WO2022004491A1 - 金属配線構造体、金属配線構造体の製造方法及びスパッタリングターゲット - Google Patents
金属配線構造体、金属配線構造体の製造方法及びスパッタリングターゲット Download PDFInfo
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- WO2022004491A1 WO2022004491A1 PCT/JP2021/023626 JP2021023626W WO2022004491A1 WO 2022004491 A1 WO2022004491 A1 WO 2022004491A1 JP 2021023626 W JP2021023626 W JP 2021023626W WO 2022004491 A1 WO2022004491 A1 WO 2022004491A1
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- Prior art keywords
- film
- metal wiring
- alloy
- wiring structure
- cap layer
- Prior art date
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Images
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- H01L29/40—Electrodes ; Multistep manufacturing processes therefor
- H01L29/43—Electrodes ; Multistep manufacturing processes therefor characterised by the materials of which they are formed
- H01L29/49—Metal-insulator-semiconductor electrodes, e.g. gates of MOSFET
- H01L29/4908—Metal-insulator-semiconductor electrodes, e.g. gates of MOSFET for thin film semiconductor, e.g. gate of TFT
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- 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
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- 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
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- 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
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- 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
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- 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
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- H01L21/00—Processes or apparatus adapted for the manufacture or treatment of semiconductor or solid state devices or of parts thereof
- H01L21/02—Manufacture or treatment of semiconductor devices or of parts thereof
- H01L21/04—Manufacture or treatment of semiconductor devices or of parts thereof the devices having potential barriers, e.g. a PN junction, depletion layer or carrier concentration layer
- H01L21/18—Manufacture or treatment of semiconductor devices or of parts thereof the devices having potential barriers, e.g. a PN junction, depletion layer or carrier concentration layer the devices having semiconductor bodies comprising elements of Group IV of the Periodic Table or AIIIBV compounds with or without impurities, e.g. doping materials
- H01L21/28—Manufacture of electrodes on semiconductor bodies using processes or apparatus not provided for in groups H01L21/20 - H01L21/268
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L21/00—Processes or apparatus adapted for the manufacture or treatment of semiconductor or solid state devices or of parts thereof
- H01L21/02—Manufacture or treatment of semiconductor devices or of parts thereof
- H01L21/04—Manufacture or treatment of semiconductor devices or of parts thereof the devices having potential barriers, e.g. a PN junction, depletion layer or carrier concentration layer
- H01L21/18—Manufacture or treatment of semiconductor devices or of parts thereof the devices having potential barriers, e.g. a PN junction, depletion layer or carrier concentration layer the devices having semiconductor bodies comprising elements of Group IV of the Periodic Table or AIIIBV compounds with or without impurities, e.g. doping materials
- H01L21/30—Treatment of semiconductor bodies using processes or apparatus not provided for in groups H01L21/20 - H01L21/26
- H01L21/31—Treatment of semiconductor bodies using processes or apparatus not provided for in groups H01L21/20 - H01L21/26 to form insulating layers thereon, e.g. for masking or by using photolithographic techniques; After treatment of these layers; Selection of materials for these layers
- H01L21/3205—Deposition of non-insulating-, e.g. conductive- or resistive-, layers on insulating layers; After-treatment of these layers
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- H01L21/00—Processes or apparatus adapted for the manufacture or treatment of semiconductor or solid state devices or of parts thereof
- H01L21/70—Manufacture or treatment of devices consisting of a plurality of solid state components formed in or on a common substrate or of parts thereof; Manufacture of integrated circuit devices or of parts thereof
- H01L21/71—Manufacture of specific parts of devices defined in group H01L21/70
- H01L21/768—Applying interconnections to be used for carrying current between separate components within a device comprising conductors and dielectrics
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- H—ELECTRICITY
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- H01L23/00—Details of semiconductor or other solid state devices
- H01L23/52—Arrangements for conducting electric current within the device in operation from one component to another, i.e. interconnections, e.g. wires, lead frames
- H01L23/522—Arrangements for conducting electric current within the device in operation from one component to another, i.e. interconnections, e.g. wires, lead frames including external interconnections consisting of a multilayer structure of conductive and insulating layers inseparably formed on the semiconductor body
- H01L23/532—Arrangements for conducting electric current within the device in operation from one component to another, i.e. interconnections, e.g. wires, lead frames including external interconnections consisting of a multilayer structure of conductive and insulating layers inseparably formed on the semiconductor body characterised by the materials
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L29/00—Semiconductor devices specially adapted for rectifying, amplifying, oscillating or switching and having potential barriers; Capacitors or resistors having potential barriers, e.g. a PN-junction depletion layer or carrier concentration layer; Details of semiconductor bodies or of electrodes thereof ; Multistep manufacturing processes therefor
- H01L29/40—Electrodes ; Multistep manufacturing processes therefor
- H01L29/41—Electrodes ; Multistep manufacturing processes therefor characterised by their shape, relative sizes or dispositions
- H01L29/423—Electrodes ; Multistep manufacturing processes therefor characterised by their shape, relative sizes or dispositions not carrying the current to be rectified, amplified or switched
- H01L29/42312—Gate electrodes for field effect devices
- H01L29/42316—Gate electrodes for field effect devices for field-effect transistors
- H01L29/4232—Gate electrodes for field effect devices for field-effect transistors with insulated gate
- H01L29/42384—Gate electrodes for field effect devices for field-effect transistors with insulated gate for thin film field effect transistors, e.g. characterised by the thickness or the shape of the insulator or the dimensions, the shape or the lay-out of the conductor
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L29/00—Semiconductor devices specially adapted for rectifying, amplifying, oscillating or switching and having potential barriers; Capacitors or resistors having potential barriers, e.g. a PN-junction depletion layer or carrier concentration layer; Details of semiconductor bodies or of electrodes thereof ; Multistep manufacturing processes therefor
- H01L29/66—Types of semiconductor device ; Multistep manufacturing processes therefor
- H01L29/68—Types of semiconductor device ; Multistep manufacturing processes therefor controllable by only the electric current supplied, or only the electric potential applied, to an electrode which does not carry the current to be rectified, amplified or switched
- H01L29/76—Unipolar devices, e.g. field effect transistors
- H01L29/772—Field effect transistors
- H01L29/78—Field effect transistors with field effect produced by an insulated gate
- H01L29/786—Thin film transistors, i.e. transistors with a channel being at least partly a thin film
Definitions
- the present invention relates to a metal wiring structure, a method for manufacturing the metal wiring structure, and a sputtering target.
- TFTs thin film transistors
- a low resistance metal such as Al may be used as a wiring material.
- the gate electrode since the gate electrode is formed in the middle of the manufacturing process, it receives a thermal history due to the annealing process after the gate electrode is formed. Therefore, as the material of the gate electrode, a refractory metal (for example, Mo) having a heat resistance capable of withstanding the heat history is often used (see, for example, Patent Document 1).
- a refractory metal for example, Mo
- a refractory metal such as Mo
- the refractory metal does not have sufficient bending resistance. Therefore, the electrode may break due to bending.
- refractory metals such as Mo have a higher resistivity than low resistance metals such as Al. This can lead to display delays on the display as the size of the display increases.
- an object of the present invention is to provide a metal wiring structure having low resistance and excellent heat resistance and flexibility, a method for manufacturing the metal wiring structure, and a sputtering target.
- the metal wiring structure according to one embodiment of the present invention has a main component composed of aluminum and an additive element composed of 0.005 at% or more and 0.88% or less of iron added to the main component. It is provided with a metal wiring film having the above and a first cap layer laminated on the metal wiring film.
- the metal wiring structure may further contain vanadium of 0.01 at% or more and 0.05 at% or less as the additive element.
- the metal wiring structure may be composed of the main component, the additive element, and the unavoidable component.
- the metal wiring film is provided with a second cap layer on the opposite side of the first cap layer, and the metal wiring film is the first cap layer and the second cap. It may be provided between layers.
- a main component made of aluminum and an iron added to the main component of 0.005 at% or more and 0.88% or less are used.
- a metal wiring film having an additive element is formed on a substrate, a first cap layer is laminated on the metal wiring film, and the metal wiring film is heat-treated at 500 ° C. or lower.
- a second cap layer is formed on the metal wiring film on the opposite side of the first cap layer, and the metal wiring film forms the first cap layer and the second cap. It may be arranged between layers.
- a sputtering target for forming the above metal wiring structure is provided.
- a metal wiring structure having low resistance and excellent heat resistance and flexibility, a method for manufacturing the metal wiring structure, and a sputtering target.
- FIGS. (A) and (b) are schematic cross-sectional views of a thin film transistor having a metal wiring structure according to the present embodiment.
- FIGS. (C) and (d) are schematic cross-sectional views of the metal wiring structure according to the present embodiment.
- FIG. (A) is a graph showing changes in surface roughness immediately after film formation and after heat treatment of a plurality of Al alloy films when no nitride film is provided.
- FIG. (B) is a graph showing a change in surface roughness after heat treatment of a plurality of Al alloy films when a nitride film is provided.
- FIG. (A) is a graph showing changes in resistivity ⁇ ( ⁇ ⁇ cm) immediately after film formation of an Al pure metal film and a plurality of Al alloy films and after heat treatment.
- FIG. (B) is a graph showing the resistivity ⁇ ( ⁇ ⁇ cm) of the Al alloy film on which the nitride film as the cap layer is formed before the heat treatment.
- FIG. (C) is a graph showing the resistivity ⁇ ( ⁇ ⁇ cm) of the Al alloy film on which the nitride film as the cap layer is formed after the heat treatment. It is a surface SEM image of the Al pure metal film and a plurality of Al alloy films after the heat treatment when the nitride film is not provided.
- FIG. 1 (a) and 1 (b) are schematic cross-sectional views of a thin film transistor having a metal wiring structure according to the present embodiment.
- FIG. 1C is a schematic cross-sectional view of the metal wiring structure according to the present embodiment.
- FIG. 1A shows a top gate type thin film transistor 1.
- an active layer (semiconductor layer) 11, a gate insulating film 12, a gate electrode 13, and a protective layer 15 are laminated on a glass substrate 10.
- the active layer 11 is composed of, for example, LTPS (low temperature poly-silicon).
- the active layer 11 is electrically connected to the source electrode 16S and the drain electrode 16D.
- the substrate is not limited to a glass substrate, and may be a SiOx substrate, a SiNx substrate, a glass substrate with a SiOx film, a glass with a SiNx film, or the like.
- the glass substrate 10 will be described as an example.
- the thin film transistor 2 shown in FIG. 1 (b) is a bottom gate type thin film transistor.
- the gate electrode 13, the gate insulating film 22, the active layer 21, the source electrode 26S, and the drain electrode 26D are laminated on the glass substrate 10.
- the active layer 21 is made of, for example, an IGZO (In—Ga—Zn—O) -based oxide semiconductor material.
- the active layer 21 is electrically connected to the source electrode 26S and the drain electrode 26D.
- the thickness of the gate electrode 13 is not particularly limited, and is, for example, 100 nm or more and 600 nm or less, preferably 200 nm or more and 400 nm or less. If the thickness is less than 100 nm, it becomes difficult to reduce the resistance of the gate electrode 13. If the thickness exceeds 600 nm, the bending resistance of the thin film transistor 2 tends to decrease.
- the gate electrode 13 is composed of the metal wiring structure according to the present embodiment.
- the specific resistance of the gate electrode 13 is set to, for example, 15 ⁇ ⁇ cm or less, preferably 10 ⁇ ⁇ cm or less, more preferably 6.0 ⁇ ⁇ cm or less, still more preferably 3.7 ⁇ ⁇ cm or less.
- the gate electrode 13 is formed by forming a solid Al alloy film by a sputtering method, laminating a cap layer such as a nitride film and a metal film, and then patterning the gate electrode 13 into a predetermined shape.
- a sputtering method for example, a DC sputtering method, a pulse DC sputtering method, an RF sputtering method, or the like is applied.
- Either wet etching or dry etching is applied to the patterning of the solid Al alloy film. Further, either dry etching or wet etching is applied to the patterning of the cap layer.
- the film formation and patterning of the gate electrode 13 are generally performed in the middle of the manufacturing process of the thin film transistors 1 and 2.
- heat treatment is performed during the manufacturing process as needed.
- heat treatment at 500 ° C. or lower may be performed to activate the active layer 11 or to supplement the active layer 11 with hydrogen.
- the heating time is appropriately changed, and is, for example, 90 minutes or less at 450 ° C. and 60 minutes or less at 500 ° C.
- the same heat treatment is performed on the thin film transistor 2.
- heat treatment at 500 ° C. or lower may be performed in order to repair the defect. In this case as well, the heating time is appropriately changed, for example, 90 minutes or less at 450 ° C. and 60 minutes or less at 500 ° C.
- thin film transistors 1 and 2 are not only flat type display devices, but also curved type display devices with curved peripheral edges, bendable type display devices bent in an arc shape, and 180 degrees. It may be applied to foldable display devices and the like.
- a gate electrode containing a refractory metal (for example, Mo) as a main component When a gate electrode containing a refractory metal (for example, Mo) as a main component is applied to the curved surface of such a display device, the refractory metal does not have sufficient bending resistance. A part may be cracked and the electrode may be broken.
- the gate electrode has a role of forming a channel in the active layer facing each other via the gate insulating film. Therefore, when the gate electrode is applied to the curved surface portion of the display device, it is desirable that the gate electrode has no cracks or breaks and has excellent bending resistance.
- the resistivity of the refractory metal is relatively high among the metals, and as the size of the display in which the thin film transistor 1 or 2 is incorporated increases, display delay in the display may occur.
- the gate electrode may have high resistance or the gate electrode may be disconnected. Further, when another film is formed on the hillock, this film receives the shape of the underlying hillock, resulting in high resistance or disconnection of the film.
- the gate electrode 13 is required to be processed without residue by wet etching and dry etching.
- the low resistance of the gate electrode 13 has excellent bending resistance (flexibility) and excellent heat resistance at which hillock is less likely to occur. It is required to have it and to be able to perform etching processing without residue.
- the metal wiring structure shown in FIG. 1 (c) is applied as the material of the gate electrode 13.
- the metal wiring structure is formed, for example, by sputtering film formation in a vacuum chamber.
- a metal wiring film having a main component made of aluminum and an additive element made of iron added to the main component is formed on a substrate such as a glass substrate by a sputtering method. After that, the cap layer is laminated on the metal wiring film. Further, the metal wiring structure is heat-treated at 500 ° C. or lower together with the heat treatment applied to the active layers 11 and 21, for example. Vanadium may be added to the metal wiring film.
- the metal wiring structure is laminated on the Al alloy film 131, which is a metal wiring film, and TiN, MoN, WN, which are hard to be diffused in the Al alloy film 131. It has a cap layer 132 (first cap layer) composed of TaN, Ti, Mo, W, Ta and the like.
- the Al alloy film according to the present embodiment is a metal wiring film having a main component made of aluminum and an additive element added to the main component and made of iron of 0.005 at% or more and 0.88% or less (at%). : Atom%).
- the metal wiring film may contain vanadium of 0.01 at% or more and 0.05 at% or less as an additive element.
- the Al alloy film may also contain an unavoidable component.
- the Al alloy film is composed of a main component, a group of elements of iron and vanadium, and an unavoidable component.
- examples of the unavoidable component include Si, Cu, Mn, and Zn.
- the iron content is less than 0.005 at%, hillock is likely to occur in the Al alloy film when the Al alloy film is heat-treated, which is not preferable.
- the iron content is larger than 0.88 at%, it becomes difficult to control the target composition and the uniformity of the film quality cannot be obtained, which is not preferable.
- the vanadium content is less than 0.01 at%, hillock is likely to occur in the Al alloy film when the Al alloy film is heat-treated, which is not preferable.
- the vanadium content is larger than 0.05 at%, the resistivity of the Al alloy film becomes high, which is not preferable.
- a low resistance gate electrode 13 having a resistivity of 3.7 ⁇ ⁇ cm or less, preferably 3.3 ⁇ ⁇ cm or less is formed. Further, the Al alloy film has excellent bending resistance and exhibits an excellent effect by adding an element of Fe or V.
- the Al alloy film is heat-treated (500 ° C. max, heating time is 90 minutes or less at 450 ° C., 60 minutes or less at 500 ° C.) as an action due to the addition of an element of Fe or V. Hillock is less likely to occur in the Al alloy film.
- the Al alloy film is heat-treated (500 ° C max, heating time is 90 minutes or less at 450 ° C, 60 minutes or less at 500 ° C)
- the iron concentration between Al particles in the Al alloy film Is relatively high, the bond between adjacent Al particles is suppressed, and the Al particles remain in the state of fine particles (fine particle size: 1 ⁇ m or less).
- the average particle size of the particles in this embodiment is determined by a laser diffraction method, image analysis using an electron microscope image, or the like.
- vanadium when vanadium is contained in the Al alloy film, vanadium is a solid solution strengthening element for aluminum, so that solid solution of Al and V is promoted in Al particles.
- the intermetallic compound of Al—V is dispersed and formed, and the movement of Al in the Al particles (Al migration) is suppressed.
- the Al alloy film 131 is physically covered with the cap layer 132. Therefore, in synergy with the above-mentioned effect of the added element, the generation of hilok in the Al alloy film is further suppressed. As a result, even if the Al alloy film is heat-treated, the Al particles become enormous, that is, the formation of hillock is suppressed, and an Al alloy film having high heat resistance is formed.
- both the cap layer 132 and the Al alloy film 131 can be etched by dry etching.
- the cap layer 132 may be provided not only between the Al alloy film 131 and the gate insulating film 22, but also between the Al alloy film 131 and the glass substrate 10.
- the metal wiring film (Al alloy film 131) is provided with a cap layer 133 (second cap layer) different from the cap layer 132 on the side opposite to the cap layer 132.
- the cap layer 133 is composed of TiN, MoN, WN, TaN, Ti, Mo, W, Ta and the like.
- the action of the cap layer acts on the Al alloy film 131 not only from above the Al alloy film 131 but also from below, and Al The generation of hillock in the alloy film 131 is further suppressed.
- the cap layer 133 is formed on the Al alloy film 131 on the opposite side of the cap layer 132.
- the Al alloy film 131 is arranged between the cap layer 132 and the cap layer 133.
- Voids pores
- the element that does not melt with Al precipitates at the crystal grain boundary of the Al alloy after the heat treatment, and the element other than the place where this element is precipitated is deposited.
- Voids pores
- the present embodiment by adding two kinds of elements such as Fe or V to the Al film or by using a cap layer, it is possible to surely suppress the generation of hillock without generating voids. can.
- Al alloy target An aluminum alloy target (Al alloy target) is used as the sputtering target used for forming the Al alloy film.
- the Al alloy target a target having the same composition as the Al alloy film is prepared.
- the Al alloy target includes a pure metal piece of Al having a purity of 5N (99.999%) or higher, which is the main component, and an element group added to the main component of aluminum.
- the element group includes iron (Fe) of 0.005 at% or more and 0.88% or less, iron (Fe) of 0.005 at% or more and 0.88% or less, and vanadium of 0.01 at% or more and 0.05 at% or less. It consists of (V) (at%: atomic%).
- the Al alloy target may also contain an unavoidable component of 20 ppm or less in total.
- the Al alloy target consists of a principal component, a group of elements, and an unavoidable component.
- examples of the unavoidable component include Si, Cu, Mn, and Zn.
- Si is 4 ppm or less
- Cu is 3 ppm or less
- Mn is 1 ppm or less
- Zn is 0.3 ppm or less.
- the Al alloy target is formed as an Al alloy ingot by mixing element groups with Al pure metal pieces and melting these mixed materials in a crucible by a melting method such as induction heating.
- the Al alloy ingot is subjected to plastic working such as forging, rolling, and pressing, and the Al alloy ingot is processed into a plate shape or a disk shape to produce an Al alloy target.
- each metal material (metal piece, metal powder) of Al, Fe, or V is installed in the crucible.
- each metal material is heated to a melting temperature (for example, 955 ° C.) that is 300 ° C. or higher higher than the melting point of the Al alloy (for example, 655 ° C.), and each metal material is melted in the crucible.
- a melting temperature for example, 955 ° C.
- the molten metal is cooled to room temperature to form an aluminum alloy ingot.
- the aluminum alloy ingot is forged as needed, and the aluminum alloy ingot is cut out into a plate shape or a disk shape. This forms an Al alloy target.
- the metal material is melted at a melting temperature slightly higher than the melting point of the metal material, and the metal material is cooled from the slightly higher melting temperature to form an alloy ingot.
- the melting temperature is set to a temperature slightly higher than the melting point, so that the metal material may not be sufficiently mixed.
- the metal materials are heated and melted at a melting temperature 300 ° C. or higher higher than the melting point of the Al alloy, so that the metal materials are sufficiently mixed with each other.
- the higher the melting temperature the longer the cooling time from the melting temperature to room temperature, and the easier it is for the intermetallic compound to precipitate.
- the metal-to-metal compound is added so as to be difficult to precipitate in the Al alloy ingot. The concentration of the element is adjusted.
- the addition amount of the element group to be added in the above range By setting the addition amount of the element group to be added in the above range, the temperature difference between the solid phase line and the liquid phase line in the phase diagram of the metal compound becomes small, and the primary crystals due to the intermetallic compound or the like are formed in the pit. An Al alloy ingot that does not easily settle is formed. Additive elements are uniformly dispersed in the Al alloy ingot.
- the Al alloy film formed by sputtering using such an Al alloy target exhibits the above-mentioned excellent effects.
- the Al ingot may receive heat during plastic working such as forging, rolling, and pressing, and Al crystal grains may grow in the Al ingot.
- Al crystal grains are also present in the Al target produced from such an Al ingot, and the Al crystal grains receive heat from the plasma during film formation to form protrusions on the surface of the Al target. These protrusions may cause abnormal discharge, or the protrusions may pop out from the Al target during film formation.
- the Al alloy target of the present embodiment Fe or V is added to the Al pure metal in the above-mentioned addition amount.
- Fe or V is added to the Al pure metal in the above-mentioned addition amount.
- the Fe content at the grain boundary between the particles is higher than the Fe content in the particles.
- the Al alloy ingot (or Al alloy target) contains vanadium, which is a solid solution strengthening element, the solid solution of Al and V is promoted in the Al particles, and the Al—V intermetallic compound is dispersed. It is formed. As a result, the movement of Al in the Al particles is suppressed.
- the average particle size of the particles in the Al alloy ingot (or Al alloy target) is adjusted to be 100 ⁇ m or more and 200 ⁇ m or less.
- the grain boundary becomes a barrier, and the phenomenon that adjacent fine particles are bonded and the fine particles are coarsened is suppressed.
- the heat resistance of the Al alloy target is further improved.
- the film formation conditions of the metal wiring structure and the characteristics of each of the plurality of metal wiring structures are shown below.
- the metal wiring structure shown below is an example of the above composition, and the metal wiring structure in the present embodiment is not limited to the following example.
- the heat treatment is, for example, a nitrogen atmosphere, 450 ° C., 0.5 hours.
- Discharge power DC discharge, 5 W / cm 2 Film formation temperature: Room temperature Film formation pressure: 0.3Pa Film thickness: 300 nm
- Discharge power DC discharge, 5 W / cm 2 Film formation temperature: Room temperature Film formation pressure: 0.3Pa Film thickness: 70 nm, 50 nm, and 30 nm
- Al pure metal film Al-0.05at% Fe film, Al-0.1at% Fe film, Al-0.05at% Fe-0.05at% V film, Al-0. .1at% Fe-0.02at% V film, Al-0.2at% Fe-0.02at% V film, Al-0.2at% Fe-0.05at% V film, Al-0.8at% Fe- A 0.02 at% V film was formed.
- a nitride film as an example of the cap layer was further laminated on these Al pure metal film and Al alloy film.
- the purpose is that the metal wiring structure after the heat treatment has no hillock and has low resistance.
- FIG. 2A is a graph showing changes in surface roughness immediately after film formation of a plurality of Al alloy films and after heat treatment when no nitride film is provided.
- FIG. 2B is a graph showing a change in surface roughness after heat treatment of a plurality of Al alloy films when a nitride film is provided.
- the vertical axis of FIGS. 2A and 2B is the maximum valley depth (PV) of the roughness curve measured by AFM.
- PV maximum valley depth
- FIGS. 2 (a) and 2 (b) the results of the Al pure metal film (PureAl) are shown on the leftmost side, and the results of each of the plurality of Al alloy films are shown other than this.
- the ⁇ PV of the Al pure metal film was larger than that of the Al alloy film.
- the value was smaller than that in the Al pure metal film.
- the higher the Fe content the smaller the ⁇ PV tends to be.
- the addition of V further reduced ⁇ PV. That is, it was found that the generation of hillock was suppressed by adding an additive of Fe or V to Al pure metal.
- FIG. 2B shows the result after the heat treatment when the nitride film is provided.
- three types of thickness of the nitride film (TiN) of 30 nm, 50 nm, and 70 nm are prepared.
- ⁇ PV was lower than that in the case where the nitride film was not provided, but the ⁇ PV did not gradually approach 0.
- the V film, Al-0.2at% Fe-0.02at% V film, Al-0.2at% Fe-0.05at% V film, and Al-0.8at% Fe-0.02at% V film are nitrided. It was found that when the film was provided, ⁇ PV became smaller than that of the Al pure metal film.
- FIG. 3A is a graph showing changes in resistivity ⁇ ( ⁇ ⁇ cm) after heat treatment of an Al pure metal film and a plurality of Al alloy films.
- the broken line in the figure is the target value of the resistivity of the single-layer Al alloy film after the heat treatment, and the maximum resistivity of the single-layer Al alloy film is 3.7 ⁇ ⁇ cm or less.
- V is 0.05 at% or less, there is no weight segregation in the Al alloy, and the target can be prepared. Further, the diffusion coefficient in Al is small, dislocations are less likely to move, and good heat resistance is maintained. Therefore, even if the nitride film is formed thin, low ⁇ PV is maintained.
- FIG. 3B is a graph showing the resistivity ⁇ ( ⁇ ⁇ cm) of the Al alloy film on which the nitride film as the cap layer is formed before the heat treatment.
- FIG. 3C is a graph showing the resistivity ⁇ ( ⁇ ⁇ cm) of the Al alloy film on which the nitride film as the cap layer is formed after the heat treatment.
- the heating temperature is 450 ° C.
- 3 (b) and 3 (c) show a TiN film of an Al pure metal film, an Al-0.1at% Fe-0.02at% V film, and an Al-0.2at% Fe-0.05at% V film.
- the resistivity ⁇ (vertical axis) with is shown.
- the thickness of the cap layer is set to 30 nm, 50 nm, or 70 nm in each film as shown by the horizontal axes of FIGS. 3 (b) and 3 (c).
- the resistivity of the Al alloy film on which the cap layer is formed is preferably lower than that when a single-layer Mo film is used as the gate electrode 13, and is set to, for example, half or less of the resistivity of the Mo film. Is desirable. For example, it is desirable that the resistivity of the Al alloy film on which the cap layer is formed is set to 6 ⁇ ⁇ cm or less.
- the resistance of the Al alloy film was higher than that of the Al pure metal film.
- the resistivity of the Al-0.2at% Fe-0.05at% V film having a higher Fe concentration is higher than the resistivity of the Al-0.1at% Fe-0.02at% V film. It was also found that the resistivity increases as the thickness of the TiN film increases.
- the specific resistance is larger than 6 ⁇ ⁇ cm, but in other cases, the ratio is high.
- the resistance is 6 ⁇ ⁇ cm or less.
- the resistivity of the Al alloy film with a TiN film may be relatively lowered to 6 ( ⁇ ⁇ cm) or less at any film thickness of the TiN film. Do you get it.
- the resistivity of the TiN / Al-0.2at% Fe-0.05at% V film was 4.1 ( ⁇ ⁇ cm).
- the resistivity of the TiN / Al-0.1at% Fe-0.02at% V film is 3.7.
- the resistivity of the ( ⁇ ⁇ cm) and TiN / Al-0.2at% Fe-0.05at% V films was 3.5 ( ⁇ ⁇ cm), both of which were 3.7 ⁇ ⁇ cm or less.
- 4 (a) to 4 (h) are surface SEM images of the Al pure metal film and the plurality of Al alloy films after the heat treatment when the nitride film is not provided.
- 5 (a) to 5 (h) are surface SEM images of the Al pure metal film and the plurality of Al alloy films after the heat treatment when the nitride film is provided. In the surface SEM image, when the hillock is deposited on the surface of the Al alloy film, the hillock is projected as white particles.
- FIGS. 4 (a) to 5 (h) are the results of the heat treatment in a nitrogen atmosphere at 450 ° C. for 0.5 hours, but the Al combination provided with the nitride film (70 nm). It was found that in the metal film, hillock does not occur even if the heat treatment is longer than 0.5 hours or the heating temperature is raised to 500 ° C.
- FIGS. 6 (a) to 6 (f) show the surfaces of an Al pure metal film, an Al alloy film, and a laminated film with a cap layer when the heating temperature is 450 ° C. and the heating time is 1.5 hours. It is an SEM image.
- FIG. 6A shows a surface SEM image of the Al pure metal film
- FIG. 6B shows a surface SEM image of the Al pure metal film with a nitride film.
- FIG. 6C shows a surface SEM image of an Al-0.1at% Fe-0.02at% V film
- FIG. 6D shows an Al-0.1at% Fe-0 with a nitride film.
- a surface SEM image of the .02 at% V film is shown.
- FIG. 6E shows a surface SEM image of an Al-0.2at% Fe-0.05at% V film
- FIG. 6F shows an Al-0.2at% Fe-0 with a nitride film.
- a surface SEM image of the 0.05 at% V film is shown.
- FIG. 6A it was confirmed that hillock was generated in the Al pure metal film. Further, as shown in FIG. 6 (b), it was confirmed that hillock was generated even if a nitride film was provided on the Al pure metal film.
- FIG. 6 (c) although hillock is generated in the Al-0.1 at% Fe-0.02 at% V film, as shown in FIG. 6 (d), Al with a nitrided film is generated. It was confirmed that hillock did not occur in the -0.1 at% Fe-0.02 at% V film. Further, as shown in FIG. 6 (e), although hillock is generated in the Al-0.2at% Fe-0.05at% V film, as shown in FIG. 6 (f), Al-0 with a nitrided film is generated. It was confirmed that hillock did not occur in the .2 at% Fe-0.05 at% V film.
- FIG. 7 (a) to 7 (f) are surface SEM images of an Al pure metal film, an Al alloy film, and a laminated film with a cap layer when the heating temperature is 500 ° C. and the heating time is 1.0 hour.
- FIG. 7A shows a surface SEM image of the Al pure metal film
- FIG. 7B shows a surface SEM image of the Al pure metal film with a nitride film
- FIG. 7C shows a surface SEM image of an Al-0.1at% Fe-0.02at% V film
- FIG. 7D shows an Al-0.1at% Fe-0 with a nitride film.
- a surface SEM image of the .02 at% V film is shown.
- FIG. 7 (e) shows a surface SEM image of an Al-0.2at% Fe-0.05at% V film
- FIG. 7 (f) shows an Al-0.2at% Fe-0 with a nitride film.
- a surface SEM image of the 0.05 at% V film is shown.
- FIG. 7 (a) it was confirmed that hillock was generated in the Al pure metal film. Further, as shown in FIG. 7 (b), it was confirmed that hillock was generated even if a nitride film was provided on the Al pure metal film.
- FIG. 7 (c) although hillock is generated in the Al-0.1 at% Fe-0.02 at% V film, as shown in FIG. 7 (d), Al with a nitrided film is generated. It was confirmed that hillock did not occur in the -0.1 at% Fe-0.02 at% V film. Further, as shown in FIG. 7 (e), although hillock is generated in the Al-0.2at% Fe-0.05at% V film, as shown in FIG. 7 (f), Al-0 with a nitrided film is generated. It was confirmed that hillock did not occur in the .2 at% Fe-0.05 at% V film.
- the specific resistance of the Al alloy film is 450 ° C. and 0 heating time. It was about the same as the case of 5.5 hours.
- FIG. 8A shows an example of etching an Al-0.1at% Fe film
- FIG. 8B shows an example of etching an Al-0.05at% Fe-0.05at% V film.
- An example of etching is shown
- FIG. 8C shows an example of etching an Al-0.1at% Fe-0.02at% V film
- FIG. 8D shows an example of etching Al-0.2at.
- An example of etching a% Fe-0.05 at% V film is shown.
- the etching gas is a mixed gas of Cl 2 (50 sccm) / Ar (20 sccm).
- the etching pressure is 1.0 Pa.
- the discharge power is 600 W when the substrate bias power is 400 W.
- a fluorine-based gas CF 4 , SF 6 , CHF 3, etc.
- a chlorine-based gas BCl 3, etc.
- Wet etching solutions include ammonium fluoride / nitric acid / water mixed solution (eg Kanto Kagaku KSMF-260), KSMF series (Kanto Kagaku), and phosphoric acid / nitric acid / acetic acid / water mixed solution (Kanto Kagaku mixed acid).
- Al etching solution a hydrogen peroxide solution, a mixed solution containing a hydrogen peroxide solution, or the like is used.
- the liquid temperature is 40 ° C.
- the etching gas and the etching solution may be used properly, and dry etching and wet etching may be combined.
- FIG. 9 (a) and 9 (b) show an example of an SEM image of the surface of the glass substrate after etching a film in which a nitride film (TiN, 70 nm) is further attached to an Al alloy film formed on the glass substrate.
- a nitride film TiN, 70 nm
- FIG. 9A shows an example in which the TiN film / Al-0.1at% Fe-0.02at% V film is etched
- FIG. 9B shows an example of etching the TiN film / Al-0.
- An example of etching a .2 at% Fe-0.05 at% V film is shown.
- TMAH Tetramethylammonium hydroxide
- Table 1 shows the results of the bending test of the Al alloy film.
- a polyimide layer (25 ⁇ m) substrate was prepared as a substrate for bending test.
- Three types of Al alloys on the polyimide layer Al-0.1at% Fe film, Al-0.1at% Fe-0.02at% V film, and Al-0.2at% Fe-0.05at% V film.
- a film was formed.
- the thickness of the Al alloy film is 300 nm.
- a TiN film was formed on each Al alloy film.
- Three types of TiN film thicknesses of 30 nm, 50 nm, and 70 nm were prepared. That is, nine kinds of evaluation samples (samples 1 to 9) were formed.
- Each of the evaluation samples was annealed at 450 ° C for 30 minutes before the bending test.
- the bending radius in the bending test is 1 mm.
- the test speed is 30 rpm.
- the number of bends is 1, 1000, 10000, and 100,000.
- the resistance (seat resistance ( ⁇ / square)) before and after the bending test was measured.
- the resistance before the bending test is R0
- the resistance after the test is R
- R / RO is shown in Table 1. The closer R / R0 is to "1", the more there is no change in resistance before and after the bending test.
- the thickness of the TiN film is preferably set to 50 nm or less in order to obtain more reliable bending resistance.
- Table 2 shows another result of the bending test of the Al alloy film.
- Table 2 shows the case where the bending radius in the bending test is 1.5 mm.
- Three kinds of samples were prepared (samples 10 to 12).
- each of three types of Al alloy films Al-0.1at% Fe film, Al-0.1at% Fe-0.02at% V film, and Al-0.2at% Fe-0.05at% V film.
- a 70 nm TiN film was formed on the surface.
- the material of the cap layer not only the TiN film but also any film composed of MoN, WN, TaN, Ti, Mo, W, Ta and the like may be used.
- the resistivity of the W / Al-0.2at% Fe-0.05at% V film is 4.4 ( ⁇ ⁇ cm)
- the Ta film is 70 nm
- Ta / Al- the resistivity of the Mo / Al-0.2 at% Fe-0.05 at% V film is The resistivity was 4.4 ( ⁇ ⁇ cm), and the resistivity was about the same as that of the Al alloy film with TiN.
- FIGS. 10 (a) to 10 (d) are surface SEM images of a laminated film with a cap layer when the heating temperature is 500 ° C. and the heating time is 1.0 hour.
- the cap layer Mo having a film thickness of 30 nm (FIG. 10 (a)), Mo having a film thickness of 70 nm (FIG. 10 (b)), W having a film thickness of 30 nm (FIG. 10 (c)), or a film thickness. W of 70 nm (FIG. 10 (d)) is used.
- the Al alloy film is an Al-0.2at% Fe-0.05at% V film (film thickness: 300 nm).
- Table 3 shows the case where the bending radius in the bending test is 1.0 mm.
- a cap layer of Mo and W is formed on an Al-0.2at% Fe-0.05at% V film having a film thickness of 300 nm, and for example, Mo (70 nm) /Al-0.2at%Fe-0. 05at% V film (sample 13), Mo (30nm) /Al-0.2at%Fe-0.05at% V film (sample 14), W (70nm) /Al-0.2at%Fe-0.05at%
- V film sample 15
- W (30 nm) /Al-0.2at%Fe-0.05at% V film
- the cap layer is not limited to TiN, and any material having mechanical properties similar to TiN can exhibit the same heat resistance effect as TiN as the cap layer. Further, by optimizing the type and film thickness of the cap layer, it is possible to achieve both heat resistance and flexibility.
- the material exemplified in this embodiment is an example, and the film thickness of each film can be adjusted and the structure of two layers and three layers can be adjusted according to the specifications of heat resistance, resistivity, and bending resistance. can.
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Abstract
Description
成膜温度:室温
成膜圧力:0.3Pa
膜厚:300nm
成膜温度:室温
成膜圧力:0.3Pa
膜厚:70nm、50nm、及び30nm
10…ガラス基板
11、21…活性層
12、22…ゲート絶縁膜
13…ゲート電極
15…保護層
16D、26D…ドレイン電極
16S、26S…ソース電極
131…Al合金膜
132、133…キャップ層
Claims (8)
- アルミニウムからなる主成分と、前記主成分に添加され、0.005at%以上0.88%以下の鉄からなる添加元素とを有する金属配線膜と、
前記金属配線膜に積層された第1キャップ層と
を具備する金属配線構造体。 - 請求項1に記載された金属配線構造体であって、
前記添加元素として、0.01at%以上0.05at%以下のバナジウムをさらに有する金属配線構造体。 - 請求項2に記載された金属配線構造体であって、
前記主成分と、前記添加元素と、不可避成分とからなる
金属配線構造体。 - 請求項1~3のいずれか1つに記載された金属配線構造体であって、
前記金属配線膜には、前記第1キャップ層とは反対側において、第2キャップ層が設けられ、前記金属配線膜が前記第1キャップ層と前記第2キャップ層との間に設けられている
金属配線構造体。 - アルミニウムからなる主成分と、前記主成分に添加され、0.005at%以上0.88%以下の鉄からなる添加元素とを有する金属配線膜を基板に形成し、
前記金属配線膜に第1キャップ層を積層し、
前記金属配線膜が500℃以下で加熱処理される
金属配線構造体の製造方法。 - 請求項5に記載された金属配線構造体の製造方法であって、
前記第1キャップ層とは反対側の前記金属配線膜に第2キャップ層を形成し、前記金属配線膜を前記第1キャップ層と前記第2キャップ層との間に配置する
金属配線構造体の製造方法。 - アルミニウムからなる主成分と、
前記主成分に添加され、0.005at%以上0.88%以下の鉄からなる添加元素と
を具備するスパッタリングターゲット。 - 請求項7に記載されたスパッタリングターゲットであって、
前記添加元素として、0.01at%以上0.05at%以下のバナジウムをさらに有するスパッタリングターゲット。
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JP2008098611A (ja) * | 2006-09-15 | 2008-04-24 | Kobe Steel Ltd | 表示装置 |
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US20050112019A1 (en) * | 2003-10-30 | 2005-05-26 | Kabushiki Kaisha Kobe Seiko Sho(Kobe Steel, Ltd.) | Aluminum-alloy reflection film for optical information-recording, optical information-recording medium, and aluminum-alloy sputtering target for formation of the aluminum-alloy reflection film for optical information-recording |
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JP2004260194A (ja) * | 1995-10-12 | 2004-09-16 | Toshiba Corp | 配線膜、配線膜形成用のスパッタターゲットおよびそれを用いた電子部品 |
JP2008098611A (ja) * | 2006-09-15 | 2008-04-24 | Kobe Steel Ltd | 表示装置 |
JP2017092330A (ja) * | 2015-11-13 | 2017-05-25 | 株式会社神戸製鋼所 | デバイス用配線膜 |
JP2017092331A (ja) * | 2015-11-13 | 2017-05-25 | 株式会社神戸製鋼所 | デバイス用配線膜、およびAl合金スパッタリングターゲット材料 |
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