CN104212997A - Cu-Mn alloy film, Cu-Mn alloy sputtering target material and Cu-Mn alloy film manufacturing method - Google Patents
Cu-Mn alloy film, Cu-Mn alloy sputtering target material and Cu-Mn alloy film manufacturing method Download PDFInfo
- Publication number
- CN104212997A CN104212997A CN201410239491.5A CN201410239491A CN104212997A CN 104212997 A CN104212997 A CN 104212997A CN 201410239491 A CN201410239491 A CN 201410239491A CN 104212997 A CN104212997 A CN 104212997A
- Authority
- CN
- China
- Prior art keywords
- alloy
- alloy film
- film
- atom
- sputtering target
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
Classifications
-
- 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
-
- 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
-
- 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
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Mechanical Engineering (AREA)
- Metallurgy (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Physical Vapour Deposition (AREA)
- Conductive Materials (AREA)
Abstract
The invention provides a Cu-Mn alloy film, Cu-Mn alloy sputtering target material and Cu-Mn alloy film manufacturing method meeting new requirements for low reflection required by electrode films or wiring films to improve display quality of plane display elements with high definition. The Cu-Mn alloy film is formed by in a way that when metal component is viewed as 100atom%, the metal component comprises 32 to45atom% Mn, Cu and unavoidable impurities; visible light reflectance of the Cu-Mn alloy film is 30% below; and the reflectance is suitable for the electrode films or the wiring films for the plane display element.
Description
Technical field
The present invention relates to require antiradar reflectivity, Cu-Mn alloy film that the electrode film of such as plane display element or wiring membrane use and for the formation of its Cu-Mn alloy sputtering target and the film of Cu-Mn alloy film.
Background technology
Flat display apparatus (the Flat Panel Display of the electrophoretype indicating meter utilized along with the liquid-crystal display (hereinafter referred to as " LCD "), plasma display (hereinafter referred to as " PDP "), Electronic Paper etc. that form thin-film device on transparent glass substrate etc. etc., hereinafter referred to as " FPD ") large picture, high-resolution, fast response, require its wiring membrane low resistance.In addition, the new product of the flexible FPD of the touch panel adding operability or use resin substrate or very thin glass substrate etc. is developed in FPD in recent years.
In addition, the touch panel substrate picture giving direct operability while the picture of viewing FPD also advances maximization, and the goods carrying out touch panel operation in smart mobile phone, panel computer and desktop computer etc. are also popularized.The position detection electrode of touch panel is generally used as the indium tin oxide (hereinafter referred to as " ITO ") of nesa coating.
In addition; in recent years; can multiple spot detect capacitive touch panels in develop into be configured with tetragon ito film be commonly called as rhombus configuration; protective membrane as the electrode film or wiring membrane that connect tetragon ito film uses metallic membrane, and this metallic membrane employs Mo or the Mo alloy easily obtained with the contact of ito film.
In addition, the flexible FPD employing the resin film substrate or very thin glass substrate etc. beyond glass substrate, the goods employing touch panel are just developed energetically.
But; form the metallic membrane of above-mentioned Mo or Mo alloy in these purposes and curved substrate time; knownly produce following problem sometimes: easily crack in Mo film or Mo alloy film, the adaptation with substrate can not be guaranteed, the effect of protection wiring membrane Cu film cannot be maintained fully.Therefore, as the method not using Mo or Mo alloy, Cu alloy again receives publicity and proposes by means of it above-mentioned with adaptation that is substrate to guarantee.(with reference to patent documentation 1 ~ patent documentation 3)
Prior art document
Patent documentation
Patent documentation 1: Japanese Unexamined Patent Publication 2012-211378 publication
Patent documentation 2: Japanese Unexamined Patent Publication 2012-212811 publication
Patent documentation 3: Japanese Unexamined Patent Publication 2013-67857 publication
Summary of the invention
the problem that invention will solve
About the Cu alloy film proposed in patent documentation 1 and patent documentation 2, propose to obtain there is low-resistance wiring membrane and form the basilar membrane of the Cu-Mn-X alloy film containing at least one element be selected from the group that is made up of Ag, Au, C, W, Ca, Mg, Al, Sn, B and Ni in Cu as Cu film, be used for guaranteeing the adaptation of Cu alloy film and substrate, insulating film or semiconductor film.
In addition, in order to ensure the shielding for the semiconductor film be made up of indium-gallium-zinc-oxygen (hereinafter referred to as " IGZO film ") in patent documentation 3, propose to be formed and be 8 more than atom % and the method for Cu alloy film that formed of the Cu-Mn alloy of the Mn of 30 below atom % and inevitably impurity by comprising concentration.
On the other hand, there are 4 times use in the large-scale 4K-TV of the more high-resolution of full HD pixel and increase as the method for main wiring material with the lower Cu of Al phase ratio resistance in nearest main flow.In addition, though to have expanded the little high-definition realizing full HD display of picture for the smart mobile phone at the super close distance operating display frame apart from about eyes several tens cm.Along with this high-definition, incident light is significantly changed gradually by the problem that Metal film reflector makes display quality reduce.Therefore, metallic membrane has the requirement of this new features of antiradar reflectivity (below sometimes also referred to as " low reflection ") just at rapid growth.
In addition, in the manufacturing process of plane display element, touch panel, in the heating treatment step forming photo-resist when to carry out patterning after electrode film/wiring membrane, owing to carrying out the heat treated of about 230 DEG C in air atmosphere, if it is therefore desirable that the metallic membrane obtaining low reflection when may heat at 200 DEG C below this temperature.
Now, the Al film that the wiring membrane of flat display apparatus midplane display element is used is the metallic membrane of the high-reflectivity in visible region with more than 90%.In addition, be that the wiring membrane of plane display element Cu film used has the reflectivity of 70%, to have the high-reflectivity of with Ag film equal more than 95% in the long wavelength region of more than 600nm in visible region equally.On the other hand, in order to protect these wiring membranes and stacked Mo film or Mo alloy film have about 60% reflectivity.Even if these metallic membranes are through the manufacturing process of plane display element, reflectivity also changes hardly, and therefore the reflection of metallic membrane especially becomes the principal element that display quality is reduced in the display unit of high-resolution.
Therefore, in the display unit of high-resolution, require the electrode film/wiring membrane of the lower reflection of less than 30% about the half of Mo etc.
As mentioned above, develop various Cu alloy film so far, but these patent documentations are conceived to wiring membrane, screened film is studied, about reply high-resolution from now on display unit needed for this new features of low reflection do not carry out any research.
The object of the present invention is to provide the display quality can tackling the plane display element making high-resolution promote needed for, the Cu-Mn alloy film of the new demand of low reflection in electrode film or wiring membrane and for the formation of its Cu-Mn alloy sputtering target and the film of Cu-Mn alloy film.
for the scheme of dealing with problems
The present inventor in view of the above problems, in order to obtain the characteristic of low reflection in the manufacturing process of plane display element, touch panel, takes to take Cu as main component, optimization Addition ofelements and addition.Its result, the Cu-Mn alloy film finding to add in Cu the Mn of specified quantitative can obtain the characteristic of low reflection, thus achieves the present invention.
Namely, the present invention relates to Cu-Mn alloy film, wherein, when metal ingredient being totally considered as 100 atom %, metal ingredient contain the Mn of 32 ~ 45 atom %, surplus by Cu and inevitably impurity form, the visible reflectance of described Cu-Mn alloy film is less than 30%.
In addition, Cu-Mn alloy film of the present invention contains metal ingredient and oxygen, when metal ingredient being totally considered as 100 atom %, aforementioned metal composition contain the Mn of 32 ~ 45 atom %, surplus by Cu and inevitably impurity form, oxygen relative to the ratio of the summation of aforementioned metal composition and aforementioned oxygen with atomic ratio measuring for 0.3 ~ 0.6.
In addition, Cu-Mn alloy film of the present invention is suitably for electrode film or the wiring membrane of plane display element.
In addition, the present invention is by Cu and the inevitable Cu-Mn alloy sputtering target that forms of impurity containing the Mn of 32 ~ 45 atom %, surplus.
Cu-Mn alloy sputtering target of the present invention preferably has the tissue containing recrystallized structure in the crystal boundary of Cu-Mn alloy powder.
Cu-Mn alloy film of the present invention can obtain as follows: by the Cu-Mn alloy film sputtering the Mn of formation containing 32 ~ 45 atom %, surplus is made up of Cu and inevitable impurity in the atmosphere of oxygen containing 30 ~ 60 volume %.
In addition, Cu-Mn alloy film of the present invention also can obtain as follows: by the Cu-Mn alloy film that the Mn of sputtering formation containing 32 ~ 45 atom %, surplus are made up of Cu and inevitable impurity in inert atmosphere, then in the air atmosphere of 200 ~ 225 DEG C, heat aforementioned Cu-Mn alloy film.
the effect of invention
Cu-Mn alloy film of the present invention can realize this new features of the unavailable low reflection of existing electrode film/wiring membrane, therefore can improve the display quality of such as FPD etc.Therefore, the intelligent terminals of future generation such as the such as 4K-TV, smart mobile phone or the panel computer that the FPD as more high-resolution are received publicity or use resin substrate flexible FPD be very useful technology.This is because especially the low reflectionization of metallic membrane is extremely important in these goods.
Accompanying drawing explanation
Fig. 1 is the macrograph of the section with observation by light microscope Cu-Mn alloy sputtering target of the present invention.
Embodiment
Key character of the present invention is, as being suitably for the electrode film of such as plane display element, the Cu alloy film of wiring membrane, by adopting the Cu-Mn alloy that with the addition of the Mn of specified quantitative in Cu, thus finds the new features that reflectivity is low.It should be noted that, in the following description, " reflectivity " refers to the average reflectance of the scope of the wavelength 360 ~ 740nm belonging to visible region.Below, the present invention is described in detail.
About Cu-Mn alloy film of the present invention, add in Cu one of reason of the Mn of specified quantitative be because through above-mentioned carry out the heating treatment step of the photo-resist of patterning after make reflectance reduction.As mentioned above, the Al film that the wiring membrane of plane display element is used is now the metallic membrane of the high-reflectivity in visible region with more than 90%.In addition, be that the wiring membrane of plane display element Cu film used has the reflectivity of 70%, to have the high-reflectivity of with Ag film equal more than 95% in the long wavelength region of more than 600nm in visible region equally.
On the other hand, in order to protect these wiring membranes and stacked Mo film or Mo alloy film have about 60% reflectivity.Even if these metallic membranes are through the process of above-mentioned display element manufacturing process, reflectivity also changes hardly.
In contrast, Cu-Mn alloy film of the present invention with the addition of the Cu-Mn alloy of the Mn of specified quantitative in Cu by adopting, thus achieve antiradar reflectivity.According to the research of the present inventor, confirm this reflectance reduction effect when metal ingredient being totally considered as 100 atom %, performance is obviously when being 32 ~ 45 atom % for the addition of metal ingredient Mn.Though its reason is indefinite, Cu-Mn alloy is the alloy of complete solid solution system, its fusing point is minimum when Mn amount is 38 atom %.Further, if the fusing point of Cu-Mn alloy film is low, then in the process of carrying out above-mentioned heat treated, the movement of recrystallize, atom is easily caused.In addition, about the Mn in Cu-Mn alloy film, oxygen deposit carry out heat treated in case time, Mn is easily through crystal boundary and move to film surface.
So, consider as follows about Cu-Mn alloy film of the present invention: when metal ingredient being totally considered as 100 atom %, be 32 ~ 45 atom % by making the addition of metal ingredient Mn, thus become the compositing range that fusing point is low scope, when carrying out the heat treated of 200 ~ 225 DEG C in air atmosphere, the Mn in Cu-Mn alloy film is diffused into film surface and forms oxide compound and make reflectance reduction.
In addition, in order to make the lower Cu-Mn alloy film of reflectivity, preferably, when metal ingredient being totally considered as 100 atom %, making the addition of metal ingredient Mn be 32 ~ 40 atom %, being more preferably 32 ~ 39 atom %.
Cu-Mn alloy film of the present invention, by containing metal ingredient and oxygen, when metal ingredient being totally considered as 100 atom %, aforementioned metal composition contain the Mn of 32 ~ 45 atom %, surplus by Cu and inevitably impurity form, make oxygen relative to the ratio of the summation of aforementioned metal composition and aforementioned oxygen with atomic ratio measuring for 0.3 ~ 0.6, lower reflectivity can be obtained thus.For Cu-Mn alloy film, if carry out heat treated in air atmosphere, film forming in oxygen containing atmosphere, then aerobic can be contained in film.Especially Mn is easier than Cu with oxygen bonding, and therefore the Cu-Mn alloy film of the Mn containing specified quantitative of the present invention easily absorbs a large amount of oxygen, thus can obtain antiradar reflectivity.
In pure Cu film, oxygen is with Cu
2the mode of the linear compound on the equilibrium phase diagram of O, CuO exists.On the other hand, think that Cu-Mn alloy film is by containing Mn, thus form stable region field width comprise MnO, Mn
3o
4with the nonequilibrium phase of Cu, absorb oxygen with wide compositing range, therefore easily obtain lower reflectivity.
About Cu-Mn alloy film of the present invention, by make oxygen in this film relative to the ratio of the summation of metal ingredient and oxygen with atomic ratio measuring for more than 0.3, thus the reflection with metalluster can be suppressed, can antiradar reflectivity be realized.In addition, about Cu-Mn alloy film of the present invention, by make oxygen in this film relative to the ratio of the summation of metal ingredient and oxygen with atomic ratio measuring for less than 0.6, thus the transmission of light can be suppressed, realize antiradar reflectivity and the adaptation with substrate etc. can be improved.Therefore, the oxygen contained in Cu-Mn alloy film of the present invention relative to the ratio of the summation of aforementioned metal composition and aforementioned oxygen with atomic ratio measuring for 0.3 ~ 0.6.Be preferably 0.33 ~ 0.57.
The thickness of Cu-Mn alloy film of the present invention is preferably 20 ~ 200nm.In the present invention, by the thickness of Cu-Mn alloy film is set to more than 20nm, thus the transmission of light can be suppressed, obtains the Cu-Mn alloy film of antiradar reflectivity.In addition, in the present invention, by the thickness of Cu-Mn alloy film is set to below 200nm, thus the time that can shorten for film forming and the warpage of the substrate caused by membrane stress after can suppressing film forming or after heat treated.In the present invention, in order to stably obtain the low Cu-Mn alloy film of reflectivity with higher productivity, more preferably the thickness of Cu-Mn alloy film is set to 50 ~ 100nm.
In order to form Cu-Mn alloy film of the present invention, the sputtering method using sputtering target material is most suitable.As sputtering method, can apply use the Cu-Mn alloy sputtering target identical with the composition of Cu-Mn alloy film carry out film forming method, such as use the sputtering target material of Cu sputtering target material and Mn or Mn-Cu alloy to carry out the method for film forming by cosputtering.
Wherein, the Cu-Mn alloy sputtering target identical with the composition of Cu-Mn alloy film is preferably used to carry out the method for film forming.And, by using containing the Mn of 32 ~ 45 atom %, surplus by Cu and the inevitable Cu-Mn alloy sputtering target that form of impurity in the present invention, thus can easy and stably formation Cu-Mn alloy film.In addition, as mentioned above, in order to stably obtain the Cu-Mn alloy film with lower reflectivity, the Cu-Mn alloy sputtering target that the Mn containing 32 ~ 40 atom %, surplus are made up of Cu and inevitable impurity is preferably used.In Cu-Mn alloy sputtering target of the present invention, the content range of Mn is more preferably 32 ~ 39 atom %.
Cu-Mn alloy sputtering target of the present invention can manufacture with the following method: will be modulated to the melting sources/casting of composition requirement and make ingot casting, utilizes mechanical workout and the method manufactured; To be modulated to the atomizing raw materials of composition requirement or pulverize ingot casting and make Cu-Mn powdered alloy, employing hot isostatic pressing (hereinafter referred to as " HIP ") etc. are by the method for its pressure sintering.
About the manufacture method of Cu-Mn alloy sputtering target of the present invention, can according to the size of sputtering target material, shape, suitably selected can the cheap and method stably manufactured.Cu-Mn alloy sputtering target of the present invention preferably uses the atomized powder formed by Cu-Mn alloy, optimizes sintering temperature and manufactures, thus make the tissue containing recrystallized structure in the crystal boundary of Cu-Mn alloy powder.Thus, Cu-Mn alloy sputtering target of the present invention has the tissue not having to strain of recrystallize, thus suppresses splashing to wait generation abnormal grain, stably can obtain even and high-grade Cu-Mn alloy film.
In Cu-Mn alloy sputtering target of the present invention, in order to ensure antiradar reflectivity, the content occupying the inevitable impurity except Cu of surplus beyond essential element Mn is more few more preferred, can contain inevitably impurity such as nitrogen, carbon, Fe, Si etc. in the scope not damaging effect of the present invention.Such as, nitrogen is below 1000 quality ppm, carbon be below 200 quality ppm, Fe be below 500 quality ppm, Si is that 100 quality ppm are such as the following, and the purity of removing gaseous constituent is preferably more than 99.9 quality %.
Cu-Mn alloy film of the present invention can be applied following so-called reactive sputtering method and obtain, and uses sputtering target material when sputtering, and adopts the sputter gas containing reactant gas oxygen in the non-active gas argon gas as conventional sputter gas etc.Now, the ratio that contains of the oxygen in sputter gas is preferably 30 ~ 60 volume %.
In addition, Cu-Mn alloy film of the present invention also can obtain as follows: when using sputtering target material to sputter, form Cu-Mn alloy film, then in the air atmosphere of 200 ~ 225 DEG C, heat this Cu-Mn alloy film in the inert atmosphere such as argon gas by sputtering.
Embodiment 1
First, the sputtering target material for the formation of Cu-Mn alloy film is made.Carry out weighing and make to be 80 atom %Mn-Cu, to carry out melt-casting with vacuum melting stove and make ingot casting with atomic ratio measuring.Then, mechanical workout is carried out to this ingot casting, thus make the sputtering target material of diameter 100mm, thickness 5mm.
It should be noted that, about the Al sputtering target material for the formation of the Al film as comparative example, the Al sputtering target material buying Sumitomo Chemical Co's manufacture prepares.In addition, about the Cu sputtering target material for the formation of the Cu film as comparative example, processing is carried out to make Cu sputtering target material to oxygen free copper (OFC) starting material that Hitachi Cable, Ltd. manufacture.In addition, about the Mo sputtering target material for the formation of the Mo film as comparative example, the Mo powder pressure sintering of purity 4N is made Mo sputtering target material.
Each sputtering target material by above-mentioned making is soldered on backing plate made of copper, puts into the sputter equipment (model: CS-200) that ULVAC, Inc. manufacture.Then, the glass substrate of 25mm × 50mm formed the metallic membrane of thickness shown in table 1 and make the sample evaluated.It should be noted that, for the film forming of Cu-Mn alloy film, adopt the cosputtering method Cu sputtering target material of above-mentioned preparation and 80 atom %Mn-Cu sputtering target materials simultaneously sputtered, the power being applied to each sputtering target material is changed and forms the different Cu-Mn alloy film formed.
The inductively coupled plasma atomic emission device (ICP model: ICPV-1017) using Shimadzu Scisakusho Ltd to manufacture confirms the composition of the Cu-Mn alloy film of film forming.
Then, in air atmosphere, at the temperature of 150 DEG C, 200 DEG C, each sample is carried out to the heat treated of 30 minutes, obtain the sample of measuring reflectance.The measurement result of the reflectivity of each sample obtained shown in table 1.It should be noted that, reflectivity uses Konica Minolta, the spectrocolorimeter (model: CM2500d) that Inc. manufactures.It should be noted that, the mark * in table 1 represents outside scope of the present invention.
[table 1]
As shown in table 1, have Al, Cu of low-resistance value even if known or in air atmosphere, carry out the heating of 200 DEG C for the Mo of stacked film, reflectivity also reduces hardly.
In contrast, in a slight decrease when the reflectivity of known Cu-Mn alloy film of the present invention heats with 150 DEG C, significantly reduce further when heating with 200 DEG C.Especially, when the addition confirming the Mn in Cu-Mn alloy film is the scope of 32 ~ 43 atom %, obtain the antiradar reflectivity that reflectivity is less than 30%, become be suitably for plane display element electrode film, wiring membrane Cu-Mn alloy film.
Embodiment 2
Be determined at the reflectivity of Cu-Mn alloy film when carrying out the heat treated of 225 DEG C, 250 DEG C, 300 DEG C to the sample of the specimen coding 1 in the sample of embodiment 1, numbering 5, numbering 6, numbering 7 in air atmosphere, result is shown in table 2.It should be noted that, the mark * in table 2 represents outside scope of the present invention.
[table 2]
As shown in table 2, about the reflectivity of Cu-Mn alloy film, confirm Heating temperature in air atmosphere for further reduction compared with 200 shown in table 1 DEG C when 225 DEG C.On the other hand, when the Heating temperature confirmed in air atmosphere is 250 DEG C, the reflectivity of Cu-Mn alloy film is more than 30%, significantly increase.Therefore can confirm, in order to obtain Cu-Mn alloy film of the present invention, the Heating temperature of the Cu-Mn alloy film 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 atom %Mn, make the atomized powder that composition is identical, use 100 object sieves to carry out classification, obtaining the Cu-Mn powdered alloy of median size 70 μm.Carry out chemical analysis to this Cu-Mn powdered alloy, results verification purity is 99.9%.
Then, be filled into cylinder internal diameter 133mm × height 30mm and thickness is the mild steel container of 3mm, at 450 DEG C, heating carries out degassed process in 5 hours.Then, sealing mild steel container, utilizes HIP device to sinter under sintering temperature 800 DEG C, moulding pressure 118MPa, the sintering time condition of 5 hours.
Take out from HIP device after the cooling period, take off mild steel container by mechanical workout, obtain the Cu-Mn alloy sputtering target of the present invention of diameter 100mm, thickness 5mm, cut test film by remainder.
The quantitative analysis of the metallic element of obtained test film is carried out with the inductively coupled plasma atomic emission device (ICP) (model: ICPV-1017) that Shimadzu Scisakusho Ltd manufactures, the quantitative employing non-dispersive type infrared absorption of oxygen measures, the purity of the total of the analytical value of result Cu, Mn is 99.9%, oxygen concn is 560 quality ppm, confirms to obtain highly purified Cu-Mn alloy sputtering target.
Carry out mirror ultrafinish to by test film obtained above, then corrode with aqueous nitric acid, carry out structure observation with opticmicroscope, result is shown in Fig. 1.As shown in Figure 1, confirm the tissue that Cu-Mn alloy sputtering target of the present invention has fine recrystallize in the crystal boundary of the almost spherical of atomized powder, the defect large to segregation, hole etc. unconfirmed is the Cu-Mn alloy sputtering target being suitable for spatter film forming.
In addition, to be soldered on backing plate made of copper by Cu-Mn alloy sputtering target of the present invention obtained above, then put into the sputter equipment (model: SPF-440HL) that CANON ANELVA CORPRORATION manufactures, under the condition of argon gas atmosphere, pressure 0.5Pa, power 500W, implement sputtering.
When using Cu-Mn alloy sputtering targets of the present invention to sputter, confirm there is no paradoxical discharge, can stable sputtering be carried out.
Embodiment 4
The Cu-Mn alloy sputtering target of the present invention made by embodiment 3 is put into ULVAC, Inc. the sputter equipment (model: SBH-2204) manufactured, use the sputter gas containing argon gas and oxygen, under the condition of pressure 0.8Pa, power 300W, implement sputtering.
Similarly to Example 1, use the glass substrate of 25mm × 50mm as substrate, be adjusted to the amount of oxygen in the sputtering atmosphere shown in table 3, form the Cu-Mn alloy film of thickness 100nm.Measure the reflectivity of each sample, result is shown in table 3.It should be noted that, (KRATOS company manufactures to use photoelectron spectrum device ESCA (Electoron spectroscopy for chemical analysis), model: AXIS-HS) analyze oxygen amount in Cu-Mn alloy film, represent the ratio of oxygen relative to the summation of metal ingredient and oxygen with atomic ratio.In addition, the mark * in table 3 represents outside scope of the present invention.
[table 3]
As shown in table 3, when the oxygen concentration in known sputter gas is 30 more than volume %, reflectance reduction, the oxygen amount meanwhile in Cu-Mn alloy film increases.On the other hand, confirm the ratio relative to the summation of metal ingredient and oxygen of oxygen in Cu-Mn alloy film with atomic ratio measuring more than 0.6 time, transmitted light increases and produces film to be peeled off.
Claims (7)
1. a Cu-Mn alloy film, is characterized in that, when metal ingredient being totally considered as 100 atom %, metal ingredient contain the Mn of 32 ~ 45 atom %, surplus by Cu and inevitably impurity form, the visible reflectance of described Cu-Mn alloy film is less than 30%.
2. a Cu-Mn alloy film, it is characterized in that, containing metal ingredient and oxygen, when metal ingredient being totally considered as 100 atom %, described metal ingredient contain the Mn of 32 ~ 45 atom %, surplus by Cu and inevitably impurity form, oxygen relative to the ratio of the summation of described metal ingredient and described oxygen with atomic ratio measuring for 0.3 ~ 0.6.
3. according to Cu-Mn alloy film according to claim 1 or claim 2, it is characterized in that, its electrode film for plane display element or wiring membrane.
4. a Cu-Mn alloy sputtering target, is characterized in that, the Mn containing 32 ~ 45 atom %, surplus are made up of Cu and inevitable impurity.
5. Cu-Mn alloy sputtering target according to claim 4, is characterized in that, has the tissue containing recrystallized structure in the crystal boundary of Cu-Mn alloy powder.
6. a film for Cu-Mn alloy film, is characterized in that, by the Cu-Mn alloy film sputtering the Mn of formation containing 32 ~ 45 atom %, surplus is made up of Cu and inevitable impurity in the atmosphere of oxygen containing 30 ~ 60 volume %.
7. the film of a Cu-Mn alloy film, it is characterized in that, by the Cu-Mn alloy film that the Mn of sputtering formation containing 32 ~ 45 atom %, surplus are made up of Cu and inevitable impurity in inert atmosphere, then in the air atmosphere of 200 ~ 225 DEG C, heat described Cu-Mn alloy film.
Applications Claiming Priority (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2013115232 | 2013-05-31 | ||
| JP2013-115232 | 2013-05-31 | ||
| JP2013115232 | 2013-05-31 |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN104212997A true CN104212997A (en) | 2014-12-17 |
| CN104212997B CN104212997B (en) | 2017-06-09 |
Family
ID=52094898
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| 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 |
Country Status (4)
| Country | Link |
|---|---|
| JP (1) | JP6376438B2 (en) |
| KR (1) | KR101609453B1 (en) |
| CN (1) | CN104212997B (en) |
| TW (1) | TWI504772B (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| 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 |
| CN110418855A (en) * | 2017-03-17 | 2019-11-05 | 富士胶片株式会社 | The manufacturing method of transparent optical film and the manufacturing method of transparent multilayer film |
Families Citing this family (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107407744B (en) | 2015-03-20 | 2020-06-09 | 大日本印刷株式会社 | Antireflection film, display device using the same, 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 |
Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1590580A (en) * | 1996-11-20 | 2005-03-09 | 株式会社东芝 | Antiferromagnetic film and magneto-resistance effect element formed by using the same |
| WO2006025347A1 (en) * | 2004-08-31 | 2006-03-09 | National University Corporation Tohoku University | Copper alloy and liquid-crystal display |
| JP2008135569A (en) * | 2006-11-28 | 2008-06-12 | Rohm Co Ltd | Method of manufacturing semiconductor device, and semiconductor device |
| CN101243201A (en) * | 2005-08-19 | 2008-08-13 | 三菱麻铁里亚尔株式会社 | Mn-contained copper alloy sputtering target with less occurrence of particle |
| 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 |
| CN102994952A (en) * | 2011-09-09 | 2013-03-27 | 日立电线株式会社 | Cu-Mn alloy sputtering target material, thin-film transistor layout using the same and thin-film transistor |
Family Cites Families (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH03271359A (en) * | 1990-03-20 | 1991-12-03 | Japan Steel Works Ltd:The | Method for synthesizing multiple oxide |
| AU748247B2 (en) * | 1998-08-13 | 2002-05-30 | Ppg Industries Ohio, Inc. | Compositions, apparatus and methods for forming coatings of selected color on a substrate and articles produced thereby |
| JP4851740B2 (en) * | 2005-06-30 | 2012-01-11 | 株式会社東芝 | Semiconductor device and manufacturing method thereof |
| 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 |
| 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 |
-
2014
- 2014-04-28 JP JP2014092582A patent/JP6376438B2/en active Active
- 2014-05-09 TW TW103116460A patent/TWI504772B/en active
- 2014-05-28 KR KR1020140064235A patent/KR101609453B1/en active IP Right Grant
- 2014-05-30 CN CN201410239491.5A patent/CN104212997B/en active Active
Patent Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1590580A (en) * | 1996-11-20 | 2005-03-09 | 株式会社东芝 | Antiferromagnetic film and magneto-resistance effect element formed by using the same |
| WO2006025347A1 (en) * | 2004-08-31 | 2006-03-09 | National University Corporation Tohoku University | Copper alloy and liquid-crystal display |
| CN101243201A (en) * | 2005-08-19 | 2008-08-13 | 三菱麻铁里亚尔株式会社 | Mn-contained copper alloy sputtering target with less occurrence of particle |
| 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 |
| CN102994952A (en) * | 2011-09-09 | 2013-03-27 | 日立电线株式会社 | Cu-Mn alloy sputtering target material, thin-film transistor layout using the same and thin-film transistor |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| 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 |
| CN110418855A (en) * | 2017-03-17 | 2019-11-05 | 富士胶片株式会社 | The manufacturing method of transparent optical film and the manufacturing method of transparent multilayer film |
Also Published As
| Publication number | Publication date |
|---|---|
| JP6376438B2 (en) | 2018-08-22 |
| CN104212997B (en) | 2017-06-09 |
| TWI504772B (en) | 2015-10-21 |
| KR20140141493A (en) | 2014-12-10 |
| TW201447004A (en) | 2014-12-16 |
| KR101609453B1 (en) | 2016-04-05 |
| JP2015007280A (en) | 2015-01-15 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN104425416B (en) | It is laminated wiring membrane and its manufacture method and Ni alloy sputtering targets | |
| CN108242276B (en) | Laminated wiring film and method for manufacturing same | |
| KR101613001B1 (en) | METHOD OF MANUFACTURING Mo ALLOY SPUTTERING TARGET MATERIAL AND Mo ALLOY SPUTTERING TARGET MATERIAL | |
| CN105908139B (en) | Wiring membrane and coating formation sputtering target material is laminated in electronic component-use | |
| CN104212997A (en) | Cu-Mn alloy film, Cu-Mn alloy sputtering target material and Cu-Mn alloy film manufacturing method | |
| TWI670384B (en) | Metallization for a thin-film component, process for the production thereof and sputtering target | |
| TWI447250B (en) | Method for producing molybdenum alloy sputtering target material and molybdenum alloy sputtering target material | |
| Kukreja et al. | Pulsed laser deposition of plasmonic-metal nanostructures | |
| KR20190010701A (en) | Laminate wiring layer for an electronic component and a sputtering target material for forming a coating layer | |
| CN105986233B (en) | Wiring membrane and coating formation sputtering target material is laminated in electronic component-use | |
| CN104419903B (en) | Coating formation sputtering target material and its manufacture method | |
| WO2022097635A1 (en) | Sputtering target, method for producing sputtering target, and optical functional film | |
| WO2021241687A1 (en) | Sputtering target and optical functional film |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |