.
Cu-Mn alloy films of the invention can be obtained as follows：Pass through in the atmosphere of the oxygen containing 30~60 volume %
The Cu-Mn alloy films that sputtering forms the Mn containing 32~45 atom %, surplus is made up of Cu and inevitable impurity.
In addition, Cu-Mn alloy films of the invention can also be obtained as follows：Contained by sputtering formation in inert atmosphere
The Cu-Mn alloy films that the Mn of 32~45 atom %, surplus are made up of Cu and inevitable impurity, then at 200~225 DEG C
Foregoing Cu-Mn alloy films are heated in air atmosphere.
The effect of invention
Cu-Mn alloy films of the invention can realize the unavailable low this new features of reflection of existing electrode film/wiring membrane,
Therefore the display quality of such as FPD etc. can be improved.Therefore, such as 4K- for being attracted attention for the FPD as more high-resolution
Next generation's information terminal such as TV, smart mobile phone or panel computer or using being highly useful for the flexible FPD of resin substrate
Technology.Because especially the low reflectionization of metal film is extremely important in these products.
Brief description of the drawings
Fig. 1 is the macrograph of the section with observation by light microscope Cu-Mn alloy sputtering targets of the invention.
Specific embodiment
Key character of the invention is, used as the Cu for being suitably for the electrode film of such as flat display, wiring membrane
Alloy film, by the Cu-Mn alloys using the Mn that specified quantitative is with the addition of in Cu, so as to find the low new features of reflectivity.Need
Illustrate, in the following description, " reflectivity " refers to the flat of the scope of the 360~740nm of wavelength for belonging to visible region
Equal reflectivity.Hereinafter, it is described in detail for the present invention.
On Cu-Mn alloy films of the invention, because by above-mentioned one of the reasons why the Mn of specified quantitative is added in Cu
Make reflectance reduction after the heating treatment step of photoresist when being patterned.As described above, plane shows now
Al films used by the wiring membrane of element are the metal film of the high reflectance for having more than 90% in visible region.In addition, same
Be flat display wiring membrane used by Cu films visible region have 70% reflectivity, the length in more than 600nm
Wavelength region has equal with Ag films more than 95% high reflectance.
On the other hand, the Mo films or Mo alloy films being laminated to protect these wiring membranes have 60% or so reflection
Rate.Even if these metal films also hardly change by the process of above-mentioned display element manufacturing process, reflectivity.
In contrast, Cu-Mn alloy films of the invention pass through the Cu-Mn alloys using the Mn that specified quantitative is with the addition of in Cu,
It is achieved thereby that antiradar reflectivity.According to the research of the present inventor, it is thus identified that the reflectance reduction effect is by metal ingredient totality
When being considered as 100 atom %, the addition of metal ingredient Mn when being 32~45 atom % performance it is obvious.Though its reason is indefinite,
Cu-Mn alloys be the alloy of complete solid solution system, its fusing point Mn amount for 38 atom % when it is minimum.If also, Cu-Mn alloy films
Fusing point is low, then easily cause the movement of recrystallization, atom during above-mentioned heating is carried out.In addition, being closed on Cu-Mn
Mn in golden film, when being heated in the presence of oxygen, Mn easily propagates through crystal boundary and moves to film surface.
In this way, considering as follows on Cu-Mn alloy films of the invention：When metal ingredient is totally considered as into 100 atom %, lead to
Crossing makes the addition of metal ingredient Mn for 32~45 atom %, so that as the compositing range that fusing point is low scope, in air gas
When 200~225 DEG C of heating is carried out in atmosphere, the Mn in Cu-Mn alloy films is diffused into film surface and forms oxide and make
Reflectance reduction.
In addition, the Cu-Mn alloy film lower in order to be made reflectivity, it is preferred that metal ingredient is totally considered as 100 former
During sub- %, the addition of metal ingredient Mn is set to be 32~40 atom %, more preferably 32~39 atom %.
Cu-Mn alloy films of the invention, by containing metal ingredient and oxygen, metal ingredient to be totally considered as 100 atom %
When, aforementioned metal composition contains the Mn of 32~45 atom %, surplus and is made up of Cu and inevitable impurity, makes oxygen relative to preceding
State metal ingredient and foregoing oxygen summation ratio with atomic ratio measuring be 0.3~0.6, it is hereby achieved that lower reflectivity.
For Cu-Mn alloy films, if carrying out the heating in air atmosphere, the film forming in oxygen containing atmosphere, can contain aerobic in film.
Especially Mn is easier to be closed with oxygen key than Cu, therefore the Cu-Mn alloy films of the Mn containing specified quantitative of the invention easily absorb big
The oxygen of amount, such that it is able to obtain antiradar reflectivity.
In pure Cu films, oxygen is with Cu2Linear compound mode on the equilbrium phase diagram of O, CuO is present.On the other hand, it is believed that
Cu-Mn alloy films by containing Mn so that formed stable region field width comprising MnO, Mn3O4With the nonequilibrium phase of Cu, with wide
Compositing range absorbs oxygen, therefore is readily obtained lower reflectivity.
On Cu-Mn alloy films of the invention, by making the oxygen in the film relative to the ratio of the summation of metal ingredient and oxygen
Example with atomic ratio measuring be more than 0.3, such that it is able to suppress carry metallic luster reflection, it is possible to achieve antiradar reflectivity.In addition, closing
In Cu-Mn alloy films of the invention, by making the oxygen in the film relative to the ratio of metal ingredient and the summation of oxygen with atomic ratio
Less than 0.6 is calculated as, such that it is able to suppressing the transmission of light, realizing antiradar reflectivity and adaptation with substrate etc. can be improved.Cause
This, ratio of the oxygen relative to aforementioned metal composition and the summation of foregoing oxygen contained in Cu-Mn alloy films of the invention is with atom
Than being calculated as 0.3~0.6.Preferably 0.33~0.57.
The thickness of Cu-Mn alloy films of the invention is preferably 20~200nm.In the present invention, by by Cu-Mn alloy films
Thickness is set to more than 20nm, such that it is able to the transmission for suppressing light, the Cu-Mn alloy films that obtain antiradar reflectivity.Additionally, of the invention
In, below 200nm being set to by by the thickness of Cu-Mn alloy films, such that it is able to the time shortened for film forming and can press down
It is made the warpage by substrate caused by membrane stress after film or after heating.In the present invention, in order to productivity ratio higher
The low Cu-Mn alloy films of reflectivity are stably obtained, the thickness of Cu-Mn alloy films is more preferably set to 50~100nm.
The use of the sputtering method of sputtering target material is most suitable to form Cu-Mn alloy films of the invention.As sputtering
Method, can apply using and the composition identical Cu-Mn alloy sputtering targets of Cu-Mn alloy films carry out the method, such as of film forming
The method that film forming is carried out by cosputtering using the sputtering target material of Cu sputtering target materials and Mn or Mn-Cu alloys.
Wherein, preferably using carries out the side of film forming with the composition identical Cu-Mn alloy sputtering targets of Cu-Mn alloy films
Method.And, it is made up of Cu and inevitable impurity by using the Mn containing 32~45 atom %, surplus in the present invention
Cu-Mn alloy sputtering targets, such that it is able to easy and be stably formed Cu-Mn alloy films.In addition, as described above, in order to steady
Surely obtain that there is the Cu-Mn alloy films of lower reflectivity, preferably use the Mn containing 32~40 atom %, surplus by Cu and
The Cu-Mn alloy sputtering targets of inevitable impurity composition.The content range of Mn in Cu-Mn alloy sputtering targets of the invention
More preferably 32~39 atom %.
Cu-Mn alloy sputtering targets of the invention can be manufactured with the following method：The raw material that composition requirement will be modulated to melts
Change/cast and make ingot casting, the method manufactured using machining；The atomizing raw materials of composition requirement will be modulated to or casting is crushed
Ingot and make Cu-Mn alloy powders, using high temperature insostatic pressing (HIP) (hereinafter referred to as " HIP ") etc. by the method for its pressure sintering.
Manufacture method on Cu-Mn alloy sputtering targets of the invention, can according to the size of sputtering target material, shape,
The appropriate selected method that can inexpensively and stably manufacture.Cu-Mn alloy sputtering targets of the invention are preferably used by Cu-Mn
The atomized powder that alloy is formed, optimizes sintering temperature to manufacture, and recrystallization is contained in the crystal boundary of Cu-Mn alloyed powders so as to be made
The tissue of tissue.Thus, Cu-Mn alloy sputtering targets of the invention have the tissue without strain for having recrystallized, so as to press down
System splashing etc. produces abnormal grain, can stably obtain uniform and high-grade Cu-Mn alloy films.
In Cu-Mn alloy sputtering targets of the invention, in order to ensure antiradar reflectivity, it is necessary to occupy surplus beyond element M n
Except the content of the inevitable impurity of Cu it is more few more preferred, can contain not damaging in the range of effect of the invention
The inevitable impurity such as nitrogen, carbon, Fe, Si.For example, nitrogen is below 1000 mass ppm, carbon being for below 200 mass ppm, Fe
Below 500 mass ppm, Si are that 100 mass ppm are such as the following, and the purity for removing gas componant is preferably more than 99.9 mass %.
Cu-Mn alloy films of the invention can be obtained using following so-called reactive sputtering method, use sputtering target material
When being sputtered, using the sputtering containing reactant gas oxygen in non-active gas argon gas as conventional sputter gas etc.
Gas.Now, the containing ratio of the oxygen in sputter gas is preferably 30~60 volume %.
In addition, Cu-Mn alloy films of the invention can also be obtained as follows：When being sputtered using sputtering target material, in argon gas
Deng Cu-Mn alloy films are formed by sputtering in inert atmosphere, the Cu-Mn is then heated in 200~225 DEG C of air atmosphere
Alloy film.
Embodiment 1
First, the sputtering target material for forming Cu-Mn alloy films is made.Carrying out weighing makes with atomic ratio measuring to be 80 atom %
Mn-Cu, carries out melt-casting and makes ingot casting with vacuum fusion stove.Then, the ingot casting is machined, so as to make straight
The sputtering target material of footpath 100mm, thickness 5mm.
It should be noted that on for forming the Al sputtering target materials as the Al films of comparative example, buying Sumitomo Chemical strain
The Al sputtering target materials of formula commercial firm manufacture are prepared.In addition, on for forming the Cu sputtering target materials as the Cu films of comparative example,
To Hitachi Cable, oxygen-free copper (OFC) raw material of Ltd. manufactures are processed to make Cu sputtering target materials.In addition, on
For forming the Mo sputtering target materials as the Mo films of comparative example, the Mo powder pressure sintering of purity 4N is made Mo sputtering targets
Material.
To be soldered on backing plate made of copper by each sputtering target material of above-mentioned making, put into ULVAC, the sputtering dress of Inc. manufactures
Put (model：CS-200).Then, on the glass substrate of 25mm × 50mm the metal film of thickness shown in formation table 1 and make and comment
The sample of valency.It should be noted that for the film forming of Cu-Mn alloy films, using by the Cu sputtering target materials of above-mentioned preparation and 80
The cosputtering method that atom %Mn-Cu sputtering target materials are sputtered simultaneously, makes the power for being applied to each sputtering target material change and be formed
The Cu-Mn alloy films of difference composition.
Inductively coupled plasma atomic emission device (the ICP models manufactured using Shimadzu Scisakusho Ltd：
ICPV-1017 the composition of the Cu-Mn alloy films of film forming) is confirmed.
Then the heating of 30 minutes, 150 DEG C in the air atmosphere, at a temperature of 200 DEG C is carried out to each sample, is obtained
The sample of measuring reflectance.The measurement result of the reflectivity of each sample obtained by being shown in table 1.It should be noted that anti-
Penetrate the spectrocolorimeter (model that rate uses Konica Minolta, Inc. manufactures：CM2500d).It should be noted that in table 1
Mark * represent outside the scope of the present invention.
[table 1]
As shown in table 1, it is known that even if Al, Cu with low-resistance value or the Mo for stacked film enter in air atmosphere
The heating that 200 DEG C of row, reflectivity is also hardly reduced.
In contrast, it is known that the reflectivity of Cu-Mn alloy films of the invention is in a slight decrease when being heated with 150 DEG C, with
200 DEG C are further greatly reduced when being heated.The addition for especially confirming the Mn in Cu-Mn alloy films is 32~43 originals
During the scope of sub- %, obtain the antiradar reflectivity that reflectivity is less than 30%, as be suitably for flat display electrode film,
The Cu-Mn alloy films of wiring membrane.
Embodiment 2
Determine specimen coding 1, numbering 5, numbering 6, the sample of numbering 7 in the sample in air atmosphere to embodiment 1
Carry out 225 DEG C, 250 DEG C, 300 DEG C of heating when Cu-Mn alloy films reflectivity, be as a result shown in table 2.Need explanation
It is that the mark * in table 2 is represented outside the scope of the present invention.
[table 2]
As shown in table 2, on the reflectivity of Cu-Mn alloy films, it is thus identified that when the heating-up temperature in air atmosphere is 225 DEG C
Further reduced compared with 200 DEG C shown in table 1.On the other hand, it is thus identified that when the heating-up temperature in air atmosphere is 250 DEG C,
The reflectivity of Cu-Mn alloy films more than 30%, be significantly increased.Therefore can confirm, in order to obtain Cu-Mn alloy films of the invention,
The heating-up temperature of the Cu-Mn alloy films in air atmosphere is preferably 200~225 DEG C.
Embodiment 3
In order to make with the sputtering target material of atomic ratio measuring Cu-34 atoms %Mn, composition identical atomized powder is made, used
The sieve of 100 mesh is classified, and obtains the Cu-Mn alloy powders of 70 μm of average grain diameter.Chemistry point is carried out to the Cu-Mn alloy powders
Analysis, results verification purity is 99.9%.
Then, it is filled into cylinder internal diameter 133mm × height 30mm and thickness is the mild steel container of 3mm, adds at 450 DEG C
Heat is de-gassed treatment in 5 hours.Then, mild steel container is sealed, using HIP devices in 800 DEG C of sintering temperature, moulding pressure
118MPa, sintering time are sintered under conditions of 5 hours.
Taken out from HIP devices after the cooling period, mild steel container is removed by machining, obtain diameter 100mm, thickness
The Cu-Mn alloy sputtering targets of the invention of 5mm, test film is cut by remainder.
Inductively coupled plasma atomic emission device (the ICP) (model manufactured with Shimadzu Scisakusho Ltd：
The quantitative analysis of the metallic element of the test film obtained by ICPV-1017) carrying out, the quantitative use non-dispersive type infrared ray of oxygen is inhaled
Receipts method is measured, and as a result the purity of the total of the assay value of Cu, Mn is that 99.9%, oxygen concentration is 560 mass ppm, is confirmed
The Cu-Mn alloy sputtering targets of high-purity are arrived.
To carrying out mirror ultrafinish by test film obtained above, then corroded with aqueous solution of nitric acid, used optical microphotograph
Mirror carries out structure observation, is as a result shown in Fig. 1.As shown in Figure 1, it is thus identified that Cu-Mn alloy sputtering targets of the invention are in atomized powder
There is the tissue of fine recrystallization, the defect big to segregation, hole etc. unconfirmed, is suitable in the crystal boundary of the almost spherical at end
In the Cu-Mn alloy sputtering targets of spatter film forming.
In addition, will be soldered on backing plate made of copper by Cu-Mn alloy sputtering targets of the invention obtained above, then fill
Enter the sputter equipment (model of CANON ANELVA CORPRORATION manufactures：SPF-440HL), in argon gas atmosphere, pressure
Implement sputtering under conditions of 0.5Pa, power 500W.
When being sputtered using Cu-Mn alloy sputtering targets of the invention, no paradoxical discharge is confirmed, can be stablized
Sputtering.
Embodiment 4
The Cu-Mn alloy sputtering targets of the invention that will be made by embodiment 3 put into ULVAC, the sputtering dress of Inc. manufactures
Put (model：SBH-2204), it is real under conditions of pressure 0.8Pa, power 300W using the sputter gas containing argon gas and oxygen
Apply sputtering.
Similarly to Example 1, the glass substrate of 25mm × 50mm is used as substrate, the sputtering shown in table 3 is adjusted to
Amount of oxygen in atmosphere, forms the Cu-Mn alloy films of thickness 100nm.The reflectivity of each sample is determined, table 3 is as a result shown in.Need
Illustrate, use photoelectron spectroscopy device ESCA (Electoron spectroscopy for chemical analysis)
(KRATOS companies manufacture, model：AXIS-HS) oxygen amount in analysis Cu-Mn alloy films, represents oxygen relative to metal with atomic ratio
The ratio of the summation of composition and oxygen.In addition, the mark * in table 3 is represented outside the scope of the present invention.
[table 3]
As shown in table 3, it is known that when the oxygen concentration in sputter gas is more than 30 volume %, reflectance reduction is same with this
When Cu-Mn alloy films in oxygen amount increase.On the other hand, it is thus identified that oxygen is relative to metal ingredient and oxygen in Cu-Mn alloy films
The ratio of summation with atomic ratio measuring more than 0.6 when, transmitted light increases and produces film to peel off.
Claims (6)
1. a kind of Cu-Mn alloy films, it is characterised in that when metal ingredient is totally considered as into 100 atom %, metal ingredient contains 32
The Mn of~45 atom %, surplus are made up of Cu and inevitable impurity, and oxygen is relative to the summation of the metal ingredient and oxygen
Ratio is 0.3~0.6 with atomic ratio measuring, and the visible reflectance of the Cu-Mn alloy films is less than 30%.
2. a kind of Cu-Mn alloy films, it is characterised in that containing metal ingredient and oxygen, metal ingredient is totally considered as 100 atom %
When, the metal ingredient contains the Mn of 32~45 atom %, surplus and is made up of Cu and inevitable impurity, and oxygen is relative to described
The ratio of the summation of metal ingredient and the oxygen is 0.3~0.6 with atomic ratio measuring, and the Cu-Mn alloy films are flat display
Electrode film or wiring membrane.
3. Cu-Mn alloy films according to claim 1, it is characterised in that its be flat display electrode film or
Wiring membrane.
4. a kind of Cu-Mn alloy sputtering targets, it is characterised in that it contains the Mn of 34~45 atom %, surplus by Cu and can not
The impurity for avoiding is constituted, and the tissue of recrystallized structure, the Cu-Mn alloys are contained in the crystal boundary with Cu-Mn alloyed powders
Sputtering target material is used in the case where following either condition is met：
The condition sputtered in the atmosphere of the oxygen containing 30~60 volume %,
Or sputtered in inert atmosphere, Cu-Mn alloy films are formed, then heated in 200~225 DEG C of air atmosphere
The condition of the Cu-Mn alloy films.
5. a kind of film build method of Cu-Mn alloy films, it is characterised in that lead in the atmosphere of the oxygen containing 30~60 volume %
Cross the Cu-Mn alloy films that sputtering forms the Mn containing 32~45 atom %, surplus is made up of Cu and inevitable impurity.
6. a kind of film build method of Cu-Mn alloy films, it is characterised in that in inert atmosphere by sputter formed containing 32~
The Cu-Mn alloy films that the Mn of 45 atom %, surplus are made up of Cu and inevitable impurity, then in 200~225 DEG C of air
The Cu-Mn alloy films are heated in atmosphere.
Applications Claiming Priority (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2013115232 | 2013-05-31 | ||
| JP2013-115232 | 2013-05-31 | ||
| JP2013115232 | 2013-05-31 |
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| Publication Number | Publication Date |
|---|---|
| CN104212997A CN104212997A (en) | 2014-12-17 |
| CN104212997B true CN104212997B (en) | 2017-06-09 |
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| CN201410239491.5A Active CN104212997B (en) | 2013-05-31 | 2014-05-30 | The film build method of Cu Mn alloy films and Cu Mn alloy sputtering targets and Cu Mn alloy films |
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| JP (1) | JP6376438B2 (en) |
| KR (1) | KR101609453B1 (en) |
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| CN104690266A (en) * | 2015-03-18 | 2015-06-10 | 宁波广博纳米新材料股份有限公司 | Copper-manganese alloy powder used for preparing front surface and back surface electrodes of wafer resistor |
| US10670776B2 (en) | 2015-03-20 | 2020-06-02 | Dai Nippon Printing Co., Ltd. | Antireflection film, display device in which said antireflection film is used, and method for selecting antireflection film |
| JP6190847B2 (en) * | 2015-06-16 | 2017-08-30 | 株式会社神戸製鋼所 | Low reflective electrode for flat display or curved display |
| JP6042520B1 (en) * | 2015-11-05 | 2016-12-14 | デクセリアルズ株式会社 | Mn—Zn—O-based sputtering target and method for producing the same |
| WO2018168244A1 (en) * | 2017-03-17 | 2018-09-20 | 富士フイルム株式会社 | Method for producing transparent optical film and method for producing transparent multilayer film |
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| JPH03271359A (en) * | 1990-03-20 | 1991-12-03 | Japan Steel Works Ltd:The | Method for synthesizing multiple oxide |
| KR100315556B1 (en) * | 1996-11-20 | 2002-01-12 | 니시무로 타이죠 | Sputtering target, anti-ferromagnetic material film formed using thereof and magneto-resistance effect element formed using the same |
| JP2002522347A (en) * | 1998-08-13 | 2002-07-23 | ピーピージー・インダストリーズ・オハイオ・インコーポレイテッド | Compositions, apparatus, methods, and articles made thereby for forming a selected color coating on a substrate |
| US7626665B2 (en) * | 2004-08-31 | 2009-12-01 | Tohoku University | Copper alloys and liquid-crystal display device |
| JP4851740B2 (en) * | 2005-06-30 | 2012-01-11 | 株式会社東芝 | Semiconductor device and manufacturing method thereof |
| JP4756458B2 (en) * | 2005-08-19 | 2011-08-24 | 三菱マテリアル株式会社 | Mn-containing copper alloy sputtering target with less generation of particles |
| JP2008135569A (en) * | 2006-11-28 | 2008-06-12 | Rohm Co Ltd | Method of manufacturing semiconductor device, and semiconductor device |
| JP2010080607A (en) * | 2008-09-25 | 2010-04-08 | Rohm Co Ltd | Method of manufacturing semiconductor device |
| JP2012189725A (en) * | 2011-03-09 | 2012-10-04 | Kobe Steel Ltd | WIRING FILM AND ELECTRODE USING Ti ALLOY BARRIER METAL AND Ti ALLOY SPUTTERING TARGET |
| JP5662874B2 (en) * | 2011-05-31 | 2015-02-04 | 株式会社神戸製鋼所 | Recording film for optical information recording medium, optical information recording medium, and sputtering target used for forming the recording film |
| KR101323151B1 (en) * | 2011-09-09 | 2013-10-30 | 가부시키가이샤 에스에이치 카퍼프로덕츠 | Cu-Mn ALLOY SPUTTERING TARGET MATERIAL, THIN FILM TRANSISTOR WIRE AND THIN FILM TRANSISTOR USING THE SAME |
| JP5632821B2 (en) * | 2011-12-06 | 2014-11-26 | 株式会社神戸製鋼所 | Cu alloy wiring film for touch panel sensor, manufacturing method thereof, and touch panel sensor |
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| CN104212997A (en) | 2014-12-17 |
| TWI504772B (en) | 2015-10-21 |
| JP6376438B2 (en) | 2018-08-22 |
| KR20140141493A (en) | 2014-12-10 |
| JP2015007280A (en) | 2015-01-15 |
| KR101609453B1 (en) | 2016-04-05 |
| TW201447004A (en) | 2014-12-16 |
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