Processing solution for semiconductor device, method for processing substrate, and method for manufacturing semiconductor device

Abstract

To provide a processing solution for a semiconductor device which exhibits excellent removal capability for residues generated after etching while delivering excellent anti-corrosion effect on a substrate on which a metal layer is formed; a method for processing a substrate; and a method for manufacturing a semiconductor device.SOLUTION: The present invention provides a processing solution for a semiconductor device including a fluorine-containing compound, water, a cyclic ether compound, and a water-soluble organic solvent that is not the cyclic ether compound; a method for processing a substrate; and a method for manufacturing a semiconductor device.SELECTED DRAWING: None

Description

[Technical field]

[0001] The present invention relates to a processing liquid for semiconductor devices, a method for processing a substrate, and a method for manufacturing a semiconductor device. [Background technology]

[0002] Semiconductor elements such as ICs and LSIs and liquid crystal panel elements are manufactured, for example, by uniformly applying a resist onto an insulating film such as a metal film or an SiO2 film deposited on a substrate by CVD, selectively exposing and developing the resist to form a resist pattern, and selectively etching the substrate on which the CVD-deposited metal film or the SiO2 film or other insulating film has been formed using this pattern as a mask to form a fine circuit, and then removing unnecessary resist layers.

[0003] Various types of metal films are used as the above-mentioned CVD-deposited metal films. These metal films are laminated in a single layer or multiple layers on a substrate.

[0004] Meanwhile, with the recent trend towards higher density integrated circuits, dry etching, which allows finer etching at higher density, has become mainstream. These etching processes can leave residues such as altered films on the sides and bottoms of patterns, or residues derived from other components. In addition, metal deposition occurs when removing metal films during etching. If such residues and depositions are not sufficiently removed, problems such as a decrease in the yield of semiconductor manufacturing occur. For this reason, processing liquids (sometimes called cleaning liquids, stripping liquids, etc.) are used to remove such residues and depositions.

[0005] For example, Patent Document 1 discloses a resist stripping liquid composition comprising hydrofluoric acid, a water-soluble organic solvent, and at least one anticorrosive agent selected from the group consisting of aromatic hydroxy compounds, acetylene alcohols, carboxyl group-containing organic compounds and their anhydrides, and triazole compounds. [Prior art documents] [Patent documents]

[0006] [Patent Document 1] Patent No. 3255551 Summary of the Invention [Problem to be solved by the invention]

[0007] However, the above-mentioned residues and depositions are generated with different compositions depending on the type of etching gas, the type of metal formed on the substrate, the type of insulating film, the type of resist used, etc. Due to the recent improvements in semiconductors, the processing conditions in various processes have become more severe and the metals, insulating films, and resists used have become more diverse, which makes it difficult to remove the residues. Due to these and other factors, there is still room for improvement in conventional processing solutions.

[0008] The present invention has been made in consideration of the above circumstances, and aims to provide a semiconductor device treatment liquid, a substrate treatment method, and a semiconductor device manufacturing method that are excellent in removing residues generated after etching and have an excellent corrosion prevention effect on a substrate on which a metal layer is formed. [Means for solving the problem]

[0009] As a result of intensive research into solving the above-mentioned problems, the present inventors have found that the above-mentioned problems can be solved by providing a treatment liquid for semiconductor devices containing a fluorine-containing compound, water, a cyclic ether compound, and a water-soluble organic solvent other than the cyclic ether compound.

[0010] That is, the present invention is as follows. <1> The semiconductor device treatment liquid contains a fluorine-containing compound, water, a cyclic ether compound, and a water-soluble organic solvent other than the cyclic ether compound. <2> The number of carbon atoms forming a ring in the cyclic ether compound is 2 to 4, and the number of oxygen atoms forming the ring is 1 to 2. <1> 2. The semiconductor device treating liquid according to claim 1 . <3> the mass ratio of the water-soluble organic solvent to the cyclic ether compound is 100,000 to 15,000,000; <1> or <2> 2. The semiconductor device treating liquid according to claim 1 . <4> The content of the cyclic ether compound is 0.000001% by mass to 10% by mass. <1> or <2> 2. The semiconductor device treating liquid according to claim 1 . <5> The semiconductor device includes a substrate having a metal layer containing Al, and the treatment liquid is used for treatment of the metal layer. <1> or <2> 2. The semiconductor device treating liquid according to claim 1 . <6> The semiconductor device includes a substrate having a metal layer containing Cu, and the treatment liquid is used for treatment of the metal layer. <1> or <2> 2. The semiconductor device treating liquid according to claim 1 . <7> It is used for removing residues generated after an etching process is performed on a substrate having a metal layer, which is used in the manufacture of the semiconductor device. <1> or <2> 2. The semiconductor device treating liquid according to claim 1 . <8> The method for treating a substrate includes the steps of: forming a resist pattern on a substrate having a metal layer containing Al and / or Cu; dry etching the substrate using the resist pattern as a mask; and removing residual matter from the substrate using a semiconductor device treatment liquid containing a fluorine-containing compound, a water-soluble organic solvent, water, and a cyclic ether compound. <9> The method for manufacturing a semiconductor device includes the steps of: forming a resist pattern on a substrate having a metal layer containing Al and / or Cu; dry etching the substrate using the resist pattern as a mask; and removing residues from the substrate using a semiconductor device treatment liquid that contains a fluorine-containing compound, a water-soluble organic solvent, water, and a cyclic ether compound. Effect of the Invention

[0011] According to the present invention, it is possible to provide a semiconductor device treatment liquid that is excellent in removing residues generated after etching and has an excellent corrosion prevention effect on a substrate on which a metal layer is formed, a substrate treatment method, and a semiconductor device manufacturing method. DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS

[0012] Hereinafter, an embodiment for carrying out the present invention (hereinafter, simply referred to as "the present embodiment") will be described in detail. The present embodiment is an example for explaining the present invention, and is not intended to limit the present invention to the following content. The present invention can be carried out by appropriately modifying it within the scope of its gist.

[0013] <Semiconductor device processing solution>

[0014] The semiconductor device treatment liquid according to this embodiment is a semiconductor device treatment liquid containing a fluorine-containing compound, water, a cyclic ether compound, and a water-soluble organic solvent other than the cyclic ether compound.

[0015] (Component (a))

[0016] (a) The fluorine-containing compound is a compound containing a fluorine atom. The fluorine-containing compound is preferably a compound that does not contain metal ions. Specific examples of the fluorine-containing compound include ammonium fluoride (AF), hydrogen fluoride (HF), ammonium borofluoride, methylamine hydrogen fluoride, ethylamine hydrogen fluoride, propylamine hydrogen fluoride, tetramethylammonium fluoride, tetraethylammonium fluoride, ethanolamine hydrogen fluoride, methylethanolamine hydrogen fluoride, dimethylethanolamine hydrogen fluoride, hydroxylamine hydrogen fluoride, dimethylhydroxylamine hydrogen fluoride, and triethylenediamine hydrogen fluoride. Among these, ammonium fluoride (AF) and hydrogen fluoride (HF) are preferred, and ammonium fluoride is more preferred. These may be used alone or in combination of two or more.

[0017] When two or more kinds are used in combination as the (a) component, the combination preferably contains two kinds of ammonium fluoride and hydrogen fluoride, and more preferably contains only two kinds of ammonium fluoride and hydrogen fluoride as the (a) component. When ammonium fluoride and hydrogen fluoride are used in combination, the mass ratio of hydrogen fluoride to ammonium fluoride (hydrogen fluoride / ammonium fluoride) is preferably 0.01 (e.g., ammonium fluoride:hydrogen fluoride=1:0.01) or more and 0.1 or less (e.g., ammonium fluoride:hydrogen fluoride=1:0.1). The lower limit of this mass ratio is preferably 0.03 (e.g., ammonium fluoride:hydrogen fluoride=1:0.03) or more. The upper limit of this mass ratio is preferably 0.07 (e.g., ammonium fluoride:hydrogen fluoride=1:0.07) or less.

[0018] The content of component (a) is preferably 0.01 to 10 mass %, more preferably 0.5 mass % or more, and even more preferably 0.8 mass % or more, and more preferably 5 mass % or less, more preferably 3 mass % or less, and even more preferably 2 mass % or less.

[0019] ((b) component)

[0020] (b) As the water, for example, from the viewpoint of suitability for manufacturing semiconductor devices, deionized water (DIW), ultrapure water (UPW), pure water, high-purity ionized water, etc. can be used. Among these, deionized water is preferred.

[0021] The content of component (b) is preferably 10 to 50% by mass. The lower limit of the content of component (b) is more preferably 20% by mass or more, and even more preferably 25% by mass or more. The upper limit of the content of component (b) is more preferably 40% by mass or less, and even more preferably 35% by mass or less.

[0022] ((c) component)

[0023] (c) The cyclic ether compound preferably contains one ring containing an oxygen atom in the molecule. The number of carbon atoms forming the ring in (c) the cyclic ether compound is preferably 2 to 4. The number of carbon atoms forming the ring here means the number of carbon atoms forming one ring. The number of oxygen atoms forming the ring in the cyclic ether compound is preferably 1 to 2.

[0024] The molecular weight of the (c) cyclic ether compound is not particularly limited, but is preferably not more than 200, more preferably not more than 150, even more preferably not more than 105, even more preferably not more than 90, and even more preferably not more than 50. The lower limit of the molecular weight of the (c) component is preferably 40 or more.

[0025] Specific examples of the (c) component include ethylene oxide (ethylene oxide, oxirane; molecular weight 44.5), 1,4-dioxane (molecular weight 88.1), tetrahydrofuran (THF, molecular weight 72.1), and 4-methyltetrahydropyran (MTHP, molecular weight 100). Among these, ethylene oxide and 1,4-dioxane are preferred, and ethylene oxide is more preferred. These may be used alone or in combination of two or more. The (c) component preferably contains only ethylene oxide and / or 1,4-dioxane. When ethylene oxide and 1,4-dioxane are used in combination, the mass ratio (ethylene oxide:1,4-dioxane) is, for example, 10:90 to 90:10, preferably 15:85 to 85:15, more preferably 15:85 to 60:40, and even more preferably 15:85 to 55:45.

[0026] The content of the (c) component is preferably 0.000001% by mass to 10% by mass. The lower limit of the content of the (c) component is more preferably 0.000005% by mass or more, even more preferably 0.000008% by mass or more, and even more preferably 0.00001% by mass or more. The upper limit of the content of the (c) component is more preferably 5% by mass or less, even more preferably 1% by mass or less, even more preferably 0.01% by mass or less, even more preferably 0.001% by mass or less, and even more preferably 0.0003% by mass or less.

[0027] ((d) component)

[0028] The (d) water-soluble organic solvent may be any water-soluble organic solvent that is miscible with the (a), (b), and (c) components, and an appropriate water-soluble organic solvent can be selected in consideration of the types and contents of the (a), (b), and (c) components used. Note that the (d) component is preferably a solvent other than the compound corresponding to the (c) component. In addition, the (d) component is preferably a water-soluble organic solvent other than a cyclic ether compound.

[0029] Specific examples of the component (d) include sulfoxides such as dimethyl sulfoxide (DMSO); sulfones such as dimethyl sulfone, diethyl sulfone, bis(2-hydroxyethyl) sulfone, and tetramethylene sulfone; amides such as N,N-dimethylformamide (DMF), N-methylformamide, N,N-dimethylacetamide, N-methylacetamide, and N,N-diethylacetamide; lactams such as N-methyl-2-pyrrolidone (NMP), N-ethyl-2-pyrrolidone, N-propyl-2-pyrrolidone, N-hydroxymethyl-2-pyrrolidone, and N-hydroxyethyl-2-pyrrolidone; 1,3-dimethyl-2-imidazolidino Examples of the imidazolidinones include γ-butyrolactone, 1,3-diethyl-2-imidazolidinone, 1,3-diisopropyl-2-imidazolidinone, etc.; lactones include γ-butyrolactone, δ-valerolactone, etc.; and polyhydric alcohols and derivatives thereof, such as ethylene glycol, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monobutyl ether, ethylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether acetate, diethylene glycol, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol monobutyl ether, etc. Among these, from the viewpoint of further improving the effects of the present embodiment, sulfoxides, amides, and lactams are preferred, dimethyl sulfoxide, N,N-dimethylformamide, N-methyl-2-pyrrolidone, etc. are more preferred, and dimethyl sulfoxide is even more preferred.

[0030] The combination of the (c) component and the (d) component preferably contains only at least one selected from the group consisting of ethylene oxide and 1,4-dioxane as the (c) component, and at least one selected from the group consisting of dimethyl sulfoxide, N,N-dimethylformamide, and N-methyl-2-pyrrolidone as the (d) component; it is more preferable to contain only ethylene oxide and / or 1,4-dioxane as the (c) component, and at least one selected from the group consisting of dimethyl sulfoxide, N,N-dimethylformamide, and N-methyl-2-pyrrolidone as the (d) component.

[0031] The content of component (d) is preferably 50 to 80% by mass. The lower limit of the content of component (d) is more preferably 60% by mass or more, and even more preferably 65% ​​by mass or more. The upper limit of the content of component (d) is more preferably 75% by mass or less, and even more preferably 70% by mass or less.

[0032] The mass ratio ((d) / (c)) of the (d) water-soluble organic solvent to the (c) cyclic ether compound is, for example, 100,000 to 15,000,000, and preferably 200,000 to 10,000,000. The lower limit of this mass ratio is more preferably 600,000 or more, and even more preferably 650,000 or more. The upper limit of this mass ratio is more preferably 9,000,000 or less, even more preferably 8,000,000 or less, and even more preferably 7,000,000 or less.

[0033] By blending the components (c) and (d) in the above ratio, it is possible to achieve both the removability of residues generated after etching and the inhibition of metal corrosion. Surprisingly, the effect obtained by setting this ratio within the above range is particularly excellent when the solvent contains only the component (d) (however, the action of this embodiment is not limited to this).

[0034] (Other Ingredients)

[0035] The semiconductor device treatment liquid according to this embodiment may further contain any component other than the components (a) to (d) as long as the effects of this embodiment can be obtained. Examples of the component include an anticorrosive agent and a surfactant. The anticorrosive agent is preferably at least one selected from the group consisting of aromatic hydroxy compounds, acetylene alcohols, carboxyl group-containing organic compounds and their anhydrides, triazole compounds, and sugars. The surfactant may be a nonionic surfactant, an anionic surfactant, a cationic surfactant, or an amphoteric surfactant, and a nonionic surfactant is preferred from the viewpoint of corrosion prevention.

[0036] The semiconductor device treating liquid according to this embodiment preferably does not contain a water-insoluble organic solvent as a solvent. Examples of the water-insoluble organic solvent include halogen-substituted or unsubstituted hydrocarbon solvents.

[0037] The semiconductor device processing liquid according to this embodiment having the above-mentioned composition can be suitably used as an aqueous processing liquid containing (b) water. Such a semiconductor device processing liquid can be suitably used as a processing liquid for a substrate as described below. Also, it can be suitably used in a substrate processing method as described below. Preferred examples of the usage mode of the semiconductor device processing liquid will be described below.

[0038] <Substrate using treatment liquid and method for treating substrate>

[0039] (substrate)

[0040] The semiconductor device treatment liquid according to the present embodiment is suitable for removing residues generated after a resist pattern is formed on a substrate having a metal layer used in the manufacture of a semiconductor device and etching is performed on the substrate. More specifically, the substrate can be etched using a resist pattern (e.g., photoresist) formed on the substrate as a mask. Furthermore, an ashing process may be performed thereafter. The semiconductor device treatment liquid according to the present embodiment can then be used to treat the substrate. Alternatively, the treatment liquid may be used as a treatment liquid (cleaning liquid) after a chemical mechanical polishing (CMP) process. The substrate may be treated by a single-wafer method. The treatment may be performed, for example, by immersing the substrate in the treatment liquid, applying the treatment liquid, or the like.

[0041] Regarding the composition of the substrate, the semiconductor device treatment liquid according to the present embodiment is suitable for use in treating a substrate having a metal layer containing Al, the metal layer being a semiconductor device. Examples of the metal layer containing Al include metal layers containing Al, Al alloys, AlCu alloys, etc.

[0042] Alternatively, the semiconductor device treatment liquid according to the present embodiment is suitable for use in treating a semiconductor device including a substrate having a metal layer containing Cu, the treatment liquid being used to treat the metal layer. Examples of the metal layer containing Cu include metal layers containing Cu, Cu alloys, AlCu alloys, and the like.

[0043] The semiconductor device treatment liquid according to the present embodiment can be suitably used for cleaning a substrate. A step of forming a resist pattern on a substrate having a metal layer containing Al and / or Cu; dry etching the substrate using the resist pattern as a mask; removing residues from a substrate using a semiconductor device treatment liquid containing a fluorine-containing compound, a water-soluble organic solvent, water, and a cyclic ether compound; The present invention relates to a method for treating a substrate comprising the above-mentioned. The above-mentioned semiconductor device treatment liquid may be, for example, a treatment liquid having the above-mentioned composition. The metal layer containing Al and / or Cu may be, for example, a metal layer containing at least one selected from the group consisting of Cu, Cu alloy, Al, Al alloy, and AlCu alloy, and specific examples of the substrate having the metal layer will be described later.

[0044] <Method of manufacturing semiconductor devices>

[0045] As a suitable example of the method for manufacturing a semiconductor device according to this embodiment, for example, (i) forming a resist pattern on a substrate having a metal layer containing Al and / or Cu; (ii) dry etching the substrate using the resist pattern as a mask; (iii) removing residues from the substrate using a semiconductor device treatment liquid containing a fluorine-containing compound, a water-soluble organic solvent, water, and a cyclic ether compound; The present invention relates to a method for producing a semiconductor device comprising the steps of:

[0046] Then, if necessary, an ashing step may be performed after the step (ii) (dry etching step). That is, the step (ii) may be a step of performing (ii-1) dry etching the substrate using a resist pattern as a mask, and (ii-2) ashing the resist pattern. In the manufacturing method (or processing method) according to this embodiment, the substrate is subjected to etching and ashing using a resist pattern (such as a photoresist pattern) provided on the substrate as a mask, and then the substrate is processed using the above-mentioned semiconductor device processing liquid.

[0047] The process (i) will be described. For example, a photoresist layer is formed on a substrate such as a silicon wafer or glass. If desired, an insulating film such as a conductive metal film, a metal oxide film, or a SiO2 film may be formed on the substrate by deposition or the like. Examples of metals for the conductive metal film or metal oxide film include aluminum (Al); aluminum alloys such as aluminum-silicon (Al-Si); copper (Cu); copper (Cu alloys) such as copper-silicon (Cu-Si); aluminum-copper alloys (AlCu alloys) such as aluminum-copper (Al-Cu) and aluminum-silicon-copper (Al-Si-Cu); titanium (Ti); titanium alloys (Ti alloys) such as titanium nitride (TiN) and titanium tungsten (TiW); tantalum (Ta), tantalum nitride (TaN), tungsten (W), tungsten nitride (WN), etc., which are formed on the substrate in a single layer to multiple layers. In particular, when the above treatment is performed on a substrate having a metal layer containing at least one selected from the group consisting of Al, Al alloy, Cu, Cu alloy, AlCu alloy, Ti, Ti alloy, etc., residues are likely to adhere and deposition is likely to occur. In this regard, the semiconductor device treatment liquid according to this embodiment can exhibit particularly excellent residue removal properties. Furthermore, in the case of a substrate having a first metal layer containing at least one selected from the group consisting of Al, Al alloy, Cu, Cu alloy, AlCu alloy, etc., and a second metal layer containing at least one selected from the group consisting of Ti, Ti alloy, etc., a more excellent effect can be exhibited.

[0048] The process (ii) will be described. For example, a photoresist pattern is formed on a substrate as a resist. In this case, the exposure conditions and development conditions can be appropriately selected according to the purpose and the photoresist to be used. For example, the photoresist layer can be exposed through a desired mask pattern by a light source (e.g., a low-pressure mercury lamp, a high-pressure mercury lamp, an ultra-high-pressure mercury lamp, a xenon lamp, etc.) that emits active light such as ultraviolet light, far ultraviolet light, an excimer laser, X-rays, and an electron beam. Alternatively, the photoresist layer may be irradiated with an electron beam while being scanned. Thereafter, if necessary, a post-exposure bake treatment (post-exposure bake) may be performed.

[0049] Then, a pattern is developed using a photoresist developer to obtain a desired photoresist pattern. The development method is not particularly limited, and a known method can be adopted. For example, a development method suitable for the purpose can be adopted, such as immersion development in which a substrate coated with photoresist is immersed in a developer for a certain period of time, then washed with water and dried; paddle development in which a developer is dropped onto the surface of the coated photoresist, left to stand for a certain period of time, then washed with water and dried; spray development in which a developer is sprayed onto the surface of the photoresist, then washed with water and dried, etc.

[0050] Next, the conductive metal film, metal oxide film, and insulating film are selectively etched by dry etching or the like using the formed photoresist pattern as a mask to form a fine circuit. Thereafter, unnecessary photoresist layers are removed by plasma ashing, if necessary.

[0051] The step (iii) will be described. When etching or etching and ashing are performed in the step (ii), resist residues and metal depositions generated during etching of the metal film are attached and left as residues on the substrate surface. These residues are removed by immersing or contacting them with the semiconductor device treatment liquid according to this embodiment. By using the semiconductor device treatment liquid according to this embodiment, these residues are easily removed. In particular, the corrosion prevention effect is excellent for a substrate having a metal layer containing metals such as Al, Al alloy, Cu, Cu alloy, and AlCu alloy. Furthermore, in the case of a substrate having a first metal layer containing at least one selected from the group consisting of Al, Al alloy, Cu, Cu alloy, and AlCu alloy, and a second metal layer containing at least one selected from the group consisting of Ti and Ti alloy, the corrosion prevention effect and residue removability can be more excellent.

[0052] The treatment conditions using the semiconductor device treatment liquid according to the present embodiment can be selected in consideration of the configuration, material, and characteristics of the target semiconductor device, as well as the etching and ashing conditions. For example, when the treatment is performed by immersion in the treatment liquid, the immersion time is preferably 1 to 60 minutes, and more preferably 1 to 15 minutes. The temperature during immersion is preferably 5 to 30°C, and more preferably 20 to 25°C.

[0053] After treatment with the semiconductor device treatment liquid, the substrate can be rinsed as necessary. For example, the substrate (or semiconductor device) can be rinsed with at least one selected from the group consisting of methanol, isopropanol, ethylene glycol, water, a mixture of water and a surfactant, and mixtures thereof. After rinsing, the substrate can be dried with nitrogen gas, a spin dry cycle, steam drying, or the like.

[0054] As described above, the semiconductor device treatment liquid according to this embodiment is excellent in removing residues generated after etching, and is also excellent in corrosion prevention effect for a substrate on which a metal layer is formed. Furthermore, it can exert an excellent effect even when used after etching and ashing. As residues, not only residues generated from the resist (resist residues) but also residues generated from the substrate and metal layer (metal oxide residues) can be efficiently removed.

[0055] The semiconductor device processing liquid according to the present embodiment can be an aqueous processing liquid, which not only reduces the environmental load but also allows the processing liquid to be efficiently removed from the processed substrate (semiconductor device) in the subsequent rinsing step. Furthermore, the semiconductor device processing liquid according to the present embodiment can also be used as a processing liquid that does not contain metal ions (metal-free processing liquid). EXAMPLES

[0056] The present invention will be described in more detail with reference to the following examples and comparative examples, but the present invention is not limited to the following examples. In the following, unless otherwise specified, the quantities are based on mass, and the experiments were performed under conditions of 25° C. and atmospheric pressure.

[0057] <Ingredients used>

[0058] The fluorine-containing compound, water, cyclic ether compound, and water-soluble organic solvent used in this example are as follows. Each component was prepared to have the concentration shown in Table 1, to obtain each treatment liquid. The water-soluble organic solvent (d) was prepared as the remainder of each treatment liquid. The mass % value of (d) in Table 1 is shown as the basis for calculating the mass ratio of (d) / (c).

[0059] (a) Fluorine-containing compounds Ammonium fluoride (AF) Hydrogen fluoride (HF) (b) water ·Ultra pure water (DIW) (c) Cyclic ether compounds Ethylene oxide (EO: ethylene oxide, 3-membered ring, 1 oxygen atom) 1,4-Dioxane (DO: 6-membered ring, 2 oxygen atoms) (d) Water-soluble organic solvent Dimethyl sulfoxide (DMSO) N,N-Dimethylformamide (DMF) N-Methyl-2-pyrrolidone (NMP)

[0060] <Example 1>

[0061] A silicon wafer substrate with a TiN / Ti / AlCu / TiN / Ti / SiO2 stack was used for the test. The stack was then dry etched with a chlorine-based gas in a commercially available etching device using a resist pattern as a mask, followed by dechlorination with an oxygen-fluorine mixed gas and removal of the resist pattern by ashing. AlCu is an aluminum-copper alloy. The side of the AlCu in the stack was exposed, and resist residues and TiO-based residues (hereinafter, these may be collectively referred to as "residues") were attached to the side and the surface of the wafer substrate where the stack was not present.

[0062] Next, the wafer substrate was cut into small sample pieces of about 1 cm x about 2 cm, and the small sample pieces were immersed and washed in the treatment liquid of Example 1 (see Table 1) for 5 minutes or 10 minutes. (In the evaluation of the residue removability, the immersion time was 5 minutes, and in the evaluation of the corrosion prevention property against AlCu, the immersion time was 10 minutes.) After immersion, the small sample pieces were taken out and rinsed with ultrapure water. Then, the interface between the AlCu layer and the Ti-containing layer on the side of the stack was observed with an SEM (scanning electron microscope: magnification 20,000 times), and the residue removability and the corrosion prevention property against AlCu were evaluated according to the following criteria.

[0063] <Examples 2 to 11 and Comparative Examples 1 to 4>

[0064] A treatment solution was prepared in the same manner as in Example 1, except that the conditions were changed to those shown in Table 1. Small sample pieces were prepared in the same manner as in Example 1, and the residue removal properties and corrosion prevention properties for AlCu were evaluated according to the following criteria.

[0065] <Evaluation conditions>

[0066] -Evaluation of residue removal ◎: When a small sample piece was immersed in the treatment solution for 5 minutes and then observed with a SEM, the 2 No residue was observed within the imaging area, and the layer interface was visible. ◯: When a small sample piece was immersed in the treatment solution for 5 minutes and then observed with a SEM, the 2 Although some residue was observed within the imaging area, the layer interface was visible. ×: When a small sample piece was immersed in the treatment solution for 5 minutes and then observed by SEM, a residue was observed within the imaging area, and the layer interface could not be confirmed.

[0067] ·Evaluation of corrosion prevention properties for AlCu ⊚: When a small sample piece was immersed in the treatment solution for 10 minutes and then the AlCu surface was observed using an SEM photograph, no corrosion was observed. ◯: No corrosion was observed after a small sample piece was immersed in the treatment solution for 5 minutes, but slight corrosion was observed when the AlCu surface was observed in an SEM photograph after immersion for 10 minutes. △: No corrosion was observed after a small sample piece was immersed in the treatment solution for 5 minutes, but corrosion was confirmed when the AlCu surface was observed in an SEM photograph after immersion for 10 minutes. ×: Corrosion was observed after the small sample piece was immersed in the treatment solution for 5 minutes.

[0068] Table 1 shows the compositions of the treatment solutions of the Examples and Comparative Examples, and Table 2 shows the evaluation results of the Examples and Comparative Examples.

[0069] [Table 1]

[0070] [Table 2]

[0071] From the above, it was at least confirmed that the treatment liquid according to each Example is excellent in removing residues generated after etching, and is also excellent in corrosion prevention effect for a substrate on which a metal layer is formed.

Claims

1. A fluorine-containing compound, Water, A cyclic ether compound, a water-soluble organic solvent other than the cyclic ether compound; A semiconductor device treatment solution comprising:

2. The number of carbon atoms forming a ring in the cyclic ether compound is 2 to 4, and the number of oxygen atoms forming the ring is 1 to 2. The semiconductor device treating solution according to claim 1 .

3. The mass ratio of the water-soluble organic solvent to the cyclic ether compound is 100,000 to 15,000,000; The semiconductor device treating liquid according to claim 1 or 2.

4. The content of the cyclic ether compound is 0.000001% by mass to 10% by mass. The semiconductor device treating liquid according to claim 1 or 2.

5. the semiconductor device includes a substrate having a metal layer including Al; The treatment liquid is used for treatment of the metal layer. The semiconductor device treating liquid according to claim 1 or 2.

6. the semiconductor device includes a substrate having a metal layer containing Cu; The treatment liquid is used for treatment of the metal layer. The semiconductor device treating liquid according to claim 1 or 2.

7. A substrate provided with a metal layer for use in the manufacture of the semiconductor device, 3. The semiconductor device treating solution according to claim 1, which is used to remove residues generated after the substrate is subjected to an etching treatment.

8. forming a resist pattern on a substrate having a metal layer containing Al and / or Cu; dry etching the substrate using the resist pattern as a mask; removing residues from the substrate using a semiconductor device treatment liquid containing a fluorine-containing compound, a water-soluble organic solvent, water, and a cyclic ether compound; A method for treating a substrate comprising the steps of:

9. forming a resist pattern on a substrate having a metal layer containing Al and / or Cu; dry etching the substrate using the resist pattern as a mask; removing residues from the substrate using a semiconductor device treatment liquid containing a fluorine-containing compound, a water-soluble organic solvent, water, and a cyclic ether compound; A method for manufacturing a semiconductor device comprising the steps of:

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