WO2012118039A1 - 表示装置もしくは半導体装置用Al合金膜、Al合金膜を備えた表示装置もしくは半導体装置、およびスパッタリングターゲット - Google Patents
表示装置もしくは半導体装置用Al合金膜、Al合金膜を備えた表示装置もしくは半導体装置、およびスパッタリングターゲット Download PDFInfo
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- WO2012118039A1 WO2012118039A1 PCT/JP2012/054837 JP2012054837W WO2012118039A1 WO 2012118039 A1 WO2012118039 A1 WO 2012118039A1 JP 2012054837 W JP2012054837 W JP 2012054837W WO 2012118039 A1 WO2012118039 A1 WO 2012118039A1
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- alloy film
- display device
- precipitate
- semiconductor device
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Images
Classifications
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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
- 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
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- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22F—CHANGING THE PHYSICAL STRUCTURE OF NON-FERROUS METALS AND NON-FERROUS ALLOYS
- C22F1/00—Changing the physical structure of non-ferrous metals or alloys by heat treatment or by hot or cold working
- C22F1/04—Changing the physical structure of non-ferrous metals or alloys by heat treatment or by hot or cold working of aluminium or alloys based thereon
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- C—CHEMISTRY; METALLURGY
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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
- C23C14/00—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material
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- C23C14/16—Metallic material, boron or silicon on metallic substrates or on substrates of boron or silicon
- C23C14/165—Metallic material, boron or silicon on metallic substrates or on substrates of boron or silicon by cathodic sputtering
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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
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- 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
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- C23C14/3414—Metallurgical or chemical aspects of target preparation, e.g. casting, powder metallurgy
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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
- H01L21/28—Manufacture of electrodes on semiconductor bodies using processes or apparatus not provided for in groups H01L21/20 - H01L21/268
- H01L21/283—Deposition of conductive or insulating materials for electrodes conducting electric current
- H01L21/285—Deposition of conductive or insulating materials for electrodes conducting electric current from a gas or vapour, e.g. condensation
- H01L21/28506—Deposition of conductive or insulating materials for electrodes conducting electric current from a gas or vapour, e.g. condensation of conductive layers
- H01L21/28512—Deposition of conductive or insulating materials for electrodes conducting electric current from a gas or vapour, e.g. condensation of conductive layers on semiconductor bodies comprising elements of Group IV of the Periodic Table
- H01L21/2855—Deposition of conductive or insulating materials for electrodes conducting electric current from a gas or vapour, e.g. condensation of conductive layers on semiconductor bodies comprising elements of Group IV of the Periodic Table by physical means, e.g. sputtering, evaporation
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- 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
- H01L23/53204—Conductive materials
- H01L23/53209—Conductive materials based on metals, e.g. alloys, metal silicides
- H01L23/53214—Conductive materials based on metals, e.g. alloys, metal silicides the principal metal being aluminium
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L27/00—Devices consisting of a plurality of semiconductor or other solid-state components formed in or on a common substrate
- H01L27/02—Devices consisting of a plurality of semiconductor or other solid-state components formed in or on a common substrate including semiconductor components specially adapted for rectifying, oscillating, amplifying or switching and having potential barriers; including integrated passive circuit elements having potential barriers
- H01L27/12—Devices consisting of a plurality of semiconductor or other solid-state components formed in or on a common substrate including semiconductor components specially adapted for rectifying, oscillating, amplifying or switching and having potential barriers; including integrated passive circuit elements having potential barriers the substrate being other than a semiconductor body, e.g. an insulating body
- H01L27/1214—Devices consisting of a plurality of semiconductor or other solid-state components formed in or on a common substrate including semiconductor components specially adapted for rectifying, oscillating, amplifying or switching and having potential barriers; including integrated passive circuit elements having potential barriers the substrate being other than a semiconductor body, e.g. an insulating body comprising a plurality of TFTs formed on a non-semiconducting substrate, e.g. driving circuits for AMLCDs
- H01L27/124—Devices consisting of a plurality of semiconductor or other solid-state components formed in or on a common substrate including semiconductor components specially adapted for rectifying, oscillating, amplifying or switching and having potential barriers; including integrated passive circuit elements having potential barriers the substrate being other than a semiconductor body, e.g. an insulating body comprising a plurality of TFTs formed on a non-semiconducting substrate, e.g. driving circuits for AMLCDs with a particular composition, shape or layout of the wiring layers specially adapted to the circuit arrangement, e.g. scanning lines in LCD pixel circuits
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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
- H01L21/28—Manufacture of electrodes on semiconductor bodies using processes or apparatus not provided for in groups H01L21/20 - H01L21/268
- H01L21/28008—Making conductor-insulator-semiconductor electrodes
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L2924/00—Indexing scheme for arrangements or methods for connecting or disconnecting semiconductor or solid-state bodies as covered by H01L24/00
- H01L2924/0001—Technical content checked by a classifier
- H01L2924/0002—Not covered by any one of groups H01L24/00, H01L24/00 and H01L2224/00
Definitions
- the present invention is used in display devices such as liquid crystal displays and semiconductor devices such as IGBTs, and is useful as an electrode and wiring material that can be processed by both dry etching and wet etching.
- Al alloy film for semiconductor devices The present invention relates to a display device or a semiconductor device provided with a film, and a sputtering target for forming the Al alloy film.
- Al alloy films for display devices are mainly used as electrodes and wiring materials.
- electrodes and wiring materials gate electrodes, source and drain electrodes and wiring materials for thin film transistors in liquid crystal displays (LDC), organic EL (OELD) Gate, source and drain electrodes and wiring materials for thin film transistors, cathode and gate electrodes and wiring materials for field emission display (FED), anode and wiring materials for fluorescent vacuum tube (VFD), address electrodes for plasma display (PDP) and Examples include wiring materials and back electrodes in inorganic EL.
- Al alloy films for semiconductor devices are mainly used as electrodes and wiring materials.
- the electrodes and wiring materials include semiconductor emitter electrodes such as IGBTs, wiring materials, collector electrodes, and wiring materials.
- liquid crystal display is typically taken up and described as a liquid crystal display device, but the present invention is not limited to this.
- TFTs active matrix liquid crystal displays that use thin film transistors (hereinafter referred to as TFTs) for switching pixels have high-precision image quality. Because it can support high-speed video, it is the mainstay.
- TFTs using polycrystalline silicon or continuous grain boundary crystalline silicon as a semiconductor layer are used in liquid crystal displays that require further low power consumption and high-speed pixel switching.
- an active matrix liquid crystal display includes a TFT substrate having a TFT that is a switching element, a pixel electrode made of a conductive oxide film, and a wiring including a scanning line and a signal line. Are electrically connected to the pixel electrode.
- An Al-based alloy thin film is used as a wiring material constituting the scanning lines and signal lines.
- a scanning line 25 is formed on a glass substrate 21a, and a part of the scanning line 25 functions as a gate electrode 26 for controlling on / off of the TFT.
- the gate electrode 26 is electrically insulated by a gate insulating film (such as a silicon nitride film) 27.
- a semiconductor silicon layer 30 as a channel layer is formed through the gate insulating film 27, and a protective film (silicon nitride film or the like) 31 is further formed.
- the semiconductor silicon layer 30 is bonded to the source electrode 28 and the drain electrode 29 via the low resistance silicon layer 32 and has electrical conductivity.
- the drain electrode 29 has a structure in direct contact with a transparent electrode 35 such as ITO (Indium Tin Oxide) [referred to as a direct contact (DC). ]have.
- a transparent electrode 35 such as ITO (Indium Tin Oxide) [referred to as a direct contact (DC).
- DC Direct contact
- Examples of the electrode wiring material used for direct contact include Al alloys described in Patent Documents 1 to 5. This is because Al has a small electrical resistivity and excellent fine workability. These Al alloys are directly connected to the oxide transparent conductive film constituting the transparent electrode or directly to the silicon semiconductor layer without interposing a barrier metal layer made of a refractory metal such as Mo, Cr, Ti, and W. Has been.
- These wiring films and electrodes are covered with an insulating protective film 33 such as silicon nitride, and supply electricity to the drain electrode 29 through the transparent electrode 35.
- an insulating protective film 33 such as silicon nitride
- the manufacturing process of a liquid crystal display or the like includes a heat treatment step for TFTs.
- a part or the whole of the semiconductor silicon layer 30 having an amorphous structure is microcrystallized / polycrystallized. The degree becomes higher and the response speed of the TFT is improved.
- the insulating protective film 33 is deposited at a relatively low temperature of about 250 to 350 ° C.
- a high temperature heat treatment at about 450 ° C. or higher may be performed.
- such low temperature or high temperature heat treatment may be performed a plurality of times.
- Patent Document 1 described above discloses that an Al alloy thin film having an electric resistance value of 10 ⁇ cm or less is obtained by precipitating a part or all of a solid solution element in an Al alloy thin film as a metal compound by heat treatment at 100 to 600 ° C.
- Patent Document 2 discloses heat resistance up to 500 ° C., but does not evaluate heat resistance when exposed to high temperatures of 500 ° C. or higher.
- Patent Documents 3 to 5 are only 450 ° C. or less and do not evaluate the heat resistance when exposed to high temperatures exceeding 450 ° C. Of course, no consideration is given to the heat resistance when exposed to such high temperatures multiple times.
- Patent Document 6 discloses an Al alloy film excellent in dry etching processability, but the example shows only a result when heated at a temperature of 350 ° C., and is 450 ° C. or higher. The heat resistance when exposed to high temperatures is not evaluated.
- Japanese Unexamined Patent Publication No. 7-90552 Japanese Unexamined Patent Publication No. 2003-73810 Japanese Unexamined Patent Publication No. 2002-322528 Japanese Unexamined Patent Publication No. 8-250494 Japanese Patent Laid-Open No. 2001-93862 Japanese Unexamined Patent Publication No. 2000-294556
- the hydrogenated amorphous silicon is microcrystallized and carrier mobility is improved.
- the heat treatment temperature is increased, problems such as the occurrence of protrusion-like shape abnormalities (hillocks) occur in the Al alloy wiring thin film due to thermal stress.
- the temperature was about 350 ° C. at most. Therefore, when heat treatment is performed at a temperature higher than this, a refractory metal thin film such as Mo is generally used, but there is a problem that the wiring resistance is high and the display cannot be enlarged.
- a display device it may be required to exhibit a low contact resistance (contact resistance) when directly connected to a transparent pixel electrode.
- the TFT substrate manufacturing process passes through a plurality of wet processes.
- a metal nobler than Al is added, a problem of galvanic corrosion appears and corrosion resistance deteriorates.
- an alkaline developer containing TMAH tetramethylammonium hydroxide
- the barrier metal layer is omitted, the Al alloy film is exposed, and the developer It becomes easy to receive damage by. Therefore, it is required to be excellent in alkali corrosion resistance such as alkali developer resistance.
- wet etching wiring patterning by chemical etching
- dry etching reactive plasma etching
- the present invention has been made in view of the above circumstances.
- the object of the present invention is to generate no hillock even when exposed to a high temperature of about 450 to 600 ° C. and to be excellent in high-temperature heat resistance. Wiring resistance) is also kept low, and it is also excellent in alkali corrosion resistance such as alkali developer resistance.
- an Al alloy film for display devices or semiconductor devices that can be processed by both wet etching methods and dry etching methods. It is to provide.
- Another object of the present invention is to provide an Al alloy film for a display device or a semiconductor device that is excellent in a stripping solution (stripping solution resistance) of a photosensitive resin.
- Still another object of the present invention is an Al alloy for display devices that has a low contact resistance when directly connected to a transparent pixel electrode (transparent conductive film) and can be directly connected to the transparent conductive film (direct contact). It is to provide a membrane.
- the present invention provides the following display device or Al alloy film for a semiconductor device, sputtering target, Al alloy wiring, a display device provided with an Al alloy film, and a semiconductor device.
- An Al alloy film used for a display device or a semiconductor device wherein the Al alloy film has 0.01 to 2.0 atomic% of Ge, Ta, Ti, Zr, Hf, W, Cr, Nb. And at least one element selected from the group consisting of Mo, Ir, Pt, Re, and Os (group X), An Al alloy film for a display device or a semiconductor device, which satisfies the following requirement (1) when the Al alloy film is heated at 450 to 600 ° C.
- concentration of the equivalent circle diameter of 50 nm or more is a density of 200,000 piece / mm ⁇ 2 > or more.
- the Al alloy film further includes at least one selected from the group consisting of rare earth elements.
- the Al alloy film is subjected to a heat treatment at 450 to 600 ° C., the following requirement (3) is further satisfied.
- the deposit with a circle equivalent diameter of 10 nm or more is 1,000,000. It exists at a density of 000 / mm 2 or more.
- the Al alloy film further contains at least one element selected from the group consisting of Ni, Co, and Fe.
- the Al alloy film is subjected to a heat treatment at 450 to 600 ° C., the following ( The Al alloy film for a display device or a semiconductor device according to any one of [1] to [4], which satisfies the requirement 5).
- Precipitates of 250 nm or more are present at a density of 2,000 pieces / mm 2 or more.
- the content of at least one element selected from the group consisting of Ni, Co, and Fe is 0.1 to 0.35 atomic%, according to any one of [5] to [12] Al alloy film for display devices or semiconductor devices.
- the Al alloy film is connected to the transparent conductive film via a film containing at least one element selected from the group consisting of Mo, Ti, W, and Cr [1] to [15] ] Al alloy film for display apparatuses or semiconductor devices as described in any one of.
- a sputtering target comprising 0.1 to 5 atomic% of at least one element.
- a display device comprising the Al alloy film for a display device according to any one of [1] to [17].
- a liquid crystal display comprising the Al alloy film for a display device according to any one of [1] to [17].
- a field emission display comprising the Al alloy film for a display device according to any one of [1] to [17].
- a fluorescent vacuum tube comprising the Al alloy film for a display device according to any one of [1] to [17].
- a plasma display comprising the Al alloy film for a display device according to any one of [1] to [17].
- a semiconductor device comprising the Al alloy film for a semiconductor device according to any one of [1] to [17].
- a semiconductor element comprising the Al alloy film for a semiconductor device according to any one of [1] to [17].
- the first Al alloy film (Al—Ge—X group element) includes a predetermined alloy element and a first precipitate (preferably a first precipitate and a second precipitate). Therefore, it is excellent in heat resistance when exposed to high temperatures of about 450 to 600 ° C., and the electric resistance (wiring resistance) of the film itself after high temperature processing can be kept low, and corrosion resistance, etching Combines processability and resistance to stripping solution.
- the second Al alloy film (Al—Ge—X group element-rare earth element) according to the present invention, which is a preferred embodiment, includes a predetermined alloy element and a first precipitate (preferably a first precipitate and a second precipitate). ) And the third precipitate (preferably the third precipitate and the fourth precipitate), it exhibits higher heat resistance and also better resistance to alkali corrosion.
- a third Al alloy film (Al—Ge—X group element— [Ni, Co, Fe] alloy according to the present invention, which is a more preferred embodiment, preferably Al—Ge—X group element—rare earth element— [Ni, Co, Fe] alloy) is a predetermined alloy element and a first precipitate (preferably a first precipitate and a second precipitate, more preferably a first precipitate, a second precipitate and a third precipitate). And, more preferably, the first precipitate, the second precipitate, the third precipitate and the fourth precipitate), and the fifth precipitate. Since low contact resistance with a transparent conductive film can also be achieved, direct connection with a transparent conductive film is possible.
- the high-temperature heat treatment at about 450 to 600 ° C., and the high-temperature heat treatment is performed at least twice. Even when exposed to harsh high-temperature environments, the carrier mobility of the semiconductor silicon layer is increased, improving the TFT response speed and providing high-performance display devices that can handle energy savings and high-speed video. it can. In wiring processing, both a wet etching method and a dry etching method can be applied.
- the Al alloy film is excellent in heat resistance (particularly high temperature heat resistance), for example, in the manufacturing process of an IGBT provided with this as an electrode / electric wiring of a semiconductor element, the ion activity of the collector layer Heat treatment for crystallization can be performed at a high temperature. As a result, it is possible to realize a semiconductor element having the Al alloy film and improved characteristics, and the semiconductor device having the semiconductor element and exhibiting excellent characteristics. In wiring processing, both a wet etching method and a dry etching method can be applied.
- FIG. 1 is a diagram illustrating a cross-sectional structure of a core portion of a thin film transistor.
- FIG. 2 is a diagram showing a Kelvin pattern (TEG pattern) used for measuring the contact resistance between the Al alloy film and the transparent pixel electrode.
- FIG. 3 is a schematic cross-sectional view showing an example of a liquid crystal display.
- FIG. 4 is a schematic cross-sectional view showing an example of an organic EL display.
- FIG. 5 is a schematic cross-sectional view showing an example of a field emission display.
- FIG. 6 is a schematic cross-sectional view showing an example of a fluorescent vacuum tube.
- FIG. 7 is a schematic cross-sectional view showing an example of a plasma display.
- FIG. 1 is a diagram illustrating a cross-sectional structure of a core portion of a thin film transistor.
- FIG. 2 is a diagram showing a Kelvin pattern (TEG pattern) used for measuring the contact resistance between the Al alloy film and the transparent pixel electrode.
- FIG. 8 is a schematic cross-sectional view showing an example of an inorganic EL display.
- FIG. 9 is a schematic cross-sectional view showing a configuration of a general IGBT.
- FIG. 10 is a schematic cross-sectional view showing the configuration of the dry etching apparatus.
- the inventors of the present invention have excellent heat resistance at high temperatures without generating hillocks even when exposed to a high temperature of about 450 to 600 ° C., and are sometimes referred to as dry etching characteristics and wet etching characteristics (hereinafter referred to as etching characteristics). ),
- the electrical resistance (wiring resistance) of the film itself is kept low, and the Al alloy film for a display device (first Al alloy film) having high resistance to alkali corrosion such as an alkali developer and stripping solution.
- an Al alloy film for a display device which is preferably superior in high-temperature heat resistance (sometimes referred to as a second Al alloy film);
- the Al alloy film for display devices that can be directly connected to the transparent conductive film (direct contact) because the contact resistance is kept low even when directly connected to the transparent conductive film. 3 To provide may be referred to as Al alloy film.), We have been studying.
- Al alloy film Al—Ge—X group element alloy alloy film
- a first Al that satisfies the following requirement (1) It has been found that the alloy film can solve the above problems (high heat resistance and etching characteristics during high temperature processing, low electrical resistance, and high alkali developer resistance and stripping solution resistance).
- concentration of the equivalent circle diameter of 50 nm or more is 200,000 piece / mm ⁇ 2 > or more in density Exists.
- the Al alloy film is subjected to a heat treatment at 450 to 600 ° C.
- the first Al alloy film that satisfies the requirement (1) and satisfies the requirement (2) below is more It was found to show high heat resistance.
- Al alloy film Al—Ge—X group element-REM alloy film
- Al—Ge—X group element-REM alloy film Al—Ge—X group element-REM alloy film
- the above (1) preferably further It was found that the second Al alloy film satisfying the requirement (2) and satisfying the requirement (3) below has better heat resistance than the first Al alloy film.
- the second Al alloy film satisfies the requirements of the above (1) (preferably further (2) above) and (3) above when subjected to a heat treatment at 450 to 600 ° C., and It turned out that the 2nd Al alloy film which satisfies the requirements of following (4) shows much more excellent heat resistance.
- the deposit with a circle equivalent diameter of 10 nm or more is 1,000,000. It exists at a density of 000 / mm 2 or more.
- an Al alloy film (Al—Ge—X group element—REM— [Ni, Co, Fe] alloy film) containing at least one element selected from Ni, Co, and Fe, and having a temperature of 450 to 600 ° C.
- the above (1) preferably further satisfies any one or more of the above (2), (3), (4) and satisfies the following (5)
- the third Al alloy film showed low contact resistance even when directly in contact with a transparent conductive film such as ITO, and was found to be more excellent in resistance to stripping solution at high temperatures.
- the fifth precipitate containing Al, at least one element selected from Ni, Co, and Fe, Ge, and at least one element selected from Group X, has a circle-equivalent diameter of 250 nm or more. Precipitates are present at a density of 2,000 / mm 2 or more.
- the first Al alloy film contains Ge and a refractory metal X group element (high temperature heat resistance improving element) in the Al alloy, and in the case of a single X group element, a predetermined first precipitate ( In the case of a plurality of X group elements, a predetermined first precipitate (Al—Ge—X1, Al—Ge—X2, etc .: X1 and X2 mean different X group elements ) And second precipitates (Al-X1-X2, Al-X1-X3, Al-X2-X3, etc .: when there are three types of X group elements), Excellent heat resistance) and etching characteristics, high resistance to alkali corrosion and stripping solution, and excellent electrical resistance (wiring resistance) of the film itself, so that wiring such as scanning lines and signal lines for display devices; It is suitably used as a material for electrodes such as a gate electrode, a source electrode, and a drain electrode.
- a gate electrode of a thin film transistor substrate and a related wiring film material that are easily affected by high temperature thermal history is suitably used as an electrode material such as an electrode of a power semiconductor; an emitter electrode of an IGBT.
- the second Al alloy film contains a rare earth element in addition to the Ge and refractory metal X group element (high temperature heat resistance improving element) in the Al alloy, thereby forming a single X group element.
- the predetermined first precipitate Al—Ge—X
- the third precipitate Al—X—REM: REM is a rare earth element
- the fourth precipitate Al—Ge—X.
- -REM and in the case of a plurality of X group elements, it further has a second precipitate (Al-X1-X2 etc.) (the first, third, and fourth precipitates also have an X group element).
- the heat resistance at high temperatures is particularly higher among the effects of the first Al alloy film, and scanning lines and signal lines Wiring such as:
- It is suitably used as a material for electrodes such as gate electrodes, source electrodes, and drain electrodes .
- electrodes such as gate electrodes, source electrodes, and drain electrodes .
- it is suitably used as a gate electrode of a thin film transistor substrate and a related wiring film material that are easily affected by high temperature thermal history.
- it is suitably used as an electrode material such as an electrode of a power semiconductor; an emitter electrode of an IGBT.
- the third Al alloy film is made of Ni, Co, and Fe, which are elements for reducing contact resistance with the transparent conductive film, in addition to the X group element, Ge, and preferably a rare earth element, in the Al alloy.
- a predetermined fifth precipitate Al—X—Ge— [Ni, Co, Fe] in addition to the precipitates included in the first and second Al alloy films.
- direct connection to the transparent conductive film is possible without interposing a barrier metal layer.
- -It is suitably used as a wiring material.
- high temperature heat resistance means that hillocks do not occur when exposed to a high temperature of at least about 450 to 600 ° C., and preferably, it is repeatedly exposed at least twice or more to the high temperature described above. This means that no hillock will occur.
- etching characteristics required in the manufacturing process of display devices and semiconductor devices high resistance (corrosion resistance) to chemicals (alkali developer, stripping solution) used in the manufacturing process, transparent conductive film Characteristics such as low contact resistance and low electrical resistance of the Al alloy film itself, but it is characterized in that it can be effectively exhibited not only in the low temperature range below 450 ° C. but also in the high temperature range described above.
- exposure to an alkaline environment is a stage before receiving a thermal history. Therefore, in the examples described later, the resistance to alkaline developer was examined for an Al alloy film before heating.
- alkali developer resistance may be referred to as alkali corrosion resistance in a broad sense.
- the first Al alloy film is at least one selected from the group consisting of Ta, Ti, Zr, Hf, W, Cr, Nb, Mo, Ir, Pt, Re, and Os (X group) in addition to Ge.
- the group X element (group X element) is composed of a refractory metal having a melting point of approximately 1600 ° C. or higher, and is an element that contributes to improving heat resistance at high temperatures. These elements may be added alone or in combination of two or more. Of the group X elements, Ta, Ti, Zr, and Hf are preferable, and Ta, Zr, and Hf are more preferable.
- the content of the X group element (when contained alone, it is a single amount, and when two or more types are used in combination) is preferably from 0.1 to 5 atomic%. When the content of the X group element is less than 0.1 atomic%, the above-described effect is not exhibited effectively. On the other hand, when the content of the group X element exceeds 5 atomic%, there arise problems that the electric resistance of the Al alloy film becomes too high and residues are easily generated during wiring processing.
- a more preferable content of the group X element is 0.3 atomic% or more and 3.0 atomic% or less, and more preferably 2.0 atomic% or less.
- the first Al alloy film only needs to contain at least the X group element and Ge, and may contain other elements as long as the action of these additive elements is not hindered.
- the Ge content is preferably 0.01 to 2.0 atomic%. If the Ge content is less than 0.01 atomic%, the desired effect cannot be obtained, and the density of the first precipitate that contributes to further improvement in heat resistance cannot be ensured. On the other hand, when the Ge content exceeds 2.0 atomic%, the electrical resistivity increases.
- the more preferable content of the element is 0.1 atomic% or more and 1.0 atomic% or less, and more preferably 0.2 atomic% or more and 0.6 atomic% or less.
- the first Al alloy film essentially contains a first precipitate having a predetermined size and a predetermined density defined in (1) above by high-temperature heat treatment at 450 to 600 ° C., preferably further (2) In this way, it is possible to realize high heat resistance and high resistance to stripping liquid at high temperatures.
- the first precipitate only needs to contain at least one element selected from Ge and X groups, and may contain other elements as long as the action of the precipitate is not hindered.
- the 2nd precipitate should just contain the at least 2 sort (s) of element selected from X group element, and may contain the other element, unless the effect
- the first Al alloy film contains the above elements, and the balance is Al and inevitable impurities.
- examples of the inevitable impurities include Si and B.
- the total amount of inevitable impurities is not particularly limited, it may be contained in an amount of about 0.5 atomic percent or less, and each inevitable impurity element is 0.012 atomic percent or less for B and 0.12 atomic percent or less for Si. You may contain.
- the circle equivalent diameter (size) of the first and second precipitates is 50 nm or more. According to the results of the study by the present inventors, precipitates of less than 50 nm are composed of precipitates containing Al—Ge—X group elements (first precipitates), or precipitates containing Al—X1-X2 Even if it was a thing (2nd precipitate), it turned out that a desired effect is not exhibited.
- the lower limit of the equivalent circle diameter may be 50 nm, and the upper limit is not particularly limited in relation to the above action, but the size of the precipitate is large. When it becomes a huge precipitate, it may be visually recognized by an inspection with an optical microscope, and an appearance defect is caused. Therefore, the upper limit is preferably 1 ⁇ m.
- a preferable equivalent circle diameter of the first precipitate and the second precipitate is 50 nm or more and 800 nm or less.
- the first precipitate is present at a density of 200,000 pieces / mm 2 or more with the equivalent circle diameter of 50 nm or more. According to the examination results of the present inventors, it has been found that even if the size of the first precipitate is 50 nm or more, the desired effect is not exhibited when it is less than 200,000 pieces / mm 2 . In order to effectively exhibit the effect of improving the high temperature heat resistance, the density of the precipitate is preferably as high as possible, and is preferably 2,000,000 pieces / mm 2 or more.
- the second precipitate is present at a density of 100,000 / mm 2 or more with the equivalent circle diameter of 50 nm or more. According to the examination results of the present inventors, it has been found that even if the size of the second precipitate is 50 nm or more, the desired effect is not exhibited when it is less than 100,000 pieces / mm 2 . In order to effectively exhibit the effect of improving the high temperature heat resistance, the density of the precipitate is preferably as high as possible, and is preferably 1,000,000 pieces / mm 2 or more.
- the second Al alloy film is an Al—Ge—X group element-REM alloy film containing a rare earth element (REM) in addition to the Ge and X group elements described above.
- REM rare earth element
- the rare earth element is an element that contributes to the improvement of the high temperature heat resistance when added in combination with the Ge and X group elements. Furthermore, it has an effect not found in the Ge and X group elements, which is an effect of improving corrosion resistance in an alkaline environment alone.
- the rare earth element is an element group in which Sc (scandium) and Y (yttrium) are added to a lanthanoid element (a total of 15 elements from La with atomic number 57 to Lu with atomic number 71 in the periodic table).
- the rare earth elements may be used alone or in combination of two or more.
- the rare earth elements Nd, La, Gd, and Ce are preferable, and Nd and La are more preferable.
- the rare earth element content (individual amount when contained alone, and total amount when two or more kinds are used in combination) is 0.1. It is preferably from 0.45 atomic%. If the rare earth element content is less than 0.1 atomic%, the effect of improving heat resistance and alkali corrosion resistance is not effectively exhibited. On the other hand, if the content exceeds 0.45 atomic%, the dry etching rate becomes slow. There are problems such as residue. A more preferable content of the rare earth element is 0.15 atomic% or more and 0.4 atomic% or less, and a more preferable content is 0.15 atomic% or more and 0.3 atomic% or less.
- the second Al alloy film only needs to contain at least the X group element, Ge, and rare earth element, and may contain other elements as long as the action of these additive elements is not hindered.
- the second Al alloy film contains the above elements, and the balance is Al and inevitable impurities.
- examples of the inevitable impurities include Si and B.
- the total amount of inevitable impurities is not particularly limited, it may be contained in an amount of about 0.5 atomic percent or less, and each inevitable impurity element is 0.012 atomic percent or less for B and 0.12 atomic percent or less for Si. You may contain.
- the second Al alloy film is subjected to a high-temperature heat treatment at 450 to 600 ° C. to form a first precipitate having a predetermined size and a predetermined density as defined in the above (1) to (4) (preferably further the second precipitate).
- Precipitate) and a third precipitate preferably further a fourth precipitate
- the third precipitate only needs to contain at least the X group element and REM
- the fourth precipitate only needs to contain at least the X group element, Ge, and REM. As long as the above is not inhibited, other elements may be contained.
- the circle equivalent diameter (size) of the third and fourth precipitates is 10 nm or more. According to the examination results of the present inventors, precipitates of less than 10 nm have a composition of precipitates of Al-X group element-REM-containing precipitate (third precipitate), Al-Ge-X group element- It was found that the desired effect was not exhibited even with the REM-containing precipitate (fourth precipitate).
- the lower limit of the equivalent circle diameter may be 10 nm, and the upper limit is not particularly limited in relation to the above action, but the size of the precipitate is large. When it becomes a huge precipitate, it may be visually recognized by an inspection with an optical microscope, and an appearance defect is caused. Therefore, the upper limit is preferably 1 ⁇ m.
- a preferable equivalent circle diameter of the third and fourth precipitates is not less than 10 nm and not more than 800 nm.
- the density of the precipitate is preferably as high as possible and is preferably 3,000,000 pieces / mm 2 or more.
- the third Al alloy film includes an Al—Ge—X group containing at least one selected from the group consisting of Ni, Co, and Fe in addition to the Ge, X group element, and rare earth element (REM) described above. This is an element-REM- [Ni, Co, Fe] alloy film.
- Ni, Co, and Fe are elements that enable direct connection (direct contact) with the transparent conductive film. This is because electrical conduction with the transparent conductive film becomes possible through highly conductive [Ni, Co, Fe] -containing Al-based precipitates formed by the thermal history in the TFT manufacturing process. . These may be added alone or both may be added.
- the content of [Ni, Co, Fe] (single content in the case of single, and total amount in the case of containing both) is 0.1. It is preferable to set it to ⁇ 0.35 atomic%. If the content of [Ni, Co, Fe] is less than 0.1 atomic%, the desired effect cannot be obtained, and the density of the fifth precipitate that contributes to reducing the contact resistance with the transparent conductive film cannot be ensured. That is, since the size of the fifth precipitate is small and the density is also reduced, it is difficult to stably maintain a low contact resistance with the transparent conductive film.
- the more preferable content of [Ni, Co, Fe] is 0.1 atomic% or more and 0.25 atomic% or less, and more preferably 0.1 atomic% or more and 0.2 atomic% or less.
- the third Al alloy film only needs to contain Ge, at least one element selected from the X group, and [at least one element selected from the group consisting of Ni, Co, Fe]. Other elements may be contained as long as the action by the elements is not hindered.
- the third Al alloy film contains the above elements, and the balance is Al and inevitable impurities.
- examples of the inevitable impurities include Si and B.
- the total amount of inevitable impurities is not particularly limited, it may be contained in an amount of about 0.5 atomic percent or less, and each inevitable impurity element is 0.012 atomic percent or less for B and 0.12 atomic percent or less for Si. You may contain.
- the third Al alloy film is subjected to high-temperature heat treatment at 450 to 600 ° C. to form a fifth precipitate (Al—Ge—X group element— [Ni, Co, Fe]), and this makes it possible to realize high resistance to a stripping solution at high temperatures and low contact resistance with a transparent conductive film.
- the fifth precipitate only needs to contain at least Ge, an X group element, and [at least one selected from the group consisting of Ni, Co, Fe], and unless the action by the precipitate is inhibited, It may contain other elements.
- the circle equivalent diameter (size) of the fifth precipitate is 250 nm or more. According to the examination results of the present inventors, it has been found that a precipitate having a thickness of less than 250 nm does not exhibit a desired effect even if the composition of the precipitate satisfies the above composition.
- the lower limit of the equivalent circle diameter may be 250 nm, and the upper limit is not particularly limited in relation to the above action, but the size of the precipitate increases and becomes huge. When it becomes a precipitate, it may be visually recognized by inspection with an optical microscope, and it causes an appearance defect. Therefore, the upper limit is preferably 3 ⁇ m.
- a more preferable equivalent circle diameter of the fifth precipitate is 250 nm or more and 2 ⁇ m or less.
- the precipitates having an equivalent circle diameter of 250 nm or more exist at a density of 2,000 / mm 2 or more.
- the density of the precipitate is preferably as high as possible, and is preferably 5,000 / mm 2 or more.
- the “containing” or “including” precipitate containing the predetermined element in the first to fifth precipitates preferably contains the predetermined element, and the remainder is Al and inevitable impurities. Inevitable impurities mean meanings other than a predetermined element of each precipitate.
- the heat treatment for forming the first to fifth precipitates is 450 to 600 ° C., preferably 500 to 600 ° C.
- This heat treatment is preferably performed in a vacuum or nitrogen and / or inert gas atmosphere, and the treatment time is preferably 1 minute or more and 60 minutes or less. According to the present invention, it has been found that hillocks and the like do not occur even when the above heat treatment (high temperature heat treatment) is performed twice or more.
- the TFT manufacturing process corresponding to such high temperature heat treatment includes, for example, annealing by laser for crystallizing amorphous silicon, film formation by CVD (chemical vapor deposition) for various thin film formation, impurity diffusion And the temperature of a heat treatment furnace when the protective film is thermally cured.
- the heat treatment or impurity diffusion for crystallization of amorphous silicon is often exposed to the above-described high temperature.
- the film thickness of the Al alloy film is preferably 50 nm or more, and more preferably 100 nm or more, particularly in order to ensure high temperature heat resistance, etching characteristics and reduction in wiring resistance.
- the upper limit is not particularly limited from the above viewpoint, but it is preferably 2 ⁇ m or less, more preferably 600 nm or less in consideration of the wiring taper shape and the like.
- the Al alloy film is preferably used for various wiring materials such as a source-drain electrode and a gate electrode in a display device.
- the Al alloy film is more preferably used as a wiring material for a gate electrode requiring high temperature heat resistance.
- the Al alloy film is preferably used for various electrode materials such as an emitter electrode and a collector electrode in a semiconductor device, and more preferably used as a wiring material for an emitter electrode that requires high temperature heat resistance.
- the Al alloy film is preferably formed by a sputtering method using a sputtering target (hereinafter also referred to as “target”). This is because a thin film having excellent in-plane uniformity of components and film thickness can be easily formed as compared with a thin film formed by ion plating, electron beam vapor deposition or vacuum vapor deposition.
- the Al alloy sputtering target having the same composition as that of the desired Al alloy film is used as the target, There is no fear, and an Al alloy film having a desired component composition can be formed.
- the present invention also includes a sputtering target having the same composition as that of the first, second, or third Al alloy film described above.
- the target includes (i) 0.01 to 2.0 atomic% of Ge, Ta, Ti, Zr, Hf, W, Cr, Nb, Mo, Ir, Pt, Re, and Os.
- the shape of the target includes a shape processed into an arbitrary shape (a square plate shape, a circular plate shape, a donut plate shape, etc.) according to the shape and structure of the sputtering apparatus.
- a method for producing the above target a method of producing an ingot made of an Al-based alloy by a melt casting method, a powder sintering method, or a spray forming method, or a preform made of an Al-based alloy (the final dense body is prepared)
- Examples thereof include a method obtained by producing an intermediate before being obtained) and then densifying the preform by a densification means.
- the present invention includes a display device characterized in that the Al alloy film is used in a thin film transistor.
- the Al alloy film is used for a source electrode and / or a drain electrode and a signal line of a thin film transistor, and the drain electrode is directly connected to a transparent conductive film, or used for a gate electrode and a scanning line. And the like.
- a refractory metal film or a refractory alloy film (barrier metal) containing at least one element selected from the group consisting of Mo, Ti, W, and Cr is used. Connected to the transparent conductive film.
- the third Al alloy film when used, it may be through the barrier metal or directly connected to the transparent conductive film without using the barrier metal.
- the gate electrode and the scanning line, the source electrode and / or the drain electrode, and the signal line are included in the form of an Al alloy film having the same composition.
- the transparent pixel electrode used in the present invention is not particularly limited, and examples thereof include indium tin oxide (ITO) and indium zinc oxide (IZO).
- the semiconductor layer used in the present invention is not particularly limited, and examples thereof include amorphous silicon, polycrystalline silicon, continuous grain boundary crystalline silicon, and oxide semiconductor materials.
- the liquid crystal display is typically taken up and described as the liquid crystal display device, but the above-described Al alloy film for display device of the present invention described above can be used for various liquid crystal display devices mainly as electrodes and wiring materials.
- LDC liquid crystal display
- OLED organic EL
- the cathode and gate electrodes and the wiring material in the field emission display (FED) illustrated in FIG. 5 for example, the anode electrode and the wiring material in the fluorescent vacuum tube (VFD) illustrated in FIG. 6, for example, the plasma display illustrated in FIG. 7.
- PDP Definitive address electrodes and the wiring material, such as the back electrode and the like in the inorganic EL illustrated in Figure 8, for example.
- the above-described Al alloy film for a semiconductor device of the present invention can be used for various semiconductor devices mainly as electrodes and wiring materials.
- the emitter and collector electrodes and wiring materials in the IGBT illustrated in FIG. Can be mentioned. It has been confirmed by experiments that the above-mentioned predetermined effect can be obtained when the display device of the present invention and the Al alloy film for a semiconductor device are used for these liquid crystal display devices and semiconductor devices.
- an Al alloy wiring obtained by etching the Al alloy film with a gas containing a halogen gas or a halogen-containing compound and an Al alloy wiring obtained by etching with an acidic solution having a pH of 3 or less are also included as aspects of the present invention.
- the etching method and the apparatus used for the etching process are not limited.
- a general dry etching process can be performed using a general-purpose dry etching apparatus as shown in FIG.
- an ICP (inductively coupled plasma) type dry etching apparatus shown in FIG. 10 was used.
- a dielectric window 2 is provided above the chamber 1, and a one-turn antenna 3 is placed on the dielectric window 2.
- the plasma generator shown in FIG. 10 is a so-called TCP (Transfer Coupled Plasma) in which the dielectric window 2 is a flat plate type.
- a high frequency power 4 of 13.56 MHz is introduced into the antenna 3 via a matching unit 5.
- the chamber 1 has a process gas inlet 6 from which an etching gas containing a halogen gas such as Cl 2 is introduced.
- a substrate (material to be etched) 7 is placed on a susceptor 8.
- the susceptor 8 is an electrostatic chuck 9 and can be chucked by an electrostatic force due to electric charge flowing into the substrate from the plasma.
- a member called a quartz glass collar 10 is placed around the susceptor 8.
- the halogen gas introduced into the chamber 1 is converted into plasma in an excited state by a dielectric magnetic field generated by applying high-frequency power to the antenna 3 on the dielectric window 2.
- a 400 kHz high frequency power 12 is introduced to the susceptor 8 through the matching unit 11, and a high frequency bias is applied to the substrate (material to be etched) 7 placed on the susceptor 8.
- a high frequency bias is applied to the substrate (material to be etched) 7 placed on the susceptor 8.
- a substrate material to be etched in an aqueous solution containing an organic acid (1 to 10% by weight) such as phosphoric acid (45 to 80% by weight), nitric acid (1 to 10% by weight) and acetic acid, and the balance being water. Isotropic etching is possible by immersing or spraying an aqueous solution onto the substrate.
- Al alloy targets having various compositions prepared by a vacuum melting method were used as sputtering targets.
- the content of each alloy element in various Al alloy films used in the examples was determined by an ICP emission analysis (inductively coupled plasma emission analysis) method.
- the Al alloy film formed as described above is subjected to high-temperature heat treatment at 450 to 600 ° C. twice, and the Al alloy film after the high-temperature heat treatment is subjected to heat resistance and electrical resistance (arrangement of the Al alloy film itself). Resistance), dry etching characteristics, alkali developer resistance, stripping liquid resistance, and contact resistance with ITO, and the size and density of the precipitates were measured by the methods described below. For reference, an experiment at 350 ° C. was also conducted for heat resistance. In addition, about alkali developing solution tolerance, it experimented using the Al alloy film after film-forming, and heat processing was not performed.
- the reason for exposure to an alkaline environment in the TFT manufacturing process is a photolithography process for forming an Al alloy wiring, which is a stage before receiving a thermal history.
- Ar / Cl 2 300 sccm / 180 sccm
- Substrate bias 60W
- Process pressure gas pressure
- Substrate temperature susceptor temperature (20 ° C)
- Etching was performed by changing the etching time in a range where the etching depth was 100 to 300 nm, and samples having different etching depths were produced.
- the photoresist is stripped off using an amine stripping solution or the like, and then using a stylus type film thickness meter (“Dektak II” manufactured by Vecco), pure Al or The etching thickness of the Al alloy film was measured.
- the dry etching characteristics were evaluated according to the criteria shown in Table 7, and in this example, ⁇ or ⁇ was accepted.
- the direct contact resistance with ITO was evaluated according to the judgment criteria shown in Table 7. In this example, ⁇ or ⁇ was regarded as acceptable.
- Substrate temperature 25 ° C (room temperature)
- the number of crater-like corrosion (pitting corrosion) marks (those with an equivalent circle diameter of 150 nm or more) found on the film surface after immersion was examined (observation magnification was 1000 times).
- the stripping solution resistance was evaluated according to the criteria shown in Table 7. In this example, ⁇ or ⁇ was regarded as acceptable.
- Alkali developer resistance (developer etch rate measurement) After masking the Al alloy film formed on the substrate, it was immersed in a developer (aqueous solution containing 2.38% by mass of TMAH) at 25 ° C. for 1 minute and 2 minutes. The etching rate was calculated from the difference in etching amount when immersed for 1 minute and 2 minutes. Alkali developer resistance was evaluated according to the criteria described in Table 7, and in this example, ⁇ or ⁇ was regarded as acceptable.
- Each of the Al alloy films described in 1-1 to 1-32 corresponds to the third Al alloy film according to the present invention, satisfies the alloy composition defined in the present invention, and includes the first to fifth
- it is excellent not only in heat resistance at low temperature (350 ° C.) but also in high temperature heat resistance at 450 to 600 ° C.
- the dry etching characteristics are good.
- the electrical resistance after the high-temperature heat treatment has a lower electrical resistance than that of the refractory metal, and the resistance to the alkali developer before the high-temperature heat treatment and the stripping solution after the high-temperature heat treatment is also good.
- the direct contact resistance with the transparent pixel electrode) could also be greatly reduced.
- Each of the Al alloy films described in 2-1 to 2-24 corresponds to the third Al alloy film according to the present invention, satisfies the alloy composition defined in the present invention, and includes the first, third, and third alloy films. Since the requirements (size and density) of the fifth precipitate are also satisfied, it is excellent not only in heat resistance at low temperature (350 ° C.) but also in high temperature heat resistance at 450-600 ° C. Also, the dry etching characteristics are good. Furthermore, the electrical resistance after the high-temperature heat treatment has a lower electrical resistance than that of the refractory metal, and the resistance to the alkali developer before the high-temperature heat treatment and the stripping solution after the high-temperature heat treatment is also good. The direct contact resistance with the transparent pixel electrode) could also be greatly reduced.
- Each of the Al alloy films described in 3-1 to 3-30 corresponds to the second Al alloy film according to the present invention, satisfies the alloy composition defined in the present invention, and has the first to fourth
- it is excellent not only in heat resistance at low temperature (350 ° C.) but also in high temperature heat resistance at 450 to 600 ° C.
- the dry etching characteristics are good.
- the electrical resistance after the high temperature heat treatment has an electrical resistance lower than that of the refractory metal, and the resistance to the alkali developer and the stripping solution is also good.
- direct contact resistance with ITO transparent pixel electrode
- ITO transparent pixel electrode
- Each of the Al alloy films described in 4-1 to 4-24 corresponds to the second Al alloy film according to the present invention, satisfies the alloy composition defined in the present invention, and has the first, third, and third alloy films.
- the requirements (size and density) of the fourth precipitate are also satisfied, it is excellent not only in heat resistance at low temperature (350 ° C.) but also in high temperature heat resistance at 450 to 600 ° C. Also, the dry etching characteristics are good.
- the electrical resistance after the high temperature heat treatment has an electrical resistance lower than that of the refractory metal, and the resistance to the alkali developer and the stripping solution is also good.
- the direct contact resistance with ITO transparent pixel electrode
- the contact resistance with ITO became high because none of Ni, Co, and Fe was contained.
- Each of the Al alloy films described in 5-1 to 5-3 corresponds to the first Al alloy film according to the present invention, satisfies the alloy composition defined in the present invention, and is a first precipitate. Therefore, not only is the heat resistance at low temperature (350 ° C.) excellent, but also the heat resistance at 450 to 600 ° C. is excellent. Also, the dry etching characteristics are good. Furthermore, the electrical resistance after the high temperature heat treatment has an electrical resistance lower than that of the refractory metal, and the resistance to the alkali developer and the stripping solution is also good. Regarding the direct contact resistance with ITO (transparent pixel electrode), the contact resistance with ITO became high because none of Ni, Co, and Fe was contained.
- Each of the Al alloy films described in 5-4 to 5-5 corresponds to the first Al alloy film according to the present invention, satisfies the alloy composition defined in the present invention, and has the first and second In addition to satisfying the requirements (size and density) of this precipitate, it is excellent not only in heat resistance at low temperature (350 ° C.) but also in high temperature heat resistance at 450 to 600 ° C. Also, the dry etching characteristics are good. Furthermore, the electrical resistance after the high temperature heat treatment has an electrical resistance lower than that of the refractory metal, and the resistance to the alkali developer and the stripping solution is also good. Regarding the direct contact resistance with ITO (transparent pixel electrode), the contact resistance with ITO became high because none of Ni, Co, and Fe was contained.
- each of the Al alloy films described in 6-1 to 6-7 is an example that does not satisfy the requirements of the first to third Al alloy films defined in the present invention.
- No. Examples 6-1 to 6-3 are examples that do not satisfy the alloy composition and the precipitate requirement.
- the wiring resistance shows a relatively good value because the heat resistance of the wiring is poor and the surface is rough.
- the first Al alloy film (Al—Ge—X group element) includes a predetermined alloy element and a first precipitate (preferably a first precipitate and a second precipitate). Therefore, it is excellent in heat resistance when exposed to high temperatures of about 450 to 600 ° C., and the electric resistance (wiring resistance) of the film itself after high temperature processing can be kept low, and corrosion resistance, etching Combines processability and resistance to stripping solution.
- the second Al alloy film (Al—Ge—X group element-rare earth element) according to the present invention, which is a preferred embodiment, includes a predetermined alloy element and a first precipitate (preferably a first precipitate and a second precipitate). ) And the third precipitate (preferably the third precipitate and the fourth precipitate), it exhibits higher heat resistance and also better resistance to alkali corrosion.
- a third Al alloy film (Al—Ge—X group element— [Ni, Co, Fe] alloy according to the present invention, which is a more preferred embodiment, preferably Al—Ge—X group element—rare earth element— [Ni, Co, Fe] alloy) is a predetermined alloy element and a first precipitate (preferably a first precipitate and a second precipitate, more preferably a first precipitate, a second precipitate and a third precipitate). And, more preferably, the first precipitate, the second precipitate, the third precipitate and the fourth precipitate), and the fifth precipitate. Since low contact resistance with a transparent conductive film can also be achieved, direct connection with a transparent conductive film is possible.
- the high-temperature heat treatment at about 450 to 600 ° C., and the high-temperature heat treatment is performed at least twice. Even when exposed to harsh high-temperature environments, the carrier mobility of the semiconductor silicon layer is increased, improving the TFT response speed and providing high-performance display devices that can handle energy savings and high-speed video. it can. In wiring processing, both a wet etching method and a dry etching method can be applied.
- the Al alloy film is excellent in heat resistance (particularly high temperature heat resistance), for example, in the manufacturing process of an IGBT provided with this as an electrode / electric wiring of a semiconductor element, the ion activity of the collector layer Heat treatment for crystallization can be performed at a high temperature. As a result, it is possible to realize a semiconductor element having the Al alloy film and improved characteristics, and the semiconductor device having the semiconductor element and exhibiting excellent characteristics. In wiring processing, both a wet etching method and a dry etching method can be applied.
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Abstract
Description
[1] 表示装置もしくは半導体装置に用いられるAl合金膜であって、前記Al合金膜は、Geを0.01~2.0原子%と、Ta、Ti、Zr、Hf、W、Cr、Nb、Mo、Ir、Pt、Re、およびOsよりなる群(X群)から選択される少なくとも一種の元素とを含み、
前記Al合金膜に450~600℃の加熱処理を行なったとき、下記(1)の要件を満足することを特徴とする表示装置もしくは半導体装置用Al合金膜。
上記第1のAl合金膜は、Geに加え、Ta、Ti、Zr、Hf、W、Cr、Nb、Mo、Ir、Pt、ReおよびOsよりなる群(X群)から選択される少なくとも一種の元素とを含有するAl-Ge-X群元素合金膜である。
上記第2のAl合金膜は、上述したGeおよびX群元素に加えて、希土類元素(REM)を含有するAl-Ge-X群元素-REM合金膜である。
上記第3のAl合金膜は、上述したGe、X群元素および希土類元素(REM)の他、更にNi、Co、およびFeよりなる群から選択される少なくとも一種を含有するAl-Ge-X群元素-REM-[Ni、Co、Fe]合金膜である。
表1~6に示す種々の合金組成のAl合金膜(膜厚=300nm)を、DCマグネトロン・スパッタ法(基板=ガラス基板(コーニング社製 Eagle2000)、雰囲気ガス=アルゴン、圧力=2mTorr、基板温度=25℃(室温))によって成膜した。
成膜後のAl合金膜に対し、不活性雰囲気ガス(N2)雰囲気下にて、表1~6に示す各温度にて10分間の加熱処理を2回行ない、その表面性状を光学顕微鏡(倍率:500倍)を用いて観察し、ヒロックの密度(個/m2)を測定した。表7に記載の判断基準により耐熱性を評価し、本実施例では◎または○を合格とした。
具体的には、直径4インチ、厚さ0.7mmのシリコン基板上に、厚さ200nmの酸化シリコン(SiOx)膜を成膜した後、Al合金膜を前述した条件で500nmの厚さに成膜した。次いで、g線のフォトリソグラフィーによってポジ型フォトレジスト(ノボラック系樹脂;東京応化工業(株)製のTSMR8900、厚さは1.0μm)を線幅10μmのストライプ状に形成した。次に、前述した図10に示すドライエッチング装置を用い、下記のエッチング条件でドライエッチングを行なった。
Ar/Cl2:300sccm/180sccm
アンテナに印加した電力(ソースRF):500W
基板バイアス:60W
プロセス圧力(ガス圧):14mTorr
基板温度:サセプタの温度(20℃)
成膜後のAl合金膜に10μm幅のラインアンドスペースパターンを形成したものに、不活性雰囲気ガス(N2)雰囲気下にて、450℃、550℃または600℃の各温度にて10分間の加熱処理を2回行ない、4端子法で電気抵抗率を測定した。表7に記載の判断基準により各温度の配線抵抗を評価し、本実施例では◎または○を合格とした。
成膜後のAl合金膜に対し、不活性雰囲気ガス(N2)雰囲気下にて、600℃で10分間の加熱処理を2回行なったものを用意した。このAl合金膜と透明画素電極を直接接触したときの接触抵抗は、透明画素電極(ITO;酸化インジウムに10質量%の酸化スズを加えた酸化インジウムスズ)を、下記条件でスパッタリングすることによって図2に示すケルビンパターン(コンタクトホールサイズ:10μm角)を作製し、4端子測定(ITO-Al合金膜に電流を流し、別の端子でITO-Al合金間の電圧降下を測定する方法)を行なった。具体的には、図2のI1-I2間に電流Iを流し、V1-V2間の電圧Vをモニターすることにより、コンタクト部Cのダイレクト接触抵抗Rを[R=(V2-V1)/I2]として求めた。表7に記載の判断基準によりITOとのダイレクト接触抵抗(ITOとのコンタクト抵抗)を評価し、本実施例では◎または○を合格とした。
雰囲気ガス=アルゴン
圧力=0.8mTorr
基板温度=25℃(室温)
フォトレジスト剥離液の洗浄工程を模擬し、アミン系フォトレジストと水を混合したアルカリ性水溶液による腐食実験を行った。詳細には、成膜後のAl合金膜に対し、不活性ガス雰囲気(N2)中、600℃で20分間の加熱処理を2回行った後、東京応化工業(株)製のアミン系レジスト剥離液「TOK106」水溶液をpH10.5および9.5の各pHに調整したもの(液温25℃)に浸漬させた。具体的には、まず、pH10.5の溶液に1分間浸漬後、連続してpH9.5の溶液に5分間浸漬させた。そして、浸漬後の膜表面にみられるクレータ状の腐食(孔食)痕(円相当直径が150nm以上のもの)の個数を調べた(観察倍率は1000倍)。表7に記載の判断基準により剥離液耐性を評価し、本実施例では◎または○を合格とした。
基板上に成膜したAl合金膜にマスクを施した後、現像液(TMAH2.38質量%を含む水溶液)中に25℃で1分間および2分間浸漬し、そのエッチング量を触診式段差計を用いて測定し、1分間および2分間浸漬した際のエッチング量の差からエッチングレートを算出した。表7に記載の判断基準によりアルカリ現像液耐性を評価し、本実施例では◎または○を合格とした。
成膜後のAl合金膜に対し、不活性ガス雰囲気(N2)中、550℃または600℃で10分間の加熱処理を2回行い、析出した析出物を、平面TEM(透過電子顕微鏡、倍率30万倍)で観察した。析出物のサイズ(円相当直径)および密度(個/mm2)は、走査電子顕微鏡の反射電子像を用いて求めた。具体的には、1視野(mm2)内に観察される析出物の円相当直径および個数を測定し、3視野の平均値を求めた。析出物に含まれる元素はTEM-EDX分析により判断した。そして表7に記載の判断基準により各析出物のサイズおよび密度を分類した。析出物について、サイズが◎、○、または△であり、且つ、密度が◎または○を満足するものが、本発明の要件を満足するものである。
なお、下記表1~6中、析出物サイズ及び析出物密度の結果において、左側から順に、それぞれ、第1の析出物、第2の析出物、第3の析出物、第4の析出物、第5の析出物の結果を表している。
本出願は、2011年2月28日出願の日本特許出願(特願2011-042635)に基づくものであり、その内容はここに参照として取り込まれる。
2 誘電窓
3 アンテナ
4 高周波電力(アンテナ側)
5 整合器(アンテナ側)
6 プロセスガス導入口
7 基板(被エッチング材)
8 サセプタ
9 誘電チャック
10 カラー
11 整合器(基板側)
12 高周波電力(基板側)
21a ガラス基板
25 走査線
26 ゲート電極
27 ゲート絶縁膜
28 ソース電極
29 ドレイン電極
30 半導体シリコン層
31 保護膜
32 低抵抗シリコン層
33 絶縁性保護膜
35 透明電極
Claims (34)
- 表示装置もしくは半導体装置に用いられるAl合金膜であって、前記Al合金膜は、Geを0.01~2.0原子%と、Ta、Ti、Zr、Hf、W、Cr、Nb、Mo、Ir、Pt、Re、およびOsよりなる群(X群)から選択される少なくとも一種の元素とを含み、
前記Al合金膜に450~600℃の加熱処理を行なったとき、下記(1)の要件を満足することを特徴とする表示装置もしくは半導体装置用Al合金膜。
(1)Alと、前記X群から選択される少なくとも一種の元素と、Geとを含む第1の析出物について、円相当直径50nm以上の析出物が200,000個/mm2以上の密度で存在する。 - 前記Al合金膜は、450~600℃の加熱処理を行なったとき、更に下記(2)の要件を満足するものである請求項1に記載の表示装置もしくは半導体装置用Al合金膜。
(2)Alと、前記X群から選択される少なくとも二種の元素を含む第2の析出物について、円相当直径50nm以上の析出物が100,000個/mm2以上の密度で存在する。 - 前記Al合金膜は、更に、希土類元素からなる群から選ばれる少なくとも一種とを含み、前記Al合金膜に450~600℃の加熱処理を行なったとき、更に下記(3)の要件を満足するものである請求項1に記載の表示装置もしくは半導体装置用Al合金膜。
(3)Alと、前記X群から選択される少なくとも一種の元素と、前記希土類元素の少なくとも一種とを含む第3の析出物について、円相当直径10nm以上の析出物が1,000,000個/mm2以上の密度で存在する。 - 前記Al合金膜は、450~600℃の加熱処理を行なったとき、更に下記(4)の要件を満足するものである請求項3記載の表示装置もしくは半導体装置用Al合金膜。
(4)Alと、Geと前記X群から選択される少なくとも一種の元素と、前記希土類元素の少なくとも一種とを含む第4の析出物について、円相当直径10nm以上の析出物が1,000,000個/mm2以上の密度で存在する。 - 前記Al合金膜は、更にNi、Co、Feからなる群から選ばれる少なくとも1種の元素とを含み、前記Al合金膜に450~600℃の加熱処理を行なったとき、更に下記(5)の要件を満足するものである請求項1に記載の表示装置もしくは半導体装置用Al合金膜。
(5)Alと、Ni、Co、Feからなる群から選ばれる少なくとも一種の元素と、Geと、前記X群から選択される少なくとも一種の元素とを含む第5の析出物について、円相当直径250nm以上の析出物が2,000個/mm2以上の密度で存在する。 - 前記第1の析出物の円相当直径は、1μm以下である請求項1に記載の表示装置もしくは半導体装置用Al合金膜。
- 前記第2の析出物の円相当直径は、1μm以下である請求項2に記載の表示装置もしくは半導体装置用Al合金膜。
- 前記第3の析出物の円相当直径は、1μm以下である請求項3に記載の表示装置もしくは半導体装置用Al合金膜。
- 前記第4の析出物の円相当直径は、1μm以下である請求項4に記載の表示装置もしくは半導体装置用Al合金膜。
- 前記第5の析出物の円相当直径は、3μm以下である請求項5に記載の表示装置もしくは半導体装置用Al合金膜。
- 前記X群の元素の含有量は0.1~5原子%である請求項1に記載の表示装置もしくは半導体装置用Al合金膜。
- 前記希土類元素の含有量は0.1~0.45原子%である請求項3に記載の表示装置もしくは半導体装置用Al合金膜。
- 前記Ni、Co、Feから選ばれる少なくとも1種の元素の含有量は0.1~0.35原子%である請求項5に記載の表示装置もしくは半導体装置用Al合金膜。
- 前記加熱処理は、500~600℃である請求項1に記載の表示装置もしくは半導体装置用Al合金膜。
- 前記加熱処理は、少なくとも2回実施されるものである請求項1に記載の表示装置もしくは半導体装置用Al合金膜。
- 前記Al合金膜は、透明導電膜と直接接続されるものである請求項5に記載の表示装置もしくは半導体装置用Al合金膜。
- 前記Al合金膜は、Mo、Ti、W、およびCrよりなる群から選択される少なくとも一種の元素を含む膜を介して透明導電膜と接続されるものである請求項1に記載の表示装置もしくは半導体装置用Al合金膜。
- Geを0.01~2.0原子%と、Ta、Ti、Zr、Hf、W、Cr、Nb、Mo、Ir、Pt、Re、Osよりなる群(X群)から選択される少なくとも一種の元素を0.1~5原子%を含むことを特徴とするスパッタリングターゲット。
- 更に希土類元素からなる群から選ばれる少なくとも一種を0.1~0.45原子%含むものである請求項18に記載のスパッタリングターゲット。
- 更にNi、Co、Feから選ばれる少なくとも一種の元素を0.1~0.35原子%含むものである請求項18に記載のスパッタリングターゲット。
- 残部がAlおよび不可避的不純物である請求項18に記載のスパッタリングターゲット。
- 請求項1に記載の表示装置もしくは半導体装置用Al合金膜を、ハロゲンガス、または、ハロゲン含有化合物を含むガスでエッチングしたことを特徴とする、Al合金配線。
- 請求項1に記載の表示装置もしくは半導体装置用Al合金膜を、pH3以下の酸性溶液でエッチングしたことを特徴とする、Al合金配線。
- 請求項1に記載の表示装置用Al合金膜を備えた表示装置。
- 請求項1に記載の表示装置用Al合金膜を備えた液晶ディスプレイ。
- 請求項1に記載の表示装置用Al合金膜を備えた有機ELディスプレイ。
- 請求項1に記載の表示装置用Al合金膜を備えたフィールドエミッションディスプレイ。
- 請求項1に記載の表示装置用Al合金膜を備えた蛍光真空管。
- 請求項1に記載の表示装置用Al合金膜を備えたプラズマディスプレイ。
- 請求項1に記載の表示装置用Al合金膜を備えた無機ELディスプレイ。
- 請求項1に記載の半導体装置用Al合金膜を備えた半導体装置。
- 請求項1に記載の半導体装置用Al合金膜を備えた半導体素子。
- 請求項1に記載の半導体装置用Al合金膜を備えた半導体素子の電極。
- 請求項1に記載の半導体装置用Al合金膜を備えた半導体素子の配線。
Priority Applications (3)
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US14/001,875 US9624562B2 (en) | 2011-02-28 | 2012-02-27 | Al alloy film for display or semiconductor device, display or semiconductor device having Al alloy film, and sputtering target |
CN201280010495.5A CN103403214B (zh) | 2011-02-28 | 2012-02-27 | 显示装置或半导体装置用Al合金膜、具备Al合金膜的显示装置或半导体装置、以及溅射靶 |
KR1020137022620A KR20130121959A (ko) | 2011-02-28 | 2012-02-27 | 표시 장치 또는 반도체 장치용 Al 합금막, Al 합금막을 구비한 표시 장치 또는 반도체 장치 및 스퍼터링 타깃 |
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JP2011042635A JP2012180540A (ja) | 2011-02-28 | 2011-02-28 | 表示装置および半導体装置用Al合金膜 |
JP2011-042635 | 2011-02-28 |
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US (1) | US9624562B2 (ja) |
JP (1) | JP2012180540A (ja) |
KR (1) | KR20130121959A (ja) |
CN (1) | CN103403214B (ja) |
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WO2022201461A1 (ja) * | 2021-03-25 | 2022-09-29 | シャープディスプレイテクノロジー株式会社 | 表示装置及びその製造方法 |
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US11935936B2 (en) | 2018-06-28 | 2024-03-19 | Ulvac, Inc. | Aluminum alloy film, method of producing the same, and thin film transistor |
WO2020003666A1 (ja) * | 2018-06-28 | 2020-01-02 | 株式会社アルバック | アルミニウム合金ターゲット及びその製造方法 |
KR102677079B1 (ko) * | 2019-12-13 | 2024-06-21 | 가부시키가이샤 아루박 | 알루미늄 합금 타겟, 알루미늄 합금 배선막, 및 알루미늄 합금 배선막의 제조 방법 |
KR102329426B1 (ko) * | 2020-01-03 | 2021-11-24 | 와이엠씨 주식회사 | 배선전극용 합금 조성물 및 그의 제조방법 |
CN111584501B (zh) * | 2020-05-07 | 2021-12-28 | 武汉华星光电技术有限公司 | 接触电阻监测器件及其制作方法、显示面板 |
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