TW201631122A - Etching solution, etching method and preparation method for semiconductor substrate manufacture - Google Patents

Abstract

The present invention provides an etching solution capable of removing the titanium on the substrate, and an etching method using the same and a preparation method for semiconductor substrate manufacture. Further, the present invention also provides an etching solution that can optionally inhibit the damage on the silicon or germanium containing layer on the substrate, in particular on the silicide layer, and also selectively remove the titanium containing layer, an etching method using the same and the method for producing semiconductor substrate manufacture.

Description

Etching liquid, etching method, and method of manufacturing semiconductor substrate product

The present invention relates to an etching solution, an etching method, and a method of manufacturing a semiconductor substrate product.

The fabrication of integrated circuits involves multiple stages of processing steps. In the manufacturing process, stacking, lithography, etching, etc. of various materials are repeated several times. Among them, etching becomes an important process. It is necessary to selectively etch a specific material and leave other materials without corrosion. It is sometimes required to remove only a predetermined layer in a form in which one of such a layer containing a similar metal species or a layer containing a more corrosive material remains. In recent years, the size of wiring or integrated circuits in a semiconductor substrate has become smaller and smaller, and the importance of accurately etching without causing corrosion of a member to be left is increased. In the case of a field effect transistor, as a result of rapid miniaturization, thin film formation of a germanide layer formed on the upper surface of the source region and/or the drain region or development of a novel material is strongly demanded. In a self-aligned silicide process (Salicide: Self-Aligned Silicide) for forming the germanide layer, a part of the source region and the drain region including germanium formed on the semiconductor substrate, and a portion attached to the upper surface thereof The metal layer is annealed. Thereby, a low-resistance telluride layer can be formed on the upper side of the source electrode and/or the drain electrode. After the self-aligned deuteration step, the metal layer remaining therein is removed by etching. This etching is usually performed by wet etching, and as a chemical liquid, a mixture of hydrochloric acid and nitric acid (Aqua regia) is applied. Patent Document 1 discloses an example in which a chemical solution containing toluenesulfonic acid other than nitric acid and hydrochloric acid is used as a method of removing Ni and Pt. [Prior Art Document] [Patent Literature]

[Patent Document 1]: International Publication No. 2012/125401

[Problem to be Solved by the Invention] An object of the present invention is to provide an etching solution capable of removing titanium on a substrate, an etching method using the same, and a method of manufacturing a semiconductor substrate product. Further, an object of the present invention is to provide an etching method capable of suppressing damage of a layer containing ruthenium or ruthenium on a substrate, particularly a ruthenium layer thereof, and selectively removing a layer containing titanium. And a method of manufacturing a semiconductor substrate product. [Means for solving the problem]

The problem can be solved by the following means. [1] An etching liquid which is an etching liquid for a semiconductor process and which contains a fluorine ion and a substituted hydroquinone compound. [2] The etching solution according to [1], which contains an organic solvent. [3] The etching solution according to [1] or [2] which contains water. [4] The etching liquid according to any one of [1] to [3] wherein the concentration of the fluorine ions is 0.1% by mass or more and 20% by mass or less. [5] The etching solution according to any one of [1] to [4] wherein the concentration of the substituted hydroquinone compound is 0.1% by mass or more and 10% by mass or less. [6] The etching solution according to [2], wherein the concentration of the organic solvent is 50% by mass or more and 98% by mass or less. [7] The etching solution according to [3], wherein the concentration of the water is 0.1% by mass or more and 50% by mass or less. [8] The etching solution according to any one of [1] to [7] wherein the substituted hydroquinone compound is represented by the following formula (H1). [Chemical 1] R ^H1 represents a substituent. M1 represents an integer of 1 to 4. [9] The etching solution according to [8], wherein R ^H1 is a hydrocarbon group. [10] The etching solution according to [9], wherein R ^H1 is an alkyl group. [11] The etching solution according to any one of [1] to [10] wherein the substituted hydroquinone compound has a ClogP value of 1 or more and 10 or less. [12] The etching solution according to any one of [1] to [11] wherein the substituted hydroquinone compound is 2,5-di-t-butyl hydroquinone, 2-third Butyl hydroquinone, 2,5-dimethyl hydroquinone, or 2-methyl hydroquinone. [13] The etching solution according to any one of [1] to [12] wherein the corrosion potential of the substituted hydroquinone compound with respect to the ruthenium substrate is -0.25 or more and 0.5 or less. [14] The etching solution according to [2], wherein the organic solvent contains an alcohol compound or an ether compound. [15] The etching solution according to [2], wherein the organic solvent contains a compound represented by the following formula (O-1). R ^O1 -(-OR ^O2 -) _n -OR ^O3 ····(O-1) R ^O1 and R ^O3 are each independently a hydrogen atom, an alkyl group having 1 to 12 carbon atoms, or an aryl group having 6 to 14 carbon atoms. Or an aralkyl group having 7 to 15 carbon atoms. R ^O2 is a linear or branched alkyl chain having 1 or more and 12 or less carbon atoms. When there are a plurality of R ^{O 2} , each R ^{O 2} may be different. n is an integer of 0 or more and 12 or less. Wherein, when n is 0, R ^O1 and R ^{O3 are} not hydrogen atoms at the same time. [16] The etching solution according to any one of [1] to [15] wherein the substrate for semiconductor processing has a layer containing titanium and a layer containing titanium telluride. [17] The etching solution according to [16], wherein a value obtained by dividing an etching rate of the titanium-containing layer by an etching rate of the titanium telluride-containing layer is 4 or more and 15 or less. [18] An etching method using the etching liquid according to any one of [1] to [17] to perform etching of a layer containing titanium. [19] The etching method according to [18], wherein the etching of the titanium-containing layer is performed while suppressing etching of titanium oxide. [20] A method of producing a semiconductor substrate article, which is produced by the etching method according to [18] or [19]. [Effects of the Invention]

According to the etching liquid of the present invention, the etching method using the same, and the method of manufacturing a semiconductor substrate product, titanium on the substrate can be removed. Further, it is possible to suppress damage of the layer containing ruthenium or ruthenium on the substrate, particularly the ruthenide layer thereof, and selectively remove the layer containing titanium. The above and other features and advantages of the present invention will become apparent from the accompanying drawings.

First, according to Fig. 1 (a), Fig. 1 (b), Fig. 1 (c), Fig. 2 (A), Fig. 2 (B), Fig. 2 (C), Fig. 2 (D) and Fig. 2 (E) A preferred embodiment of the etching step related to the application of the etching solution of the present invention will be described.

[Etching Step] FIGS. 1(a), 1(b), and 1(c) are views showing a semiconductor substrate before and after etching. In the production example of the present embodiment, a metal layer (second layer) 1 is disposed on the upper surface of the layer (first layer) 2 containing silicon or germanium. As a layer (first layer) containing ruthenium or osmium, a Si epitaxial layer constituting a source electrode and a drain electrode is applied. The first layer may comprise Si, or may be a SiGe epitaxial layer or a Ge epitaxial layer.

As a constituent material of the metal layer (second layer) 1, titanium (Ti) can be used. For the formation of the metal layer, a method of forming such a metal film can be generally used. Specifically, a film formation by chemical vapor deposition (CVD) can be mentioned. The thickness of the metal layer at this time is not particularly limited, and examples of the film of 5 nm or more and 50 nm or less are mentioned. In the present invention, when the metal layer is a Ti layer, the removal performance of the etching liquid is sufficiently exhibited, which is preferable. In addition to the listed metal atoms, the metal layer may contain other elements. For example, there may be oxygen or nitrogen that is inevitably mixed. The amount of unavoidable impurities is preferably suppressed to, for example, about 1 ppt to 10 ppm (mass basis). Further, in the semiconductor substrate, in addition to the above materials, there are cases in which materials which are not desired to be etched are present. In the etching liquid of the preferred embodiment of the present invention, it is preferable to further suppress corrosion or the like of such a material.

In the step (a) of FIG. 1, after the metal layer 1 is formed on the upper side of the layer 2 containing ruthenium or osmium, annealing (sintering) is performed, and a metal-Si reaction film is formed on the interface (third layer: telluride) Layer) 3 (step (b) of Figure 1). The annealing may be carried out by a condition generally applied to the production of such a device, and for example, it may be treated at 200 ° C to 1000 ° C. The thickness of the vaporized layer 3 at this time is not particularly limited, and examples thereof include a layer of 50 nm or less, and examples of the layer of 10 nm or less are also exemplified. The lower limit is not particularly present, but it is more than 1 nm. The telluride layer can be used as a low-resistance film, and functions as a conductive portion that electrically connects a source electrode and/or a drain electrode located at a lower portion thereof to a wiring disposed on an upper portion thereof. Therefore, if defects or corrosion occur in the telluride layer, the conduction is hindered, and the quality such as erroneous operation of components may be degraded. In particular, recently, the integrated circuit structure inside the substrate is being miniaturized, and even a slight damage may have a large influence on the performance of the element. Therefore, it is desirable to prevent such defects and corrosion as much as possible.

In the present specification, in a broad sense, a telluride layer is a concept included in a layer containing ruthenium or osmium of the first layer. Therefore, when the second layer is selectively removed with respect to the first layer, it means that the morphology of the second layer (metal layer) is preferentially removed not only with respect to the undeuterated layer containing ruthenium or osmium, but also includes The morphology of the second layer (metal layer) is preferentially removed. In a narrow sense, when the first layer of germanium or germanium containing layers (excluding the germanide layer) is distinguished from the third layer of germanide layer, it is referred to as the first layer and the third layer, respectively. Furthermore, the layer of germanium may be any of single crystal germanium, polycrystalline germanium or amorphous germanium. Further, when it is simply referred to as a vaporized layer, it means a composite metal layer formed by annealing each metal. Thus, when referred to as titanium telluride, it is meant to include not only tellurides of titanium and tantalum, but also tellurides comprising titanium and tantalum and niobium, or tellurides comprising titanium and niobium. In the present invention, it is preferably applied to a telluride layer (TiSi) containing titanium and tantalum or a telluride layer (TiSiGe) containing titanium, hafnium, and tantalum from the viewpoint that the effect becomes remarkable. More preferably, it is applied to the protection of a telluride layer (TiSi) containing titanium and tantalum.

Then, etching of the remaining metal layer 1 is performed (step (b) -> step (c) of Fig. 1). In the present embodiment, at this time, the etching liquid is applied, and the etching liquid is applied from the upper side of the metal layer 1 to make contact, thereby removing the metal layer 1. The form of application of the etching liquid will be described later. The layer 2 containing ruthenium or osmium may include a Si epitaxial layer or a SiGe epitaxial layer, and is formed by crystal growth of a ruthenium substrate having a specific crystallinity by a chemical vapor deposition (CVD) method. Alternatively, an epitaxial layer formed with desired crystallinity may be formed by a molecular beam epitaxy (MBE) method or the like. In order to make the layer containing ruthenium or osmium a P-type layer, boron (B) having a doping concentration of about 1 × 10 ¹⁴ cm ^-3 to 1 × 10 ²¹ cm ^{-3 is} preferable. In order to form an N-type layer, phosphorus (P) or arsenic (As) is preferably doped at a concentration of 1 × 10 ¹⁴ cm ^-3 to 1 × 10 ²¹ cm ^-3 .

When the first layer is a SiGe epitaxial layer, the Ge concentration thereof is preferably 20% by mass or more, more preferably 40% by mass or more. The upper limit is preferably 100% by mass or less, and more preferably 90% by mass or less. Further, when the ruthenium is 100% by mass, the layer formed by the alloy accompanying the second layer by annealing thereof contains bismuth and a specific metal element of the second layer, and does not contain ruthenium, but as described above, in the present specification For convenience of explanation, it is referred to as the "deuterated" layer. In the present specification, the concentration of ruthenium is a value measured by the following measurement method. Electrode Spectroscopy for Chemical Analysis (ESCA) (product name: Quantera, manufactured by ULVAC-PHI, Japan), for the substrate of a layer containing germanium (Ge) The depth direction from 0 nm to 30 nm was analyzed, and the average value of the Ge concentration in the analysis results of 3 nm to 15 nm was defined as the Ge concentration (% by mass).

After the self-aligned deuteration step, between the layer containing the germanium or antimony (first layer) and the metal layer (the second layer), a vaporized layer is formed as containing germanium (Si) or germanium (Ge) and second A layer of the composition of the layer (the particular metal species). The telluride layer is broadly included in the first layer, but is referred to as a "third layer" when it is distinguished from the first layer in a narrow sense. If the composition is Si _x Ge _y M _z (M: metal element), it is preferably set to x + y + z = 1, and 0.2 ≦ x + y ≦ 0.8, more preferably 0.3 ≦ x + Y≦0.7. With respect to z, it is preferably 0.2 ≦ z ≦ 0.8, more preferably 0.3 ≦ z ≦ 0.7. A preferred range of the ratio of x to y is preferably y = 0 (without Ge), and when Ge is contained, as specified. Among them, other elements may also be contained in the third layer. This aspect is the same as described in the metal layer (second layer).

(Processing of MOS transistor) FIGS. 2(A), 2(B), 2(C), 2(D), and 2(E) are process diagrams showing a manufacturing example of the MOS transistor. 2(A) shows the formation steps of the MOS transistor structure, FIG. 2(B) shows the sputtering process of the metal film, FIG. 2(C) shows the first annealing step, and FIG. 2(D) shows the selection of the metal film. The removal step, FIG. 2(E), is the second annealing step. As shown in the figure, the gate electrode 23 is formed via the gate insulating film 22 formed on the surface of the germanium substrate 21. An extension region may be additionally formed on both sides of the gate electrode 23 of the germanium substrate 21. A protective layer (not shown) that prevents contact with the Ti layer can be formed on the upper side of the gate electrode 23. Further, a sidewall 25 including a hafnium oxide film or a tantalum nitride film is formed, and a source region 26 and a drain region 27 are formed by ion implantation. Then, as shown in the figure, the Ti film 28 is formed and subjected to rapid annealing treatment. Thereby, the element in the Ti film 28 is diffused into the ruthenium substrate to be deuterated (in the present specification, when ruthenium is 100% by mass, for convenience of explanation, the alloying by annealing is referred to as deuteration). As a result, the upper portions of the source electrode 26 and the drain electrode 27 are deuterated to form a TiSi (Ge) source electrode portion 26A and a TiSi (Ge) drain electrode portion 27A. At this time, the second annealing is performed as shown in FIG. 2(E), whereby the electrode member is changed to a desired state (annealed telluride source electrode 26B, annealed telluride bungee Electrode 27B). The first and second annealing temperatures are not particularly limited, and can be, for example, 400 to 1100 °C.

The Ti film 28 remaining without contributing to deuteration can be removed by using the etching liquid of the present invention (Fig. 2(C), Fig. 2(D)). At this time, the person shown in the figure is largely patterned, and the Ti film remaining on the upper portion of the deuterated layers (26A, 27A) is optional. The structure of the semiconductor substrate or its product is also simplified, and may be explained as necessary as necessary.

As a preferable example of a constituent material, the following aspects are exemplified. 21 矽 Substrate: Si, SiGe, Ge 22 Gate insulating film: HfO ₂ (high dielectric constant (High-k)) 23 Gate electrode: Al, W 25 Sidewall: SiOCN, SiN, SiO ₂ (low dielectric constant (low-k) 26 source electrode: Si, SiGe, Ge 27 汲 electrode: Si, SiGe, Ge 28 metal layer: Ti not shown cover: TiN The semiconductor substrate to which the etching liquid of the present invention is applied is described above. Examples, but not limited to this specific example, can also be applied to other semiconductor substrates. For example, a semiconductor substrate including a high dielectric film/Fin Field Effect Transistor (FinFET) having a germanide pattern on a source region and/or a drain region can be cited.

Here, when referring to the residual telluride layer (third layer) or the layer (first layer) of ruthenium or the like, and only the difficulty of removing the metal layer (second layer) of the upper layer, it is exemplified that the bismuth layer includes The removed metal constitutes this aspect. That is, when a solution component having high solubility is used in order to improve the removability of the metal layer, the telluride layer containing the metal is also easily dissolved. Further, when a component having a high solubility of a metal (such as Ti, Pt, or Ni) which forms a telluride is applied, it is usually a direction in which solubility is also exhibited for bismuth (Si) and germanium (Ge). Therefore, the solubility of the metal layer is improved, and on the other hand, the damage of the telluride layer or the like is suppressed from becoming the opposite direction. According to a preferred embodiment of the present invention, such a difficult-to-existing property can be achieved, and a bismuth layer or the like remaining as a semiconductor substrate product can be protected, and a metal layer located on the upper side or the like can be effectively removed.

[Etching Solution] Next, a preferred embodiment of the etching liquid of the present invention will be described. The etching solution of this embodiment contains a fluorine ion and a substituted hydroquinone compound. Here, the substitution of the hydroquinone compound means the removal of the unsubstituted compound in the hydroquinone compound. In the etching solution, an organic solvent or water may be contained as needed. Preferably, it is preferable that the etching liquid contains substantially only fluorine ions, counter ions, substituted hydroquinone compounds, water, and an organic solvent. Here, "substantially" means that unavoidable impurities or trace addition components may be contained within the range in which the effects of the present invention are exerted. Hereinafter, each component will be described.

(Fluoride) The fluorine ion is contained in the etching liquid of the present invention. It can be understood that in the etching liquid, the fluorine ions become a ligand (a complexing agent) of the metal (Ti or the like) of the second layer and function to promote dissolution. The concentration of the fluorine ion in the etching liquid is preferably 0.1% by mass or more, more preferably 0.5% by mass or more, and particularly preferably 1% by mass or more. The upper limit is preferably 20% by mass or less, more preferably 10% by mass or less, still more preferably 5% by mass or less, and particularly preferably 2% by mass or less. It is preferred to apply a fluoride ion at the concentration to achieve good etching of the metal layer and to achieve effective protection of the layer of tantalum or niobium or the vaporized layer thereof. Further, when the amount of the compound is confirmed, the amount of the fluorine compound (salt) at the time of production can be quantified to specify the amount of the fluoride ion. The fluorine-containing compound may be used singly or in combination of two or more. As a supply source of a fluorine ion, the following list is mentioned. In the present invention, among them, hydrofluoric acid (HF) is preferred.

[Table A]

(Substituted hydroquinone compound) The etchant of the present invention contains a substituted hydroquinone compound (preferably an alkyl-substituted hydroquinone). The substituted hydroquinone compound broadly comprises a compound having a hydroquinone skeleton having a substituent. In the etching solution of the present invention, it is understood that the substituted hydroquinone compound can synergize with the fluoride ion to achieve appropriate metal removal and a layer containing ruthenium or osmium (preferably a ruthenium layer). Protective. In addition, it is understood that in the system containing a fluoride ion, the difference in hydrophilicity between Ti and Si (the latter is hydrophobic), and the specific hydroquinone skeleton in the highly hydrophobic compound. The compound is excellent in the adsorptivity (protective property) of the telluride layer or the like. As a result, it is considered that the substituted hydroquinone compound forms a specific adsorption layer with respect to the telluride layer or the like, and exhibits an effect of suppressing excessive damage (dissolution) of the fluorine ions. On the other hand, it can be understood that the action (the dissolution of the metal, etc.) expected for the fluorine ion is not inhibited, and as a result, the removal property of the metal layer and the excellent protection against the vapor layer and the like are exhibited at the same time.

The substituted hydroquinone compound is preferably represented by the following formula (H1). [Chemical 2]

R ^H1 represents a substituent. The substituent is preferably an alkyl group (the number of carbon atoms is preferably from 1 to 12, more preferably from 2 to 6, particularly preferably from 2 to 4), and the alkenyl group (the number of carbon atoms is preferably from 2 to 12, more preferably 2). ～6), aryl (carbon number is preferably 6 to 22, more preferably 6 to 14, particularly preferably 6 to 10), aralkyl (carbon number is preferably 6 to 22, more preferably 6 to 14) , particularly preferably 6 to 10), a hydroxyl group-containing group, a carboxyl group-containing group, a thiol group (thio group) group, and an amine group-containing group (the carbon number of the amine group is preferably 0 to 6, more preferably It is 0 to 3). The linking group containing a hydroxyl group, a carboxyl group-containing group, a thiol group-containing group, or an amine group-containing group is preferably a form having no linking group (single bond). When the linking group is contained, the linking group is preferably an alkyl group (having preferably 1 to 12 carbon atoms, more preferably 1 to 6 carbon atoms, particularly preferably 1 to 3 carbon atoms), and an alkenyl group (preferably having 2 carbon atoms). ～12, more preferably 2 to 6), O, CO, NR ^N , S, or a group related thereto. The number of atoms constituting the linking group is preferably from 1 to 12, more preferably from 1 to 6, particularly preferably from 1 to 3, in addition to a hydrogen atom. The number of linking atoms of the linking group is preferably 10 or less, more preferably 8 or less, and particularly preferably 3 or less. The lower limit is 1 or more. The number of linked atoms refers to the minimum number of atoms located on a path connecting the predetermined structural portions and participating in the joining. For example, in the case of -CH ₂ -C(=O)-O-, the number of atoms constituting the linking group becomes 6, but the number of linking atoms becomes 3.

Among them, R ^{H1 is} preferably a hydrocarbon group, and is preferably an alkyl group, an alkenyl group, an aryl group or an aralkyl group each having the above carbon number, and more preferably an alkyl group. In the substituted hydroquinone compound, hydrophobicity can be imparted to the present compound by selecting a hydrocarbon group as the substituent R ^H1 . Thereby, the desired etching selectivity can be obtained, which is particularly preferable.

M1 represents an integer of 1 to 4, preferably an integer of 1 to 3, preferably 1 or 2. When m1 is 2 or more, a plurality of R ^H1 may form a ring. Here, as the ring to be formed, a 3-membered ring to a 7-membered ring is preferable, and a 5-membered ring or a 6-membered ring is preferable. As an example of the ring structure, it may be an aromatic ring or an aliphatic ring. Further, it may be a hydrocarbon ring or a heterocyclic ring. Among them, in the present invention, an aliphatic ring is preferred, and an aliphatic ring of a hydrocarbon is more preferred. Specifically, the C=C bond of the hydroquinone skeleton is regarded as a double bond, and examples thereof include a cyclohexene ring, a cyclopentene ring, and a cyclobutene ring.

Specific examples of the substituted hydroquinone compound include 2,5-di-t-butyl hydroquinone, 2-t-butyl hydroquinone, and 2,5-dimethyl pair. Hydroquinone, 2-methylhydroquinone, and the like.

The ClogP value of the substituted hydroquinone compound is preferably 1 or more, more preferably 2 or more, and particularly preferably 3.5 or more. There is no particular upper limit, but it is actually 10 or less. The ClogP value is a value obtained by calculating a common logarithm logP of the partition coefficient P of 1-octanol and water. Regarding the method or software for calculating the ClogP value, a usual method or software can be used, and the ClogP program incorporated in ChemSoftDraw Ultra 12.0 of Cambridge Soft Co., Ltd. is used in the present invention unless otherwise specified. By setting the ClogP value of the substituted hydroquinone compound to the above range, the present compound can be made hydrophobic and obtains good etching selectivity, which is preferable.

In the present invention, the concentration of the substituted hydroquinone compound in the etching solution is preferably 10% by mass or less, more preferably 7% by mass or less, still more preferably 5% by mass or less, and particularly preferably 3% by mass or less. . The lower limit is preferably 0.01% by mass or more, more preferably 0.05% by mass or more, still more preferably 0.1% by mass or more, and particularly preferably 0.5% by mass or more. The substituted hydroquinone compound may be used alone or in combination of two or more. When two or more types are used in combination, the ratio of the combined use is not particularly limited, but the total amount used is preferably a total of two or more of the above concentration ranges.

(Organic solvent) An organic solvent may be contained in the etching liquid of the present invention. Among them, the organic solvent is preferably a protic polar organic solvent (wherein, when a protic polar organic solvent is used, it is not inhibited from being used in combination with an aprotic polar organic solvent). As the protic polar organic solvent, an alcohol compound solvent can be mentioned. Among them, the carbon number is preferably from 1 to 36, more preferably from 2 to 24, still more preferably from 4 to 18, particularly preferably from 4 to 12. The organic solvent is preferably an alcohol compound or an ether compound, and more preferably an alcohol compound. As a specific example, the following are mentioned. The alcohol compound may, for example, be methanol, ethanol, 1-propanol, 2-propanol, 2-butanol, ethylene glycol, propylene glycol, glycerin, 1,6-hexanediol, cyclohexanediol, sorbitol, Xylitol, polyethylene glycol (diethylene glycol and triethylene glycol, etc.), polypropylene glycol (dipropylene glycol and tripropylene glycol, etc.), 2-methyl-2,4-pentanediol, 1,3-butyl Glycol and 1,4-butanediol. Alternatively, examples of the alkylene glycol monoalkyl ether include ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monobutyl ether, propylene glycol monomethyl ether, and diethylene glycol. Monomethyl ether, triethylene glycol monomethyl ether, tetraethylene glycol monomethyl ether, dipropylene glycol monomethyl ether, tripropylene glycol monomethyl ether, diethylene glycol monobutyl ether and dipropylene glycol monobutyl Ether and the like.

Among them, the organic solvent is preferably a compound represented by the following formula (O-1). R ^O1 -(-OR ^O2 -) _n -OR ^O3 ···(O-1) ·R ^O1 R ^O1 and R ^O3 are each independently a hydrogen atom and have a carbon number of 1 to 12 (preferably 1 to 6, more preferably It is preferably an alkyl group of 1 to 3), an aryl group having 6 to 14 carbon atoms (preferably 6 to 10) or an aralkyl group having 7 to 15 carbon atoms (preferably 7 to 11). Among them, R ^{O3 is} preferably a hydrogen atom. R ^O2 R ^O2 is an alkylene group having 1 or more carbon atoms and 12 or less carbon atoms. When there are a plurality of R ^{O 2} , each R ^{O 2} may be different. R ^{O2 is} preferably a carbon number of 2 to 10, more preferably a carbon number of 2 to 6, and particularly preferably a carbon number of 2 to 4. R ^O2 may be linear or branched, and may also have a ring structure. Nn is an integer of 0 or more and 12 or less, preferably 0 or more and 6 or less. When n is 2 or more, a plurality of R ^O2s may be different from each other. Further, when n = 0, R ^O1 and R ^{O3 are} not hydrogen atoms at the same time. R ^O1 to R ^O3 may be bonded to each other to form a ring. Here, as the ring to be formed, a 3-membered ring to a 7-membered ring is preferable, and a 5-membered ring or a 6-membered ring is preferable. For example, a compound in which R ^O1 and R ^{O2 are} bonded to each other to form a tetrahydrofuran structure or a tetrahydropyran structure, and in which -OR ^O3 is substituted may be mentioned.

The concentration of the organic solvent in the etching solution is preferably 99% by mass or less, more preferably 98% by mass or less, still more preferably 97% by mass or less, and particularly preferably 96% by mass or less. The lower limit is preferably 50% by mass or more, more preferably 60% by mass or more, still more preferably 70% by mass or more, still more preferably 80% by mass or more, and particularly preferably 90% by mass or more. By setting the organic solvent to the above range, the concentration of water can be lowered. On the other hand, the action of the fluoride ion or the substituted hydroquinone compound can be appropriately promoted, and the good etching property of the metal layer (second layer) and the protective property of the first layer or the third layer can be achieved, so that Preferably. Furthermore, in the present invention, the organic solvent may be used alone or in combination of two or more. When two or more types are used in combination, the ratio of the combined use is not particularly limited, but the total amount used is preferably a total of two or more of the above concentration ranges.

In the present specification, when a compound, a substituent, a linking group or the like contains an alkyl group, an alkylene group, an alkenyl group, an alkenyl group, an alkynyl group and/or an alkynyl group, these may be cyclic or chain. Further, it may be a straight chain, may be branched, may be substituted by any base, or may be unsubstituted. In this case, an alkyl group, an alkylene group, an alkenyl group, an alkenyl group, an alkynyl group, and an alkynyl group may be substituted with a hetero atom-containing group (for example, O, S, CO, and NR ^N ), or may be formed therewith. Ring structure. Further, when an aryl group, a heterocyclic group or the like is contained, the one may be a monocyclic ring or a condensed ring, and may be substituted or unsubstituted. The R ^N is a hydrogen atom or a substituent. The substituent is preferably an alkyl group (the number of carbon atoms is preferably from 1 to 24, more preferably from 1 to 12, still more preferably from 1 to 6, particularly preferably from 1 to 3), and an alkenyl group (preferably, the carbon number is preferably 2 to 24, more preferably 2 to 12, still more preferably 2 to 6, particularly preferably 2 to 3), an alkynyl group (the carbon number is preferably 2 to 24, more preferably 2 to 12, and still more preferably 2 to 6, particularly preferably 2 to 3), an aryl group having 6 to 10 carbon atoms, and an aralkyl group having 7 to 11 carbon atoms. In the present specification, each of technical matters such as temperature and thickness, which are based on the substituents of the compound and the selection of the linking group, may be independently described in the list or may be combined with each other. In the present specification, when a specific compound such as a compound or an acid is labeled at the end, it is also included in the range of the effect of the present invention, in addition to the compound, an ion and a salt thereof. In addition, the derivative is also included in the same manner.

(Water) The etching liquid of the present invention preferably contains water (aqueous medium). The water (aqueous medium) may be an aqueous medium containing a dissolved component in the range which does not impair the effects of the present invention, or may contain an unavoidable trace mixed component. Among them, water subjected to purification treatment such as distilled water, ion-exchanged water, or ultrapure water is preferable, and ultrapure water used in semiconductor production is particularly preferably used. The concentration of the water is not particularly limited, but is preferably 0.01% by mass or more, preferably 0.1% by mass or more, and particularly preferably 1% by mass or more in the etching solution. The upper limit is preferably 50% by mass or less, more preferably 35% by mass or less, still more preferably 15% by mass or less, still more preferably 10% by mass or less, and particularly preferably 5% by mass or less. In the present invention, it is preferred to set the concentration of water in the etching solution to a predetermined range. In the absence of water, the etching action of the metal layer may not be sufficiently exhibited. From this point of view, it is preferred to apply water, and it is preferable to suppress the amount of ruthenium or osmium, and further damage the ruthenium layer and other metal layers to be protected by suppressing the amount thereof to an appropriate amount.

(Surfactant) A surfactant may be contained in the etching solution of the present invention. The surfactant is not particularly limited, and an anionic surfactant, a cationic surfactant, a nonionic surfactant, a surfactant containing a polymer compound, a fluorine-based surfactant, or a polyoxyalkylene group can be suitably used. It is a surfactant and the like. The concentration of the surfactant is preferably 20% by mass or less, more preferably 10% by mass or less, and still more preferably 1% by mass or less based on the total amount of the etching liquid. The lower limit is preferably 0.001% by mass or more, and more preferably 0.005% by mass or more. The surfactants may be used alone or in combination of two or more.

(pH Adjusting Agent) A pH adjusting agent can also be used in the etching liquid of the present invention. As the pH adjuster, in order to raise the pH, a quaternary ammonium salt such as tetramethylammonium or choline, an alkali hydroxide or alkaline earth salt such as potassium hydroxide, an amine compound such as 2-aminoethanol or hydrazine can be used. In order to lower the pH, a mineral acid such as carbonic acid, hydrochloric acid, nitric acid, sulfuric acid or phosphoric acid, or formic acid, acetic acid, propionic acid, butyric acid, valeric acid, 2-methylbutyric acid, n-hexanoic acid or 3,3-dimethylidene may be mentioned. Butyric acid, 2-ethylbutyric acid, 4-methylpentanoic acid, n-heptanoic acid, 2-methylhexanoic acid, n-octanoic acid, 2-ethylhexanoic acid, benzoic acid, glycolic acid, salicylic acid, glycerol Acid, oxalic acid, malonic acid, succinic acid, glutaric acid, adipic acid, pimelic acid, maleic acid, phthalic acid, malic acid, tartaric acid, citric acid and lactic acid. The amount of the pH adjuster to be used is not particularly limited as long as it is used in an amount required to adjust the pH to the above range. The pH adjusters may be used alone or in combination of two or more.

(Corrosion Potential) The etching liquid of the present invention is preferably adjusted in such a corrosion potential. Specifically, the corrosion potential defined by the measurement method proposed in the examples described later is preferably -0.25 or more, more preferably -0.2 or more, further preferably -0.1 or more, and still more preferably 0 or more. Very good is 0.1 or more. As the upper limit, it is practically 0.5 or less.

(Set) The etching liquid in the present invention can be a set in which the raw material is divided into a plurality of parts. For example, a liquid composition containing the fluorine ion in an aqueous medium is used as the first liquid, and a liquid composition containing the substituted hydroquinone compound in the aqueous medium is prepared as the second liquid. As an example of use, it is preferred to mix the two liquids to prepare a liquid for the etching liquid, and then apply it to the etching treatment in a timely manner. The organic solvent or the like may contain either one. In this manner, the deterioration of the liquid property is not caused by the decomposition of the substituted hydroquinone compound, and the desired etching action can be effectively exerted. The concentration of the fluoride ion in the first liquid or the concentration of the substituted hydroquinone compound in the second liquid can be appropriately set in the form of the concentration after mixing based on the amount of the one liquid described above.

(Concentrate) The etching solution of the present invention can be prepared as a concentrate. In this case, when used, it can be used by dilution with water.

(Container) The etching liquid of the present invention (whether or not it is a set) can be stored in a container, stored, transported, and used as long as it does not cause problems such as corrosiveness. Further, for semiconductor applications, it is preferred that the container has a high degree of cleanliness and a small amount of impurities are eluted. As a usable container, a "Clean Bottle" series manufactured by Aicello Chemical Co., Ltd., and a Pure Bottle manufactured by Kodama Plastics Co., Ltd. can be cited. (all are product names), etc., but are not limited to these containers.

(Impurities, Particles) The etching liquid of the present invention is preferably an impurity in a liquid, for example, a metal component, etc., in view of its use. In particular, the Na, K, and Ca ion concentrations in the liquid are preferably in the range of 1 ppt to 1 ppm (mass basis) or less. In order to achieve such an ion concentration, when preparing the constituent component (raw material) of the etching liquid of the present application, it is preferable to select a material having a small metal component, and in particular, Na, K, and Ca ions can be recommended for the organic solvent. An organic solvent having a concentration of 1 ppt to 1 ppm (mass basis). The organic solvent of the examples described later is such that the Na, K, and Ca ion concentrations are within the range. Further, in the etching liquid, the number of coarse particles (particles) having an average particle diameter of 0.5 μm or more is preferably in the range of 100/cm ³ or less, and preferably in the range of 50 / cm ³ or less.

[Etching Condition] As an application example of the etching liquid, it is preferable to prepare an etching liquid, and thereafter apply it to the form of the etching processing as appropriate. Thereby, the deterioration of the liquid property caused by the decomposition of each component is not caused, and the desired etching action can be effectively exhibited. Here, the term "in time" after mixing means a period from the time of mixing to the loss of a desired effect, and specifically, it is preferably within 60 minutes, more preferably within 30 minutes, and even more preferably within 10 minutes. Very good for less than 1 minute. There is no particular lower limit, but it is more than 1 second.

As will be described with reference to Fig. 3, the prepared etching liquid is ejected from the ejection port 13 and applied to the upper surface of the semiconductor substrate S in the processing container (processing tank) 11. In the embodiment shown in the figure, the chemical liquid is supplied from A, and is transferred to the discharge port 13 via the branching point 14 and the flow path fc. The flow path fd represents a return path for recycling the medical liquid. The semiconductor substrate S is preferably located on the turntable 12 and rotated together with the turntable by the rotary drive unit M. Further, the branching point 14 can be exemplified as a switching valve, and the supply and return of the chemical liquid can be switched to perform processing. Alternatively, a valve that adjusts the flow direction of the supply and return of the chemical solution at the same time may be applied.

Further, the etching liquid of the present invention is preferably an impurity in a liquid, for example, a metal component, etc., in view of its use. In particular, the ion concentration of each of Na, K, and Ca in the liquid is preferably in the range of 1 ppt to 1 ppm (mass basis). Further, in the etching liquid, the number of coarse particles having an average particle diameter of 0.5 μm or more is preferably in the range of 100 pieces/cm ³ or less, and preferably in the range of 50 pieces/cm ³ or less.

In the present invention, it is preferred to use a single wafer processing device. Specifically, the single wafer processing apparatus preferably includes a processing tank, and the semiconductor substrate is transported or rotated by the processing tank, and the etching is performed (discharged, ejected, flowed, dropped, etc.) into the processing tank. Liquid, which causes the etching liquid to contact the semiconductor substrate. As an advantage of the single-wafer processing apparatus, (i) a fresh etching liquid is always supplied, so that reproducibility is good and (ii) in-plane uniformity is high. The management temperature at the time of temperature adjustment of the wire is preferably set to the same range as the processing temperature to be described later. The single wafer processing apparatus preferably includes a nozzle in the processing tank, and preferably a method in which the nozzle swings in the surface direction of the semiconductor substrate to eject an etching liquid onto the semiconductor substrate. Thereby, deterioration of the liquid can be prevented, and it is preferable. Moreover, it is preferable to divide into two types of liquids by setting it as a kit, and it is preferable to make a gas etc. difficult, and it is preferable.

The treatment temperature for etching is preferably 10 ° C or higher, more preferably 20 ° C or higher. The upper limit is preferably 80 ° C or lower, more preferably 70 ° C or lower, further preferably 60 ° C or lower, more preferably 50 ° C or lower, and particularly preferably 40 ° C or lower. By setting it as the said lower limit or more, it is preferable to ensure sufficient etching rate of a 2nd layer. By setting it as the said upper limit or less, it is preferable to maintain the time-lapse stability of the etching process speed. In addition, the treatment can be performed at around room temperature, thereby reducing energy consumption. Further, the processing temperature of the etching is based on the temperature applied to the substrate in the temperature measuring method described in the examples below, but it can also be set at the storage temperature or in the case of management by batch processing. The internal temperature is set, and when it is managed by the circulation system, it is set by the temperature in the circulation flow path.

The supply rate of the etching liquid is not particularly limited, but is preferably 0.05 L/min to 5 L/min, and more preferably 0.1 L/min to 3 L/min. By setting it as the said lower limit or more, the uniformity of the in-plane of etching is more favorable, and it is preferable. By setting it as the said upper limit or less, it is preferable to ensure stable performance at the time of continuous process. When the semiconductor substrate is rotated, depending on the size and the like, it is preferable to rotate at 50 rpm to 1000 rpm from the same viewpoint as described above.

In the etching of the single wafer process according to the preferred embodiment of the present invention, it is preferable that the semiconductor substrate is transferred or rotated in a predetermined direction, and an etching liquid is sprayed in the space to bring the etching liquid into contact with the etching liquid. Semiconductor substrate. The supply speed of the etching liquid or the rotation speed of the substrate is the same as described above. In the apparatus configuration of the single wafer processing according to the preferred embodiment of the present invention, it is preferable to apply an etching liquid while moving the discharge port (nozzle) as shown in Fig. 4 . Specifically, in the present embodiment, when the etching liquid is applied to the semiconductor substrate S, the substrate is rotated in the r direction. On the other hand, the discharge port is moved along a movement trajectory t extending from the central portion of the semiconductor substrate to the end portion. As described above, in the present embodiment, the rotation direction of the substrate and the moving direction of the discharge port are set to be different directions, whereby the two are relatively moved to each other. As a result, the etching liquid can be applied to the entire surface of the semiconductor substrate without fail, and a configuration in which the uniformity of etching is appropriately ensured can be achieved. The moving speed of the discharge port (nozzle) is not particularly limited, but is preferably 0.1 cm/s or more, and more preferably 1 cm/s or more. On the other hand, as the upper limit thereof, it is preferably 30 cm/s or less, more preferably 15 cm/s or less. The moving trajectory can be a straight line or a curve (for example, an arc shape). In either case, the speed of movement can be calculated from the distance of the actual trajectory line and the time it takes to move. The time required for etching one substrate is preferably in the range of 10 seconds to 300 seconds.

The metal layer is preferably etched at a high etch rate. The etching rate [R2] of the second layer (metal layer) is not particularly limited, but in view of production efficiency, it is preferably 10 Å/min or more, more preferably 50 Å/min or more, and particularly preferably 100 Å/min or more. . There is no special upper limit, but it is more than 1000 Å/min.

The range in which the metal layer is exposed is not particularly limited. However, from the viewpoint that the advantages of the present invention become more remarkable, it is preferably 2 nm or more, and more preferably 4 nm or more. Similarly, from the viewpoint of the significance of the effect, the upper limit value is actually 1000 nm or less, preferably 100 nm or less, more preferably 20 nm or less.

The etching rate [R1] of the first layer (tantal layer or tantalum layer) or the third layer (halide layer) is not particularly limited, but is preferably not excessively removed, and is preferably 100 Å/min or less, and further It is preferably 60 Å/min or less, and particularly preferably 40 Å/min or less. There is no particular lower limit, but if the measurement limit is taken into consideration, it is more practically 0.1 Å/min or more.

In the selective etching of the second layer and the third layer or the first layer, the etching rate ratio ([R2]/[R1]) is preferably 4 or more, more preferably 4.5 or more, and still more preferably 5 or more. Very good is 5.5 or more. The upper limit is not particularly specified, and the higher the better, but the actual one is 100 or less, and the more practical is 50 or less, and the practical one is 15 or less.

Further, in the etching solution of the preferred embodiment of the present invention, a metal electrode layer such as Al or W may be suitably suppressed, and HfO, HfSiO, WO, AlO _x , SiO ₂ , SiOC, SiON, SiOCN, TiN, or the like. The insulating film layers such as SiN or TiAlC (which may be collectively referred to as the fourth layer in some cases) are preferably used for the semiconductor substrate including the semiconductor substrates. In addition, in the present specification, when the composition of the metal compound is expressed by a combination of its elements, it means that it contains a wide range of constituents. For example, the term "SiOC" (SiON) means that Si coexists with O and C(N), and does not mean that the ratio of the amount is 1:1:1. This notation is common to this specification and the same is true for other metal compounds.

The time required for etching one of the substrates is preferably 10 seconds or more, more preferably 50 seconds or more. The upper limit is preferably 300 seconds or shorter, more preferably 200 seconds or shorter.

[Production of Semiconductor Substrate Product] In the present embodiment, it is preferable to manufacture a semiconductor substrate product having a desired structure by forming the germanium layer and the metal layer on a germanium wafer to form a semiconductor substrate. a step of annealing the semiconductor substrate; a step of applying an etchant to the semiconductor substrate, contacting the etchant with the metal layer, and selectively removing the metal layer. At this time, the specific etching liquid is used in etching. The order of the steps is not limited, and other steps may be included between the steps. The wafer size is not particularly limited, and a diameter of 8 Å, a diameter of 12 Å, or a diameter of 14 Å (1 吋 = 25.4 mm) can be suitably used. In addition, when "preparation" is referred to in the present specification, it means that, in addition to preparation for synthesis or blending of a specific material, it is also included to purchase a predetermined substance by purchase or the like. In addition, in the present specification, the use of an etching liquid for etching each material of a semiconductor substrate is referred to as "application", but the embodiment thereof is not particularly limited. For example, it is widely used to bring the etching liquid into contact with the substrate. Specifically, the etching may be performed by immersion in a batch type apparatus, or may be performed by spraying by a single wafer processing apparatus. In the present specification, the semiconductor substrate is used in the meaning of not only the wafer but also the entire substrate structure in which the circuit structure is applied. The semiconductor substrate member refers to a member constituting the defined semiconductor substrate, and may include one material or a plurality of materials. Further, the processed semiconductor substrate may be referred to as a semiconductor substrate product in a different manner, and may be further distinguished as necessary, and the wafer and the processed product which are processed and cut out are referred to as a semiconductor element. That is, a semiconductor element or a semiconductor article in which a semiconductor element is incorporated is broadly classified as a semiconductor substrate product. [Examples]

Hereinafter, the present invention will be described in more detail by way of examples, but the present invention is not limited to the following examples. In addition, unless otherwise indicated, the % and the part shown as a formulation or a compounding quantity in an Example are a mass basis.

[Example 1 and Comparative Example 1] (Preparation of test substrate) The Si film was epitaxially grown on a commercially available ruthenium substrate (diameter: 12 Å), and was formed to have a thickness of 500 Å (50 nm). Further, a layer of Ti is formed on the Si epitaxial layer by CVD (chemical vapor deposition). This was annealed at 800 ° C for 10 seconds to form a telluride layer as a test substrate. The annealed telluride layer has a thickness of 15 nm and the metal layer has a thickness of 5 nm. A blanket wafer made of CVD or the like in the same manner as other films is prepared. In the tests in the table below, the etch rates of the layers were determined using each of the test wafers.

(Etching test) The blank wafer and the test substrate were subjected to the following conditions using a single wafer processing apparatus (PSS-Europe (BOS-Europe) BV company, POLOS (trade name)). Etching was performed and an evaluation test was carried out. ·Processing temperature: 24 ° C Room temperature · Supply speed: 1 L/min. · Wafer rotation speed: 500 rpm · Nozzle movement speed: 7 cm / S Further, the supply of the etching liquid is performed as a liquid (using the Line A). Each treatment test was carried out immediately after the liquid was prepared.

(Measurement Method of Processing Temperature) A radiation thermometer IT-550F (trade name) manufactured by Horiba, Ltd. was fixed at a height of 30 cm on the wafer in the single wafer processing apparatus. The thermometer was placed on the surface of the wafer 2 cm outside the center of the wafer, and the temperature was measured while flowing into the liquid. The self-radiation thermometer performs digital output and continuously records the temperature using a personal computer. Here, the value obtained by averaging the temperature-stable temperature for 10 seconds is set as the temperature on the wafer.

(etching speed [ER]) The etching rate (ER) is determined by ellipsometry (using a spectroscopic ellipsometer, JA Woollam JAPAN Co., Ltd., Vase) The film thickness before and after the etching treatment was calculated. The average value of 5 points was used (measurement conditions: measurement range: 1.2 eV-2.5 eV, measurement angle: 70 degrees, 75 degrees). The measurement results of the etching rates of the respective layers are shown in the following table.

[Table 1]

<Notes on the table> DGMBE: Diethylene glycol monobutyl ether EGMBE: Ethylene glycol monobutyl ether EGMEE: Ethylene glycol monoethyl ether TiSi: Titanium telluride Formulation amount: Parts by mass (A): Fluoride ion Source component (B): water component (C): organic solvent (proton polar organic solvent) component (D): substituted hydroquinone compound, etc.

<Method for Measuring Corrosion Potential> Device: Princeton Applied Research, Model 263A (trade name) Substrate: Si substrate treated with 5% HF for 30 sec and with a natural oxide film removed on the surface (P type) 1 Ω·cm - 35 Ω·cm) The corrosion potential was measured by a chemical solution of H ₂ O 5 mass% + solvent (diethylene glycol monobutyl ether) + NaClO ₄ 0.1 mass% + oxidizing agent 0.08 mol/kg. Specifically, the corrosion potential was measured by a chemical solution obtained by mixing H ₂ O 5 % by mass, a solvent (diethylene glycol monobutyl ether) residue, NaClO ₄ 0.1% by mass, and an oxidizing agent 0.08 mol/kg. Here, sodium perchlorate is added as a supporting electrolyte in the measurement by a solvent system. The measurement procedure is as follows. 1. A substrate (measurement material) on which a specific pretreatment is performed is sandwiched as a working electrode. 2. The Ag/AgCl reference electrode filled with a saturated KCl/AgCl solution was sandwiched as a reference electrode. 3. Clamping platinum counter electrode: TCE-1 manufactured by Princeton Applied Research was used as a counter electrode. 4. Add the assay solution to the unit. 5. Start the measurement. (1) A Tafel plot is selected in a linear sweep mode. (2) Set by scanning at an open circuit potential of ±0.5 V. 6. Read the corrosion potential according to the VI chart.

As is apparent from the results of the above table, it is understood that the etching rate of Ti according to the present invention is high, and the etching rate of the telluride layer (TiSi) can be suppressed low. Further, it was confirmed that suitable protective properties can be achieved for other metal compound materials applied to the semiconductor substrate.

The invention and the embodiments are described in detail, but we do not limit our invention in any detail of the description unless otherwise specified, and should not contradict the invention shown in the accompanying claims. The spirit and scope are widely explained.

The priority of Japanese Patent Application No. 2015-032597, filed on Jan. 23,,,,,,,,,,,,,,, In the present application.

1‧‧‧metal layer (second layer)
2‧‧‧layer containing silicon or germanium (first layer)
3‧‧‧ Telluride layer (third layer)
11‧‧‧Processing container (treatment tank)
12‧‧‧Rotating table
13‧‧‧Spray outlet
14‧‧‧ points
21‧‧‧矽 substrate
22‧‧‧gate insulating film
23‧‧‧gate electrode
25‧‧‧ side wall
26‧‧‧Source electrode
26A‧‧‧TiSi (Ge) source electrode part
26B‧‧‧Annealed Telluride Source Electrode
27‧‧‧汲electrode
27A‧‧‧TiSi (Ge) Bipolar Electrode
27B‧‧‧Annealed Telluride Bipolar Electrode
28‧‧‧Ti film
Fc, fd‧‧‧ flow path
M‧‧‧Rotary Drive Department
R‧‧‧ direction
S‧‧‧Semiconductor substrate
t‧‧‧Mobile track

1(a), 1(b), and 1(c) are cross-sectional views schematically showing an example of a manufacturing process of a semiconductor substrate according to an embodiment of the present invention. 2(A), 2(B), 2(C), 2(D), and 2(E) show a metal oxide semiconductor (MOS) according to an embodiment of the present invention. A step diagram of a manufacturing example of a transistor. Fig. 3 is a view showing a configuration of a part of a wet etching apparatus according to a preferred embodiment of the present invention. 4 is a plan view schematically showing a movement trajectory of a nozzle with respect to a semiconductor substrate in an embodiment of the present invention.

no

Claims (20)

An etching solution which is an etching solution for a semiconductor process and contains a fluorine ion and a substituted hydroquinone compound. The etching solution according to claim 1, which contains an organic solvent. The etching solution according to claim 1 or 2, which contains water. The etching liquid according to the first or second aspect of the invention, wherein the concentration of the fluorine ions is 0.1% by mass or more and 20% by mass or less. The etching liquid according to the first or second aspect of the invention, wherein the concentration of the substituted hydroquinone compound is 0.1% by mass or more and 10% by mass or less. The etching solution according to claim 2, wherein the concentration of the organic solvent is 50% by mass or more and 98% by mass or less. The etching liquid according to claim 3, wherein the concentration of the water is 0.1% by mass or more and 50% by mass or less. The etching solution according to claim 1 or 2, wherein the substituted hydroquinone compound is represented by the following formula (H1), [Chemical Formula 1] R ^H1 represents a substituent; m1 represents an integer of 1 to 4. The etching solution according to claim 8, wherein R ^H1 is a hydrocarbon group. The etching solution according to claim 9, wherein R ^H1 is an alkyl group. The etching liquid according to claim 1 or 2, wherein the substituted hydroquinone compound has a ClogP value of 1 or more and 10 or less. The etching solution according to claim 1 or 2, wherein the substituted hydroquinone compound is 2,5-di-tert-butyl hydroquinone or 2-tert-butyl-p-benzene. Diphenol, 2,5-dimethyl hydroquinone, or 2-methyl hydroquinone. The etching solution according to the first or second aspect of the invention, wherein the corrosion potential of the substituted hydroquinone compound with respect to the ruthenium substrate is -0.25 or more and 0.5 or less. The etching solution according to claim 2, wherein the organic solvent comprises an alcohol compound or an ether compound. The etching solution according to claim 2, wherein the organic solvent comprises a compound represented by the following formula (O-1), R ^O1 -(-OR ^O2 -) _n -OR ^O3 ··· O-1) R ^O1 and R ^O3 are each independently a hydrogen atom or an alkyl group having 1 to 12 carbon atoms, an aryl group having 6 to 14 carbon atoms, or an aralkyl group having 7 to 15 carbon atoms; R ² is a linear chain a chain or branched carbon chain having 1 or more and 12 or less carbon atoms; when a plurality of R ^O2 are present, each R ² may be different; n is an integer of 0 or more and 12 or less; wherein, when n is 0, R ^O1 and R ^{O3 are} not hydrogen atoms at the same time. The etching solution according to claim 1 or 2, wherein the substrate for the semiconductor process has a layer containing titanium and a layer containing titanium telluride. The etching liquid according to claim 16, wherein the etching rate of the titanium-containing layer is divided by 4 or more and 15 or less by an etching rate of the titanium telluride-containing layer. An etching method for etching a layer containing titanium by using the etching solution according to any one of claims 1 to 17. The etching method according to claim 18, wherein the etching of the titanium-containing layer is performed while suppressing etching of titanium telluride. A method of producing a semiconductor substrate article, which is manufactured by the etching method according to claim 18 or claim 19.