WO2013015322A1 - 銅/モリブデン系多層薄膜用エッチング液 - Google Patents
銅/モリブデン系多層薄膜用エッチング液 Download PDFInfo
- Publication number
- WO2013015322A1 WO2013015322A1 PCT/JP2012/068853 JP2012068853W WO2013015322A1 WO 2013015322 A1 WO2013015322 A1 WO 2013015322A1 JP 2012068853 W JP2012068853 W JP 2012068853W WO 2013015322 A1 WO2013015322 A1 WO 2013015322A1
- Authority
- WO
- WIPO (PCT)
- Prior art keywords
- copper
- acid
- etching
- etching solution
- semiconductor layer
- Prior art date
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- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 title claims abstract description 90
- 239000010949 copper Substances 0.000 title claims abstract description 89
- 229910052802 copper Inorganic materials 0.000 title claims abstract description 84
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 title claims abstract description 78
- 229910052750 molybdenum Inorganic materials 0.000 title claims abstract description 78
- 239000011733 molybdenum Substances 0.000 title claims abstract description 78
- 239000010409 thin film Substances 0.000 title claims abstract description 52
- 238000005530 etching Methods 0.000 claims abstract description 192
- 239000004065 semiconductor Substances 0.000 claims abstract description 85
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 claims abstract description 75
- 238000000034 method Methods 0.000 claims abstract description 30
- 150000007524 organic acids Chemical class 0.000 claims abstract description 20
- -1 amine compound Chemical class 0.000 claims abstract description 17
- 239000003381 stabilizer Substances 0.000 claims abstract description 17
- 125000003277 amino group Chemical group 0.000 claims abstract description 16
- 150000007522 mineralic acids Chemical class 0.000 claims abstract description 14
- 125000001153 fluoro group Chemical group F* 0.000 claims abstract description 11
- KAESVJOAVNADME-UHFFFAOYSA-N Pyrrole Chemical compound C=1C=CNC=1 KAESVJOAVNADME-UHFFFAOYSA-N 0.000 claims abstract description 10
- 229910052731 fluorine Inorganic materials 0.000 claims abstract description 10
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims abstract description 8
- 125000004432 carbon atom Chemical group C* 0.000 claims description 13
- JPVYNHNXODAKFH-UHFFFAOYSA-N Cu2+ Chemical compound [Cu+2] JPVYNHNXODAKFH-UHFFFAOYSA-N 0.000 claims description 12
- OFOBLEOULBTSOW-UHFFFAOYSA-N Malonic acid Chemical compound OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 claims description 12
- 229910001431 copper ion Inorganic materials 0.000 claims description 12
- 239000011701 zinc Substances 0.000 claims description 11
- LUBJCRLGQSPQNN-UHFFFAOYSA-N 1-Phenylurea Chemical group NC(=O)NC1=CC=CC=C1 LUBJCRLGQSPQNN-UHFFFAOYSA-N 0.000 claims description 10
- GYHNNYVSQQEPJS-UHFFFAOYSA-N Gallium Chemical compound [Ga] GYHNNYVSQQEPJS-UHFFFAOYSA-N 0.000 claims description 10
- AEMRFAOFKBGASW-UHFFFAOYSA-N Glycolic acid Chemical compound OCC(O)=O AEMRFAOFKBGASW-UHFFFAOYSA-N 0.000 claims description 10
- 229910052733 gallium Inorganic materials 0.000 claims description 10
- 229910052738 indium Inorganic materials 0.000 claims description 10
- APFVFJFRJDLVQX-UHFFFAOYSA-N indium atom Chemical compound [In] APFVFJFRJDLVQX-UHFFFAOYSA-N 0.000 claims description 10
- JVTAAEKCZFNVCJ-UHFFFAOYSA-N lactic acid Chemical compound CC(O)C(O)=O JVTAAEKCZFNVCJ-UHFFFAOYSA-N 0.000 claims description 10
- 150000003851 azoles Chemical class 0.000 claims description 9
- 238000004519 manufacturing process Methods 0.000 claims description 9
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- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 claims description 8
- 229910052725 zinc Inorganic materials 0.000 claims description 8
- BJEPYKJPYRNKOW-REOHCLBHSA-N (S)-malic acid Chemical compound OC(=O)[C@@H](O)CC(O)=O BJEPYKJPYRNKOW-REOHCLBHSA-N 0.000 claims description 7
- ULRPISSMEBPJLN-UHFFFAOYSA-N 2h-tetrazol-5-amine Chemical group NC1=NN=NN1 ULRPISSMEBPJLN-UHFFFAOYSA-N 0.000 claims description 5
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- BJEPYKJPYRNKOW-UHFFFAOYSA-N alpha-hydroxysuccinic acid Natural products OC(=O)C(O)CC(O)=O BJEPYKJPYRNKOW-UHFFFAOYSA-N 0.000 claims description 5
- KDYFGRWQOYBRFD-NUQCWPJISA-N butanedioic acid Chemical compound O[14C](=O)CC[14C](O)=O KDYFGRWQOYBRFD-NUQCWPJISA-N 0.000 claims description 5
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- 239000002253 acid Substances 0.000 claims description 4
- 229910017604 nitric acid Inorganic materials 0.000 claims description 4
- QOHMWDJIBGVPIF-UHFFFAOYSA-N n',n'-diethylpropane-1,3-diamine Chemical compound CCN(CC)CCCN QOHMWDJIBGVPIF-UHFFFAOYSA-N 0.000 claims description 3
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- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 6
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- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical class O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 5
- DHMQDGOQFOQNFH-UHFFFAOYSA-N Glycine Chemical compound NCC(O)=O DHMQDGOQFOQNFH-UHFFFAOYSA-N 0.000 description 4
- 230000001133 acceleration Effects 0.000 description 4
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- 238000011282 treatment Methods 0.000 description 4
- XFNJVJPLKCPIBV-UHFFFAOYSA-N trimethylenediamine Chemical compound NCCCN XFNJVJPLKCPIBV-UHFFFAOYSA-N 0.000 description 4
- RAXXELZNTBOGNW-UHFFFAOYSA-N 1H-imidazole Chemical compound C1=CNC=N1 RAXXELZNTBOGNW-UHFFFAOYSA-N 0.000 description 3
- KJUGUADJHNHALS-UHFFFAOYSA-N 1H-tetrazole Chemical compound C=1N=NNN=1 KJUGUADJHNHALS-UHFFFAOYSA-N 0.000 description 3
- 229910000881 Cu alloy Inorganic materials 0.000 description 3
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- 239000000654 additive Substances 0.000 description 3
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 3
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- 230000001590 oxidative effect Effects 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- JBQYATWDVHIOAR-UHFFFAOYSA-N tellanylidenegermanium Chemical compound [Te]=[Ge] JBQYATWDVHIOAR-UHFFFAOYSA-N 0.000 description 3
- VZCYOOQTPOCHFL-UHFFFAOYSA-N trans-butenedioic acid Natural products OC(=O)C=CC(O)=O VZCYOOQTPOCHFL-UHFFFAOYSA-N 0.000 description 3
- RTBFRGCFXZNCOE-UHFFFAOYSA-N 1-methylsulfonylpiperidin-4-one Chemical compound CS(=O)(=O)N1CCC(=O)CC1 RTBFRGCFXZNCOE-UHFFFAOYSA-N 0.000 description 2
- GIAFURWZWWWBQT-UHFFFAOYSA-N 2-(2-aminoethoxy)ethanol Chemical compound NCCOCCO GIAFURWZWWWBQT-UHFFFAOYSA-N 0.000 description 2
- LSBDFXRDZJMBSC-UHFFFAOYSA-N 2-phenylacetamide Chemical compound NC(=O)CC1=CC=CC=C1 LSBDFXRDZJMBSC-UHFFFAOYSA-N 0.000 description 2
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- 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
- H01L21/321—After treatment
- H01L21/3213—Physical or chemical etching of the layers, e.g. to produce a patterned layer from a pre-deposited extensive layer
- H01L21/32133—Physical or chemical etching of the layers, e.g. to produce a patterned layer from a pre-deposited extensive layer by chemical means only
- H01L21/32134—Physical or chemical etching of the layers, e.g. to produce a patterned layer from a pre-deposited extensive layer by chemical means only by liquid etching only
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- H01L21/04—Manufacture or treatment of semiconductor devices or of parts thereof the devices having at least one potential-jump barrier or surface barrier, e.g. PN junction, depletion layer or carrier concentration layer
- H01L21/34—Manufacture or treatment of semiconductor devices or of parts thereof the devices having at least one potential-jump barrier or surface barrier, e.g. PN junction, depletion layer or carrier concentration layer the devices having semiconductor bodies not provided for in groups H01L21/0405, H01L21/0445, H01L21/06, H01L21/16 and H01L21/18 with or without impurities, e.g. doping materials
- H01L21/46—Treatment of semiconductor bodies using processes or apparatus not provided for in groups H01L21/428
- H01L21/461—Treatment of semiconductor bodies using processes or apparatus not provided for in groups H01L21/428 to change their surface-physical characteristics or shape, e.g. etching, polishing, cutting
- H01L21/465—Chemical or electrical treatment, e.g. electrolytic etching
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- H01L29/40—Electrodes ; Multistep manufacturing processes therefor
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- H01L29/66—Types of semiconductor device ; Multistep manufacturing processes therefor
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- H01L29/66409—Unipolar field-effect transistors
- H01L29/66477—Unipolar field-effect transistors with an insulated gate, i.e. MISFET
- H01L29/66742—Thin film unipolar transistors
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- 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
- H01L29/7869—Thin film transistors, i.e. transistors with a channel being at least partly a thin film having a semiconductor body comprising an oxide semiconductor material, e.g. zinc oxide, copper aluminium oxide, cadmium stannate
Definitions
- the present invention relates to an etching solution for a copper / molybdenum multilayer thin film.
- an oxide semiconductor composed of indium (In), gallium (Ga), and zinc (Zn); a zinc oxide (ZnO) -based oxide semiconductor; or a zinc (Zn) tin (Sn) composite oxide
- IGZO oxide semiconductor
- ZnO zinc oxide
- Sn zinc oxide
- Patent Documents 1-3 Patent Documents 1-3
- the oxide semiconductor material generally tends to be dissolved in either an acidic or alkaline etching solution for etching a metal that is a wiring material.
- IGZO is easily etched by an acid solution or the like. Therefore, when an etching solution for patterning the wiring material is contacted The IGZO semiconductor layer is damaged and changes in electrical characteristics occur. Therefore, as shown in FIG. 2, an etching stopper layer 10 is provided to protect the channel region between the source electrode 6a and the drain electrode 6b on the IGZO semiconductor layer 9, and the IGZO semiconductor layer 9 is effectively damaged. To prevent.
- etch stopper type TFT structure increases the number of manufacturing processes for forming the etch stopper layer, and the width of the channel region is limited, which greatly limits the degree of freedom in designing the TFT element.
- a channel etch type TFT structure as shown in FIG. 3 is desirable.
- the resistance value of aluminum and the aluminum alloy itself, which are wiring materials is high, there is a concern that the characteristics of an oxide semiconductor such as IGZO cannot be fully utilized.
- Such a laminated film containing copper or a copper alloy containing copper as a main component is formed on a substrate such as glass by a film forming process such as sputtering, and then is subjected to an etching process in which etching is performed using a resist or the like as a mask. It becomes an electrode pattern.
- etching processes wet (wet) using an etching solution and dry (dry) using an etching gas such as plasma.
- the performance required for the etching solution used in wet is (ii) less damage to the oxide semiconductor layer, (ii) high processing accuracy, (iii) less etching residue, In addition to iv) less uneven etching, (v) stable etching performance against the dissolution of metal of the wiring material containing copper to be etched (the effect of extending the bus life), etc.
- it is required to (vi) obtain a good wiring cross-sectional shape after etching within a predetermined range. More specifically, a forward taper shape in which the angle (taper angle) between the etching surface of the copper wiring end portion and the lower substrate shown in FIG. 4 is 30 to 60 ° is provided under the wiring from the resist end portion.
- the distance (CD loss) to the wiring end in contact with the barrier film is required to be 1.2 ⁇ m or less, preferably 1 ⁇ m or less.
- Etching solution used in the etching process of the laminated film containing copper or a copper alloy containing copper as a main component includes, for example, at least one selected from a neutral salt, an inorganic acid, and an organic acid, hydrogen peroxide, and peroxide.
- Etching solution containing hydrogen stabilizer for example, Patent Document 4
- etching solution containing a predetermined amount of hydrogen peroxide, organic acid, phosphate, two types of nitrogen-containing additives, fluorinated compound and water for example, patents) Document 5 has been proposed.
- an etching solution composition for example, Patent Document 6 that selectively etches a metal film made of Al, Al alloy or the like from a laminated film including an amorphous oxide film and a metal film made of Al, Al alloy or the like. Proposed.
- the cross-sectional shape of the wiring after etching is not sufficiently satisfied, and as a result, there are cases where it is not possible to sufficiently cope with the increase in size and resolution of the display.
- the etching solution disclosed in Patent Document 5 contains a fluorinated compound, and damage to the oxide semiconductor layer such as IGZO is large, and it is not satisfactory from the viewpoint of environmental measures. It was.
- the present invention has been made under such circumstances, and relates to an etching solution for a copper / molybdenum multilayer thin film in which damage to an oxide semiconductor layer such as IGZO is reduced, and an oxide semiconductor layer using the same.
- An object of the present invention is to provide a selective etching method for a copper / molybdenum multilayer thin film.
- the present inventors have found that (A) hydrogen peroxide, (B) an inorganic acid not containing a fluorine atom, (C) an organic acid, (D It has been found that the object can be achieved by blending a specific combination of (a) amine compound, (E) azoles, and (F) hydrogen peroxide stabilizer, and setting the pH within the range of 2.5 to 5. It was. The present invention has been completed based on such findings. That is, the gist of the present invention is as follows.
- An etching solution capable of selectively etching a copper / molybdenum multilayer thin film in a semiconductor device including an oxide semiconductor layer and a copper / molybdenum multilayer thin film, wherein (A) hydrogen peroxide, (B) fluorine atoms (C) an organic acid, (D) an amine compound having 2 to 10 carbon atoms and having an amino group and at least one group selected from an amino group and a hydroxyl group, (E) azoles And (F) an etching solution comprising a hydrogen peroxide stabilizer and having a pH of 2.5 to 5. [2] The etching solution according to item 1, wherein (B) the inorganic acid is sulfuric acid and / or nitric acid.
- An etching solution capable of selectively etching a copper / molybdenum multilayer thin film in a semiconductor device including an oxide semiconductor layer and a copper / molybdenum multilayer thin film, wherein (A) 3 to 10% by mass of hydrogen peroxide (B) 0.01 to 5% by mass of an inorganic acid not containing a fluorine atom, (C) 1 to 15% by mass of an organic acid, (D) 2 to 10 carbon atoms, and an amino group and an amino group And 1 to 10% by mass of an amine compound having at least one group selected from hydroxyl groups, 0.001 to 1% by mass of (E) azoles, and 0.01 to 0 of (F) hydrogen peroxide stabilizer.
- Etching solution containing 5% by mass and having a pH value of 2.5-5.
- the oxide semiconductor layer is an oxide semiconductor (IGZO) layer composed of indium, gallium, and zinc.
- IGZO oxide semiconductor
- a method of manufacturing a semiconductor device comprising bringing a semiconductor device including an oxide semiconductor layer and a copper / molybdenum multilayer thin film into contact with the etching solution according to any one of items 1 to 10. .
- the manufacturing method according to item 13 wherein the oxide semiconductor layer is an oxide semiconductor layer containing at least one of indium, gallium, and zinc.
- the present invention in an etching process of a copper / molybdenum multilayer thin film, damage to an oxide semiconductor layer such as an IGZO semiconductor layer is small, processing accuracy after etching is high, etching residue and unevenness are small, and bus life is reduced.
- an etching solution that can be extended and obtain a good wiring cross-sectional shape after etching to cope with an increase in display size and resolution, and a method for etching a copper / molybdenum multilayer thin film using the same. it can.
- the etching method can selectively and collectively etch wiring having a copper / molybdenum multilayer thin film. Further, since it is not necessary to form an etching stopper layer, it can be obtained with high productivity, and the cross-sectional shape of the wiring after etching can be improved.
- the etching solution of the present invention is used for selective etching of a copper / molybdenum multilayer thin film in a semiconductor device including an oxide semiconductor layer and a copper / molybdenum multilayer thin film.
- A Hydrogen peroxide
- B Fluorine An inorganic acid containing no atom
- C an organic acid
- D an amine compound having 2 to 10 carbon atoms and having an amino group and at least one group selected from an amino group and a hydroxyl group
- E an azole And
- F a hydrogen peroxide stabilizer, having a pH of 2.5-5.
- Hydrogen peroxide used in the etching solution of the present invention has a function of oxidizing copper wiring as an oxidizing agent and a function of oxidizing and dissolving molybdenum.
- the content of hydrogen peroxide in the etching solution is preferably 3 to 10% by mass, and more preferably 4.5 to 7.5% by mass. If the content of hydrogen peroxide is within the above range, it is preferable because the management of hydrogen peroxide is easy and an appropriate etching rate can be secured, so that the etching amount can be easily controlled.
- the inorganic acid containing no fluorine atom used in the etching solution of the present invention contributes to the dissolution of copper oxidized by (A) hydrogen peroxide, and does not contain a fluorine atom from the viewpoint of environmental measures in the present invention.
- An acid is employed.
- Preferred examples of the inorganic acid containing no fluorine atom include sulfuric acid, nitric acid, hydrochloric acid, phosphoric acid, hypophosphorous acid, carbonic acid, sulfamic acid, boric acid and the like, and these can be used alone or in combination. . Of these, sulfuric acid and nitric acid are preferable.
- the content of (B) inorganic acid in the etching solution is preferably 0.01 to 5% by mass, more preferably 0.01 to 3% by mass. If the content of the inorganic acid is within the above range, an appropriate etching rate can be obtained, and a good wiring cross-sectional shape after etching can be obtained.
- the organic acid used in the etching solution of the present invention contributes to the etching of copper and molybdenum and the removal of the residue derived from molybdenum.
- the content of the organic acid in the etching solution is preferably 1 to 15% by mass, and more preferably 5 to 13% by mass. If the content of the organic acid is within the above range, etching of copper and molybdenum and removal of residues derived from molybdenum are sufficiently performed, and a good wiring cross-sectional shape after etching can be obtained. It also functions as a masking agent for copper ions contained after etching, and can suppress excessive decomposition of hydrogen peroxide by copper.
- Preferred examples of the organic acid include aliphatic carboxylic acids having 1 to 18 carbon atoms, aromatic carboxylic acids having 6 to 10 carbon atoms, and amino acids having 1 to 10 carbon atoms.
- aliphatic carboxylic acids having 1 to 18 carbon atoms include formic acid, acetic acid, propionic acid, lactic acid, glycolic acid, diglycolic acid, pyruvic acid, malonic acid, butyric acid, hydroxybutyric acid, tartaric acid, succinic acid, malic acid, maleic acid , Fumaric acid, valeric acid, glutaric acid, itaconic acid, adipic acid, caproic acid, citric acid, propanetricarboxylic acid, trans-aconitic acid, enanthic acid, caprylic acid, lauric acid, myristic acid, palmitic acid, stearic acid, olein Preferred are acid, linoleic acid, linolenic acid and the like.
- Preferred examples of the aromatic carboxylic acid having 6 to 10 carbon atoms include benzoic acid, salicylic acid, mandelic acid, phthalic acid, isophthalic acid, and terephthalic acid.
- Examples of the amino acids having 1 to 10 carbon atoms include carbamic acid, alanine, glycine, asparagine, aspartic acid, sarcosine, serine, glutamine, glutamic acid, 4-aminobutyric acid, iminodibutyric acid, arginine, leucine, isoleucine, nitrilotriacetic acid, etc. Is preferred.
- organic acid among the above-mentioned organic acids, acetic acid, succinic acid, alanine, citric acid, malic acid, lactic acid, glycolic acid, tartaric acid, malonic acid, glycine, glutaric acid, maleic acid, and trans-aconitic acid are preferable.
- succinic acid, malic acid, lactic acid, glycolic acid, and malonic acid are particularly preferable, and these can be used alone or in combination.
- the amine compound used in the etching solution of the present invention contributes to a good wiring cross-sectional shape after etching, has 2 to 10 carbon atoms, and has an amino group and at least one group selected from an amino group and a hydroxyl group. It is a compound that has. Examples of such amine compounds include ethylenediamine, trimethylenediamine, tetramethylenediamine, 1,2-propanediamine, 1,3-propanediamine, N, N-dimethyl-1,3-propanediamine, and N, N-diethyl.
- the content of the amine compound in the etching solution of the present invention is preferably 1 to 10% by mass, more preferably 2 to 7% by mass. When the content of the amine compound is within the above range, a good wiring cross-sectional shape after etching can be obtained.
- azoles used in the etching solution of the present invention triazoles such as 1H-benzotriazole, 5-methyl-1H-benzotriazole, 3-amino-1H-triazole; 1H-tetrazole, 5-methyl-1H-tetrazole Tetrazoles such as 5-phenyl-1H-tetrazole and 5-amino-1H-tetrazole; imidazoles such as 1H-imidazole and 1H-benzimidazole; and thiazoles such as 1,3-thiazole and 4-methylthiazole.
- tetrazoles are preferable, and 5-amino-1H-tetrazole is particularly preferable.
- the content of azoles in the etching solution is preferably 0.001 to 1% by mass, and more preferably 0.001 to 0.5% by mass. If the content of azoles is within the above range, a good wiring cross-sectional shape after etching can be obtained while suppressing an increase in CD loss after etching.
- the etching solution of the present invention contains a hydrogen peroxide stabilizer.
- the hydrogen peroxide stabilizer can be used without limitation as long as it is usually used as a hydrogen peroxide stabilizer, such as phenylurea, allylurea, 1,3-dimethylurea, and thiourea.
- a hydrogen peroxide stabilizer such as phenylurea, allylurea, 1,3-dimethylurea, and thiourea.
- phenylacetamide, phenylethylene glycol, and the like are preferable, and among them, phenylurea is preferable.
- the content of the (F) hydrogen peroxide stabilizer in the etching solution of the present invention is preferably 0.01 to 0.5% by mass, and 0.01 to 0.3% by mass from the viewpoint of sufficiently obtaining the addition effect. % Is more preferable.
- the etching solution of the present invention needs to have a pH of 2.5 to 5.
- the pH is less than 2.5, molybdenum oxide generated when molybdenum is dissolved by etching becomes difficult to dissolve.
- a residue derived from molybdenum oxide is generated after etching, causing leakage and reducing electrical characteristics. It may end up.
- damage to the oxide semiconductor layer such as IGZO becomes large, which is not preferable.
- the pH of the etching solution of the present invention is preferably 2.5 to 5.
- the etching solution of the present invention preferably contains copper ions in advance for the purpose of improving the etching performance from the beginning of use.
- Copper ions can be contained in the etching solution by adding a copper salt such as copper powder, copper sulfate, or copper nitrate to the etching solution.
- the concentration of copper ions in the etching solution is preferably 100 ppm or more, and more preferably 200 ppm or more.
- the upper limit of the concentration is not limited as long as the etching performance is not deteriorated, but considering the bath life and the like, it is preferably 8000 ppm or less, more preferably 6000 ppm or less, and particularly preferably 2000 ppm or less.
- the etching solution of the present invention contains water and other various additives usually used in etching solutions as long as the effects of the etching solution are not impaired.
- the water is preferably water from which metal ions, organic impurities, particle particles, and the like have been removed by distillation, ion exchange treatment, filter treatment, various adsorption treatments, and the like, and pure water and ultrapure water are particularly preferred.
- the additive for example, various ligands and chelating agents having an effect of improving the stability at the time of dissolving copper ions can be used.
- a pH adjusting agent can be used for adjusting the pH
- a buffering agent can be used for stabilizing the pH.
- the etching method of the present invention is a selective etching method of a copper / molybdenum multilayer thin film in a semiconductor device comprising an oxide semiconductor layer and a copper / molybdenum multilayer thin film.
- a copper / molybdenum multilayer thin film etching solution containing an amine compound, (E) azoles, and (F) hydrogen peroxide stabilizer and having a pH of 2.5 to 5 is used.
- etching liquid of this invention It has the process of making it contact with the etching liquid of this invention.
- etching method of the present invention a copper / molybdenum multilayer thin film can be selectively and collectively etched with respect to an oxide semiconductor layer, and a good wiring cross-sectional shape after etching can be obtained.
- a copper substrate is formed by sequentially laminating a barrier film made of a molybdenum-based material and a copper wiring made of copper or a material mainly composed of copper on a glass substrate.
- a semiconductor device provided with an oxide semiconductor layer is used as an object to be etched together with a resist applied onto a molybdenum multilayer thin film, a desired pattern mask exposed and transferred, and developed to form a desired resist pattern. .
- a semiconductor device provided with an oxide semiconductor layer as well as a so-called molybdenum / copper / molybdenum multilayer film in which a molybdenum / copper / molybdenum multilayer film is disposed on a copper / molybdenum multilayer film is also subject to etching. It can be a thing.
- Such a copper / molybdenum multilayer thin film is preferably used for wiring of a display device such as a flat panel display.
- the copper wiring is not particularly limited as long as it is formed of copper or a material containing copper as a main component (for example, a copper alloy).
- the molybdenum-based material for forming the barrier film is molybdenum (Mo) metal or Mo-based.
- Mo molybdenum
- An alloy etc. are mentioned.
- the oxide semiconductor layer is an oxide of zinc (Zn), tin (Sn), indium (In), gallium (Ga) or hafnium (Hf), or a composite oxide of two or more of these oxides
- Known semiconductors such as ZnO, SnO, In—Ga—Zn oxide (IGZO), Zn—Sn oxide (ZTO), In—Zn oxide (IZO (registered trademark)), In—Hf—Zn
- An oxide, an In—Ga oxide (IGO), an In—Sn—Zn oxide (ITZO (registered trademark)), or the like can be given.
- a method of bringing the etching solution into contact with the etching target For example, a method of bringing the etching solution into contact with the target in the form of dripping (single wafer spin treatment) or spraying, or immersing the target in the etching solution.
- a wet etching method such as a method can be employed.
- a method of contacting an object by a form such as spray or a method of contacting an object by immersing the object in an etching solution is preferably employed.
- the use temperature of the etching solution is preferably 20 to 60 ° C., particularly 30 to 50 ° C. If the temperature of the etching solution is 20 ° C. or higher, the etching rate will not be too low, and the production efficiency will not be significantly reduced. On the other hand, if the temperature is lower than 60 ° C., the change in the liquid composition can be suppressed and the etching conditions can be kept constant. Although the etching rate is increased by increasing the temperature of the etching solution, an optimum processing temperature may be appropriately determined in consideration of suppressing a change in the composition of the etching solution.
- the hydrogen peroxide contained in the etching solution is consumed as described above by oxidizing and dissolving copper and molybdenum, and the dissolved copper and molybdenum promote the decomposition of hydrogen peroxide.
- the performance of the etching solution may deteriorate due to the decrease in the hydrogen peroxide concentration.
- bath life can be extended by adding (A) hydrogen peroxide and (C) organic acid simultaneously or separately as appropriate.
- Production Example 1 (Production of copper / molybdenum multilayer thin film) Glass is used as a substrate, molybdenum (Mo) is sputtered to form a barrier film made of molybdenum, copper is then sputtered to form a copper wiring, a resist is then applied, a pattern mask is exposed and transferred, and then developed. A patterned copper / molybdenum multilayer thin film was prepared.
- the molybdenum / copper / molybdenum three-layer film was formed in the same manner as described above, except that a molybdenum layer was formed on the copper wiring by sputtering before applying the resist in the above-described preparation method. .
- Examples 1 to 5 (Etching solution composition and evaluation results)
- the etching solution shown in Table 2 it may be expressed as a low concentration region (200-1000 ppm, sometimes referred to as Cu low concentration region) and a high concentration region (3000-4000 ppm, high Cu concentration region).
- the copper powder was dissolved so as to have a copper ion concentration (may be referred to as Cu concentration).
- the copper / molybdenum multilayer thin film obtained in the production example was etched at 35 ° C. by shower spraying, and the obtained copper / molybdenum multilayer thin film sample was subjected to the taper angle, CD loss ( ⁇ m) was obtained by SEM observation.
- the time when the etching target object in the area where the resist is not patterned is judged to be visually etched is defined as the just etching time, and the etching process is performed at an arbitrary rate within the range of 40 to 100% from the just etching time.
- the (overetching) time was set as the etching time (for example, when the just etching time is 100 seconds and the overetching is 50%, the etching time is 150 seconds).
- Table 2 shows the etching solution composition and evaluation results.
- Example 4 etching was performed in the same manner as in Example 4 except that copper powder was added to the etching solution 4 to be used in advance so that the copper ion concentration was 200 ppm (Example 6) and 6000 ppm (Example 7). .
- Table 3 shows the taper angle, CD loss ( ⁇ m), and residue evaluation of the copper / molybdenum multilayer thin film obtained by etching.
- Table 3 also shows the taper angle, CD loss ( ⁇ m), and residue evaluation of the copper / molybdenum multilayer thin film obtained by etching with the etching solution 4 of Example 4 (no copper powder added beforehand). Indicated.
- Example 4 copper powder was added to the etching solution 4 to be used in advance so as to have the concentration shown in Table 4, and the etching target film was a three-layer film of molybdenum / copper / molybdenum. Etching operation similar to that of No. 4 was performed, and Examples 8 and 9 were obtained respectively.
- the etching temperature of Example 8 was 32 ° C. Table 4 shows the taper angle, CD loss ( ⁇ m), and residue evaluation of the obtained molybdenum / copper / molybdenum multilayer thin film.
- Example 1 etching was performed in the same manner as in Example 1 except that the etching solution having the composition shown in Table 4 was used.
- Table 5 shows the taper angle, CD loss ( ⁇ m), and residue evaluation of the obtained copper / molybdenum multilayer thin film.
- Table 6 shows the etching rates of the IGZO semiconductor layer obtained according to the method of measuring the etching rate of the IGZO semiconductor layer in the compositions of Examples 1 to 5 and Comparative Examples 1 to 6.
- the example using the etching solution of the present invention showed a good cross-sectional shape after etching and an excellent result in terms of residue evaluation.
- Comparative Example 1 using the etching solution containing no component (B) a so-called undercut was generated in which the lower molybdenum layer was selectively etched over the upper copper layer in the wiring cross-sectional shape.
- Comparative Examples 2 and 3 using etching solutions not containing the components (B) to (F) it was confirmed that the etching did not proceed or the resist was peeled off, and these etching solutions were not practical.
- Comparative Example 4 using an etching solution whose pH is outside the specified range of the present invention, the CD loss is larger than 1, and in Comparative Example 5 using an etching solution containing no (D) component, lower molybdenum is selected. It was confirmed that the etching end face was not forward-tapered and the taper angle was partially reverse taper exceeding 90 degrees, causing problems in terms of the wiring cross-sectional shape.
- the wiring cross-sectional shape after etching in Examples 6 and 7 using an etching solution containing 200 ppm or 6000 ppm of copper ions in advance is the same as that after etching in Example 4 (an etching solution to which no copper powder has been added in advance).
- the etching solution of the present invention can be suitably used for etching a copper / molybdenum multilayer thin film without causing substantial damage to an oxide semiconductor layer such as IGZO.
- the etching method using the etching solution can selectively and collectively etch a wiring having a copper / molybdenum-based multilayer thin film with respect to an oxide semiconductor layer such as IGZO. Therefore, high productivity can be achieved.
- Gate electrode 3 Gate insulating film 4: i layer (amorphous silicon) 5: n + layer (amorphous silicon) 6a: source electrode 6b: drain electrode 7: protective layer 8: transparent electrode 9: IGZO semiconductor layer 10: etching stopper layer
Abstract
Description
しかし、いずれもエッチング後の配線断面形状が十分に満足いくものではなく、結果としてディスプレイの大型化及び高解像度化に十分対応できない場合があった。また、特許文献5に開示されるエッチング溶液は、フッ化化合物を含有しており、IGZOのような酸化物半導体層への損傷も大きく、また環境対策の観点からも十分満足するというものではなかった。
本発明は、かかる知見に基づいて完成したものである。すなわち、本発明の要旨は下記のとおりである。
[2](B)無機酸が、硫酸及び/又は硝酸である、第1項に記載のエッチング液。
[3](C)有機酸が、コハク酸、グリコール酸、乳酸、マロン酸及びリンゴ酸から選ばれる少なくとも一種である、第1項又は第2項に記載のエッチング液。
[4](D)アミン化合物が、エタノールアミン、1-アミノ-2-プロパノール、及びN,N-ジエチル-1,3-プロパンジアミンから選ばれる少なくとも一種である、第1項~第3項のいずれかに記載のエッチング液。
[5](E)アゾール類が、5-アミノ-1H-テトラゾールである、第1項~第4項のいずれかに記載のエッチング液。
[6](F)過酸化水素安定剤が、フェニル尿素である、第1項~第5項のいずれかに記載のエッチング液。
[7]酸化物半導体層と銅/モリブデン系多層薄膜とを備える半導体装置において銅/モリブデン系多層薄膜を選択的にエッチングできるエッチング液であって、(A)過酸化水素を3~10質量%、(B)フッ素原子を含有しない無機酸を0.01~5質量%、(C)有機酸を1~15質量%、(D)炭素数2~10であり、かつアミノ基と、アミノ基及び水酸基から選ばれる少なくとも一の基とを有するアミン化合物を1~10質量%、(E)アゾール類を0.001~1質量%、及び(F)過酸化水素安定剤を0.01~0.5質量%を含み、pH値が2.5~5であることを特徴とする、エッチング液。
[8]さらに銅イオンが、予め100~8000ppm含まれる、第1項~第7項のいずれかに記載のエッチング液。
[9]酸化物半導体層が、インジウム、ガリウム及び亜鉛のうち少なくとも一つを含む酸化物半導体層である、第1項~第8項のいずれかに記載のエッチング液。
[10]酸化物半導体層が、インジウム、ガリウム及び亜鉛より構成される酸化物半導体(IGZO)層である、第9項に記載のエッチング液。
[11]酸化物半導体層と銅/モリブデン系多層薄膜とを備える半導体装置を、第1項~第10項のいずれかに記載のエッチング液に接触させることを特徴とする、半導体装置からの銅/モリブデン系多層薄膜の選択的なエッチング方法。
[12]酸化物半導体層が、インジウム、ガリウム及び亜鉛のうち少なくとも一つを含む酸化物半導体層である、第11項に記載のエッチング方法。
[13]酸化物半導体層と銅/モリブデン系多層薄膜とを備える半導体装置を、第1項~第10項のいずれかに記載のエッチング液に接触させることを特徴とする、半導体装置の製造方法。
[14]酸化物半導体層が、インジウム、ガリウム及び亜鉛のうち少なくとも一つを含む酸化物半導体層である、第13項に記載の製造方法。
本発明のエッチング液は、酸化物半導体層と銅/モリブデン系多層薄膜とを備える半導体装置における銅/モリブデン系多層薄膜の選択的なエッチングに用いられ、(A)過酸化水素、(B)フッ素原子を含有しない無機酸、(C)有機酸、(D)炭素数2~10であり、かつアミノ基と、アミノ基及び水酸基から選ばれる少なくとも一の基とを有するアミン化合物、(E)アゾール類、及び(F)過酸化水素安定剤を含み、pHが2.5~5であることを特徴とするものである。
本発明のエッチング液で用いられる過酸化水素は酸化剤として銅配線を酸化する機能を有し、かつモリブデンに対しては酸化溶解する機能を有する。該エッチング液中の過酸化水素の含有量は、3~10質量%が好ましく、4.5~7.5質量%がより好ましい。過酸化水素の含有量が上記の範囲内であれば、過酸化水素の管理が容易となり、かつ適度なエッチング速度が確保できるので、エッチング量の制御が容易となるので好ましい。
本発明のエッチング液で用いられるフッ素原子を含まない無機酸は、(A)過酸化水素により酸化した銅の溶解に寄与するものであり、本発明においては環境対策の観点からフッ素原子を含まない酸が採用される。フッ素原子を含まない無機酸としては硫酸、硝酸、塩酸、リン酸、次亜リン酸、炭酸、スルファミン酸、硼酸などが好ましく挙げられ、これらを単独で、あるいは複数を混合して用いることができる。なかでも硫酸、硝酸が好ましい。
本発明のエッチング液で用いられる有機酸は、銅及びモリブデンのエッチング、及びモリブデン由来の残渣の除去に寄与するものである。該エッチング液中の有機酸の含有量は、1~15質量%が好ましく、5~13質量%がより好ましい。有機酸の含有量が上記範囲内であれば、銅及びモリブデンのエッチング、及びモリブデン由来の残渣の除去が十分に行われ、かつエッチング後の良好な配線断面形状を得ることができる。また、エッチング後に含有される銅イオンのマスキング剤としても機能しており、銅による過酸化水素の過剰の分解を抑制することが出来る。
炭素数1~18の脂肪族カルボン酸としては、ギ酸、酢酸、プロピオン酸、乳酸、グリコール酸、ジグリコール酸、ピルビン酸、マロン酸、酪酸、ヒドロキシ酪酸、酒石酸、コハク酸、リンゴ酸、マレイン酸、フマル酸、吉草酸、グルタル酸、イタコン酸、アジピン酸、カプロン酸、クエン酸、プロパントリカルボン酸、trans-アコニット酸、エナント酸、カプリル酸、ラウリン酸、ミリスチン酸、パルミチン酸、ステアリン酸、オレイン酸、リノール酸、リノレン酸などが好ましく挙げられる。
炭素数6~10の芳香族カルボン酸としては、安息香酸、サリチル酸、マンデル酸、フタル酸、イソフタル酸、テレフタル酸などが好ましく挙げられる。
また、炭素数1~10のアミノ酸としては、カルバミン酸、アラニン、グリシン、アスパラギン、アスパラギン酸、サルコシン、セリン、グルタミン、グルタミン酸、4-アミノ酪酸、イミノジ酪酸、アルギニン、ロイシン、イソロイシン、ニトリロ三酢酸などが好ましく挙げられる。
本発明のエッチング液で用いられるアミン化合物は、エッチング後の良好な配線断面形状に寄与し、炭素数2~10であり、かつアミノ基と、アミノ基及び水酸基から選ばれる少なくとも一の基とを有する化合物である。
このようなアミン化合物としては、エチレンジアミン、トリメチレンジアミン、テトラメチレンジアミン、1,2-プロパンジアミン、1,3-プロパンジアミン、N,N-ジメチル-1,3-プロパンジアミン、N,N-ジエチル-1,3-プロパンジアミン、1,3-ジアミノブタン、2,3-ジアミノブタン、ペンタメチレンジアミン、2,4-ジアミノペンタン、ヘキサメチレンジアミン、ヘプタメチレンジアミン、オクタメチレンジアミン、ノナメチレンジアミン、N-メチルエチレンジアミン、N,N-ジメチルエチレンジアミン、トリメチルエチレンジアミン、N-エチルエチレンジアミン、N,N-ジエチルエチレンジアミン、トリエチルエチレンジアミン、1,2,3-トリアミノプロパン、ヒドラジン、トリス(2-アミノエチル)アミン、テトラ(アミノメチル)メタン、ジエチレントリアミン、トリエチレンテトラミン、テトラエチルペンタミン、ヘプタエチレンオクタミン、ノナエチレンデカミン、ジアザビシクロウンデセンなどのポリアミン;
エタノールアミン、N-メチルエタノールアミン、N-メチルジエタノールアミン、N-エチルエタノールアミン、N-アミノエチルエタノールアミン、N-プロピルエタノールアミン、N-ブチルエタノールアミン、ジエタノールアミン、トリエタノールアミン、1-アミノ-2-プロパノール、N-メチルイソプロパノールアミン、N-エチルイソプロパノールアミン、N-プロピルイソプロパノールアミン、2-アミノプロパン-1-オール、N-メチル-2-アミノ-プロパン-1-オール、N-エチル-2-アミノ-プロパン-1-オール、1-アミノプロパン-3-オール、N-メチル-1-アミノプロパン-3-オール、N-エチル-1-アミノプロパン-3-オール、1-アミノブタン-2-オール、N-メチル-1-アミノブタン-2-オール、N-エチル-1-アミノブタン-2オール、2-アミノブタン-1-オール、N-メチル-2-アミノブタン-1-オール、N-エチル-2-アミノブタン-1-オール、3-アミノブタン-1-オール、N-メチル-3-アミノブタン-1-オール、N-エチル-3-アミノブタン-1-オール、1-アミノブタン-4-オール、N-メチル-1-アミノブタン-4-オール、N-エチル-1-アミノブタン-4-オール、1-アミノ-2-メチルプロパン-2-オール、2-アミノ-2-メチルプロパン-1-オール、1-アミノペンタン-4-オール、2-アミノ-4-メチルペンタン-1-オール、2-アミノヘキサン-1-オール、3-アミノヘプタン-4-オール、1-アミノオクタン-2-オール、5-アミノオクタン-4-オール、1-アミノプパン-2,3-ジオール、2-アミノプロパン-1,3-ジオール、トリス(オキシメチル)アミノメタン、1,2-ジアミノプロパン-3-オール、1,3-ジアミノプロパン-2-オール、2-(2-アミノエトキシ)エタノール、2-(2-アミノエチルアミノ)エタノール、ジグリコールアミンなどのアルカノールアミンが好ましく挙げられ、これらを単独で又は複数を組み合わせて用いることができる。これらの中でも、エタノールアミン、1-アミノ-2-プロパノール、N,N-ジエチル-1,3-プロパンジアミンが特に好ましい。
本発明のエッチング液で用いられるアゾール類としては、1H-ベンゾトリアゾール、5-メチル-1H-ベンゾトリアゾール、3-アミノ-1H-トリアゾールなどのトリアゾール類;1H-テトラゾール、5-メチル-1H-テトラゾール、5-フェニル-1H-テトラゾール、5-アミノ-1H-テトラゾールなどのテトラゾール類;1H-イミダゾール、1H-ベンゾイミダゾールなどのイミダゾール類;1,3-チアゾール、4-メチルチアゾールなどのチアゾール類などが好ましく挙げられる。これらのうち、テトラゾール類が好ましく、なかでも5-アミノ-1H-テトラゾールが好ましい。
本発明のエッチング液は、過酸化水素安定剤を含有する。過酸化水素安定剤としては、通常、過酸化水素安定剤として用いられるものであれば制限なく使用することが可能であるが、フェニル尿素、アリル尿素、1,3-ジメチル尿素、チオ尿素などの尿素系過酸化水素安定剤のほか、フェニル酢酸アミド、フェニルエチレングリコールなどが好ましく挙げられ、なかでもフェニル尿素が好ましい。
本発明のエッチング液中の(F)過酸化水素安定剤の含有量は、その添加効果を十分に得る観点から、0.01~0.5質量%が好ましく、0.01~0.3質量%がより好ましい。
本発明のエッチング液は、pH2.5~5であることを要する。pH2.5未満であるとモリブデンがエッチング溶解される際に生成するモリブデン酸化物が溶解しにくくなり、結果、エッチング後にモリブデン酸化物由来の残渣が発生し、リークの原因となり電気特性が低下してしまうことがある。また、IGZOのような酸化物半導体層への損傷も大きくなり好ましくない。また、pH5よりも大きいと、(A)過酸化水素の安定性が低下し、銅配線のエッチング速度が減少し、バスライフも減少してしまう。このような観点から、本発明のエッチング液のpHは、2.5~5が好ましい。
本発明のエッチング液は、使用初期からエッチング性能を向上させる目的で、予め銅イオンを含有させることが好ましい。銅イオンは、エッチング液に銅粉末や硫酸銅、硝酸銅などの銅塩を加えることで、エッチング液中に含有させることができる。
エッチング液中の銅イオンの濃度は、100ppm以上が好ましく、200ppm以上がより好ましい。また、濃度の上限は、エッチング性能が低下しない限り制限はないが、バスライフなどを考慮すると、8000ppm以下が好ましく、さらに6000ppm以下が好ましく、特に2000ppm以下がより好ましい。
本発明のエッチング液は、上記した(A)~(F)成分のほか、水、その他エッチング液に通常用いられる各種添加剤をエッチング液の効果を害しない範囲で含む。水としては、蒸留、イオン交換処理、フィルター処理、各種吸着処理などによって、金属イオンや有機不純物、パーティクル粒子などが除去されたものが好ましく、特に純水、超純水が好ましい。添加剤としては、例えば、銅イオン溶解時の安定性を向上させる効果のある、各種配位子やキレート剤を用いることができる。また例えば、pHの調整のために、pH調整剤を、pHの安定化のために、緩衝剤を用いることもできる。
本発明のエッチング方法は、酸化物半導体層と銅/モリブデン系多層薄膜とを備える半導体装置における銅/モリブデン系多層薄膜の選択的なエッチング方法であり、本発明のエッチング液、すなわち(A)過酸化水素、(B)フッ素原子を含有しない無機酸、(C)有機酸、(D)炭素数2~10であり、かつアミノ基と、アミノ基及び水酸基から選ばれる少なくとも一の基とを有するアミン化合物、(E)アゾール類、及び(F)過酸化水素安定剤を含み、pHが2.5~5である銅/モリブデン系多層薄膜用エッチング液を用いることを特徴とし、エッチング対象物と本発明のエッチング液とを接触させる工程を有するものである。本発明のエッチング方法により、酸化物半導体層に対し、銅/モリブデン系多層薄膜を選択的に、かつ一括でエッチングを行うことができ、そしてエッチング後の良好な配線断面形状を得ることができる。
銅配線は、銅又は銅を主成分とする材料(例えば、銅合金)により形成されていれば特に制限はなく、当該バリア膜を形成するモリブデン系材料としては、モリブデン(Mo)金属又はMo系合金などが挙げられる。
酸化物半導体層としては、亜鉛(Zn)、錫(Sn)、インジウム(In)、ガリウム(Ga)又はハフニウム(Hf)の酸化物又はこれらの2種以上の複合酸化物であって、酸化物半導体として公知のもの、例えば、ZnO、SnO、In-Ga-Zn酸化物(IGZO)、Zn-Sn酸化物(ZTO)、In-Zn酸化物(IZO(登録商標))、In-Hf-Zn酸化物、In-Ga酸化物(IGO)又はIn-Sn-Zn酸化物(ITZO(登録商標))などが挙げられる。
実施例及び比較例で得られた、エッチングを行った後の銅/モリブデン系多層薄膜試料の断面を走査型電子顕微鏡(「S5000形(型番)」;日立製)を用いて観察倍率30000倍(加速電圧2kV、加速電流10μA)で観察した。得られたSEM画像をもとに図4で示されるテーパー角、CDロス(μm)を得た。
テーパー角、CDロス(μm)、及びIGZO半導体層のエッチング速度は、表1に記載の基準範囲内であれば合格とし、エッチング液の性能を判断した。
実施例及び比較例で得られた、エッチングを行った後の銅/モリブデン系多層薄膜試料の表面を走査型電子顕微鏡(「S5000形(型番)」;日立製)を用いて観察倍率50000倍(加速電圧2kV、加速電流10μA)で観察し、当該試料の残渣を下記の基準で評価した。
○ :残渣は全く確認できなかった
△ :残渣が若干確認されたが、配線性能への影響はなく実用上問題ない
× :著しい残渣が確認された
IGZO半導体を有するガラス基板を用いて、実施例及び比較例に示されるエッチング液に35℃で1~60分間浸漬し、蛍光X線分析装置(「SEA1200VX(型番)」;SIIナノテクノロジー社製)により浸漬前後の膜厚を測定することで、これらの差分から酸化物半導体のエッチング速度(Å/min.)を測定し、表1に記載の基準範囲内であれば合格として、エッチング液のIGZO半導体層への低腐食性を判断した。
ガラスを基板とし、モリブデン(Mo)をスパッタしモリブデンからなるバリア膜を形成し、次いで銅をスパッタして銅配線を形成し、次いでレジストを塗布し、パターンマスクを露光転写後、現像して、パターンを形成した銅/モリブデン系多層薄膜を作製した。また、モリブデン/銅/モリブデンの三層膜については、前述の作成方法におけるレジスト塗布前に、銅配線上にモリブデンをスパッタにてモリブデン層を形成させること以外は、前述の方法と同様に実施した。
表2に示されるエッチング液中に、低濃度域(200-1000ppm,Cu低濃度域と表記することがある。)及び高濃度域(3000-4000ppm,Cu高濃度域と表記することがある。)の銅イオン濃度(Cu濃度と表記することがある。)となるように銅粉末を溶解した。このエッチング液で、作製例で得られた銅/モリブデン系多層薄膜を、シャワー噴霧により35℃でエッチングする作業を行い、得られたエッチング後の銅/モリブデン系多層薄膜試料について、該テーパー角、CDロス(μm)をSEM観察により得た。
また、レジストがパターニングされていないエリアのエッチング対象物が、目視にてエッチングされたと判断した時間をジャストエッチング時間とし、該ジャストエッチング時間から40~100%の範囲内の任意の割合で長くエッチング処理(オーバーエッチング)した時間をエッチング時間として設定した(例えば、ジャストエッチングタイム100秒のとき、50%のオーバーエッチングならば、そのエッチング時間は150秒となる)。エッチング液組成及び評価結果を表2に示す。
実施例4において、使用するエッチング液4に予め銅イオン濃度が200ppm(実施例6)、6000ppm(実施例7)となるように銅粉末を加える以外は、実施例4と同様にエッチングを行った。エッチングで得られた銅/モリブデン系多層薄膜のテーパー角、CDロス(μm)、残渣の評価を表3に示す。また、表3には実施例4のエッチング液4(予め銅粉末を添加していない)によるエッチングで得られた銅/モリブデン系多層薄膜のテーパー角、CDロス(μm)、残渣の評価も同時に示した。
実施例1において、エッチング液を表4に示す配合のものを用いる以外は、実施例1と同様にして、エッチングを行った。得られた銅/モリブデン系多層薄膜のテーパー角、CDロス(μm)、残渣の評価を表5に示す。
予め銅イオンを200ppm、あるいは6000ppmを含有させたエッチング液を用いた実施例6及び7のエッチング後の配線断面形状は、実施例4(予め銅粉末を添加していないエッチング液)でのエッチング後の配線断面形状よりも良好であり、残渣の評価の点でも良好であることが確認された。すなわち、本発明のエッチング液に予め銅イオンを加えると、エッチング液の使用初期から、良好な性能を発現することが確認された。
また、IGZOのエッチング速度については、実施例1~5のいずれも合格基準内であり、銅/モリブデン系多層薄膜のエッチング性能と両立していることが確認された。
2:ゲート電極
3:ゲート絶縁膜
4:i層(アモルファスシリコン)
5:n+層(アモルファスシリコン)
6a:ソース電極
6b:ドレイン電極
7:保護層
8:透明電極
9:IGZO半導体層
10:エッチングストッパ層
Claims (14)
- 酸化物半導体層と銅/モリブデン系多層薄膜とを備える半導体装置において銅/モリブデン系多層薄膜を選択にエッチングできるエッチング液であって、(A)過酸化水素、(B)フッ素原子を含有しない無機酸、(C)有機酸、(D)炭素数2~10であり、かつアミノ基と、アミノ基及び水酸基から選ばれる少なくとも一の基とを有するアミン化合物、(E)アゾール類、及び(F)過酸化水素安定剤を含み、pHが2.5~5であることを特徴とする、エッチング液。
- (B)無機酸が、硫酸及び/又は硝酸である、請求項1に記載のエッチング液。
- (C)有機酸が、コハク酸、グリコール酸、乳酸、マロン酸及びリンゴ酸から選ばれる少なくとも一種である、請求項1又は2に記載のエッチング液。
- (D)アミン化合物が、エタノールアミン、1-アミノ-2-プロパノール、及びN,N-ジエチル-1,3-プロパンジアミンから選ばれる少なくとも一種である、請求項1~3のいずれかに記載のエッチング液。
- (E)アゾール類が、5-アミノ-1H-テトラゾールである、請求項1~4のいずれかに記載のエッチング液。
- (F)過酸化水素安定剤が、フェニル尿素である、請求項1~5のいずれかに記載のエッチング液。
- 酸化物半導体層と銅/モリブデン系多層薄膜とを備える半導体装置において銅/モリブデン系多層薄膜を選択的にエッチングできるエッチング液であって、(A)過酸化水素を3~10質量%、(B)フッ素原子を含有しない無機酸を0.01~5質量%、(C)有機酸を1~15質量%、(D)炭素数2~10であり、かつアミノ基と、アミノ基及び水酸基から選ばれる少なくとも一の基とを有するアミン化合物を1~10質量%、(E)アゾール類を0.001~1質量%、及び(F)過酸化水素安定剤を0.01~0.5質量%を含み、pH値が2.5~5であることを特徴とする、エッチング液。
- さらに銅イオンが、予め100~8000ppm含まれる、請求項1~7のいずれかに記載のエッチング液。
- 酸化物半導体層が、インジウム、ガリウム及び亜鉛のうち少なくとも一つを含む酸化物半導体層である、請求項1~8のいずれかに記載のエッチング液。
- 酸化物半導体層が、インジウム、ガリウム及び亜鉛より構成される酸化物半導体(IGZO)層である、請求項9に記載のエッチング液。
- 酸化物半導体層と銅/モリブデン系多層薄膜とを備える半導体装置を、請求項1~10のいずれかに記載のエッチング液に接触させることを特徴とする、半導体装置からの銅/モリブデン系多層薄膜の選択的なエッチング方法。
- 酸化物半導体層が、インジウム、ガリウム及び亜鉛のうち少なくとも一つを含む酸化物半導体層である、請求項11に記載のエッチング方法。
- 酸化物半導体層と銅/モリブデン系多層薄膜とを備える半導体装置を、請求項1~10のいずれかに記載のエッチング液に接触させることを特徴とする、半導体装置の製造方法。
- 酸化物半導体層が、インジウム、ガリウム及び亜鉛のうち少なくとも一つを含む酸化物半導体層である、請求項13に記載の製造方法。
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Citations (6)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JP2002141666A (ja) * | 2000-10-31 | 2002-05-17 | Mitsubishi Gas Chem Co Inc | 多層銅張板の製造方法 |
JP2002302780A (ja) * | 2000-12-20 | 2002-10-18 | Lg Phillips Lcd Co Ltd | エッチング溶液及びエッチング溶液でパターン形成された銅配線を有する電子機器用アレー基板 |
JP2004193620A (ja) * | 2002-12-12 | 2004-07-08 | Lg Phillips Lcd Co Ltd | 銅モリブデン膜で、モリブデンの残渣を除去するエッチング溶液及びそのエッチング方法 |
JP2009076601A (ja) * | 2007-09-19 | 2009-04-09 | Nagase Chemtex Corp | エッチング溶液 |
WO2009066750A1 (ja) * | 2007-11-22 | 2009-05-28 | Idemitsu Kosan Co., Ltd. | エッチング液組成物 |
JP2010232486A (ja) * | 2009-03-27 | 2010-10-14 | Nagase Chemtex Corp | エッチング用組成物 |
Family Cites Families (9)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JP4264679B2 (ja) * | 1999-04-09 | 2009-05-20 | 三菱瓦斯化学株式会社 | プリント配線板の製造方法 |
US6664186B1 (en) * | 2000-09-29 | 2003-12-16 | International Business Machines Corporation | Method of film deposition, and fabrication of structures |
JP2004137586A (ja) * | 2002-10-21 | 2004-05-13 | Mitsubishi Chemicals Corp | エッチング液及びエッチング方法 |
US7435356B2 (en) * | 2004-11-24 | 2008-10-14 | Rohm And Haas Electronic Materials Cmp Holdings, Inc. | Abrasive-free chemical mechanical polishing compositions and methods relating thereto |
CN101897031B (zh) | 2007-12-13 | 2013-04-17 | 出光兴产株式会社 | 使用了氧化物半导体的场效应晶体管及其制造方法 |
KR100958006B1 (ko) | 2008-06-18 | 2010-05-17 | 삼성모바일디스플레이주식회사 | 박막 트랜지스터, 그의 제조 방법 및 박막 트랜지스터를구비하는 평판 표시 장치 |
JP5724157B2 (ja) | 2009-04-13 | 2015-05-27 | 日立金属株式会社 | 酸化物半導体ターゲット及びそれを用いた酸化物半導体装置の製造方法 |
TWI518206B (zh) | 2010-01-28 | 2016-01-21 | 三菱瓦斯化學股份有限公司 | 銅/鈦系多層薄膜用的蝕刻液 |
WO2011099624A1 (ja) * | 2010-02-15 | 2011-08-18 | 三菱瓦斯化学株式会社 | 銅層及びモリブデン層を含む多層薄膜用エッチング液 |
-
2012
- 2012-07-25 CN CN201280037180.XA patent/CN103717787B/zh active Active
- 2012-07-25 KR KR1020147003581A patent/KR101901721B1/ko active IP Right Grant
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- 2012-07-25 WO PCT/JP2012/068853 patent/WO2013015322A1/ja active Application Filing
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Patent Citations (6)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JP2002141666A (ja) * | 2000-10-31 | 2002-05-17 | Mitsubishi Gas Chem Co Inc | 多層銅張板の製造方法 |
JP2002302780A (ja) * | 2000-12-20 | 2002-10-18 | Lg Phillips Lcd Co Ltd | エッチング溶液及びエッチング溶液でパターン形成された銅配線を有する電子機器用アレー基板 |
JP2004193620A (ja) * | 2002-12-12 | 2004-07-08 | Lg Phillips Lcd Co Ltd | 銅モリブデン膜で、モリブデンの残渣を除去するエッチング溶液及びそのエッチング方法 |
JP2009076601A (ja) * | 2007-09-19 | 2009-04-09 | Nagase Chemtex Corp | エッチング溶液 |
WO2009066750A1 (ja) * | 2007-11-22 | 2009-05-28 | Idemitsu Kosan Co., Ltd. | エッチング液組成物 |
JP2010232486A (ja) * | 2009-03-27 | 2010-10-14 | Nagase Chemtex Corp | エッチング用組成物 |
Cited By (46)
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US9466508B2 (en) | 2013-04-23 | 2016-10-11 | Mitsubishi Gas Chemical Company, Inc. | Liquid composition used in etching multilayer film containing copper and molybdenum, manufacturing method of substrate using said liquid composition, and substrate manufactured by said manufacturing method |
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JPWO2018180988A1 (ja) * | 2017-03-31 | 2020-02-06 | 三菱瓦斯化学株式会社 | 圧延銅箔の表面処理液及び表面処理方法並びに圧延銅箔の製造方法 |
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JP7074127B2 (ja) | 2017-03-31 | 2022-05-24 | 三菱瓦斯化学株式会社 | 圧延銅箔の表面処理液及び表面処理方法並びに圧延銅箔の製造方法 |
CN111051488A (zh) * | 2017-08-31 | 2020-04-21 | 富士胶片株式会社 | 药液的纯化方法及药液 |
US11491428B2 (en) | 2017-08-31 | 2022-11-08 | Fujifilm Corporation | Chemical liquid purification method and chemical liquid |
CN111472003A (zh) * | 2020-05-27 | 2020-07-31 | 湖北兴福电子材料有限公司 | 一种铜制程面板中调节蚀刻锥角的蚀刻液及调节方法 |
CN111472003B (zh) * | 2020-05-27 | 2022-09-20 | 湖北兴福电子材料股份有限公司 | 一种铜制程面板中调节蚀刻锥角的蚀刻液及调节方法 |
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JP6036691B2 (ja) | 2016-11-30 |
US20140162403A1 (en) | 2014-06-12 |
TWI531639B (zh) | 2016-05-01 |
TW201311868A (zh) | 2013-03-16 |
JPWO2013015322A1 (ja) | 2015-02-23 |
KR101901721B1 (ko) | 2018-09-28 |
CN103717787A (zh) | 2014-04-09 |
CN103717787B (zh) | 2016-08-24 |
KR20140044908A (ko) | 2014-04-15 |
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