TWI682989B - Etching liquid, etching method using the same, method for manufacturing semiconductor substrate products, and metal corrosion inhibitor - Google Patents

Abstract

An etching solution for a semiconductor process, which is an etching solution containing a compound P (P1) having a plurality of adsorption groups and a weight average molecular weight of 1000 or more, or a compound P (P2) having a plurality of adsorption groups and a stereoscopic repulsion site Of etching liquid.

Description

Etching liquid, etching method using the same, and preparation of semiconductor substrate products Manufacturing method and metal corrosion inhibitor

The invention relates to an etching solution, an etching method using the same, a manufacturing method of a semiconductor substrate product, a metal corrosion inhibitor and a metal corrosion prevention composition.

The manufacturing of integrated circuits involves multiple stages of various processing steps. During the manufacturing process, the accumulation, lithography, and etching of various materials are repeated several times. Among them, etching becomes an important process. To selectively etch specific materials, other materials must remain without being corroded. Depending on circumstances, only a predetermined layer is removed in a form in which such a layer containing a similar metal type or a layer containing a more corrosive material remains. The size of wiring or integrated circuits in semiconductor substrates is becoming smaller and smaller, and the importance of correct etching without corroding the remaining members is becoming increasingly important.

[Prior Art Literature] [Patent Literature]

[Patent Literature 1] International Publication No. 2012/125401 Specification

An object of the present invention is to provide an etching solution capable of etching a predetermined metal layer while suppressing damage to the predetermined metal layer, an etching method using the same, and Manufacturing method of semiconductor substrate products, and metal anti-corrosion agent and metal anti-corrosion composition.

The above-mentioned problems can be solved by the following means.

[1] An etchant which is an etchant for semiconductor manufacturing processes and which contains a compound P having a plurality of adsorption groups and having a weight average molecular weight of 1,000 or more.

[2] An etchant, which is an etchant for semiconductor manufacturing processes, and which contains a compound P having a plurality of adsorption groups and having a three-dimensional repulsion site.

[3] The etching solution according to [1] or [2], further containing at least one of a metal-dissolved component, an acid auxiliary agent having a pKa of 4 or less, an organic solvent, and water.

[4] The etching solution according to [3], wherein the acid auxiliary agent is a boric acid compound, a phosphoric acid compound, a phosphonic acid compound, HBF ₄ , HBr, or HCl.

[5] The etching solution according to [3] or [4], wherein the organic solvent is a protic polar organic solvent.

[6] The etching solution according to any one of [3] to [5], wherein the concentration of the metal dissolved component is 0.1% by mass or more and 20% by mass or less.

[7] The etching solution according to any one of [3] to [6], wherein the metal-dissolved component is a halide ion.

[8] The etching solution according to [7], wherein the halogen ion is a fluoride ion.

[9] The etching solution according to any one of [1] to [8], wherein the compound P is a compound represented by the following formula (1) or has a portion represented by the following formula (II) Structured compound: (A) _n -P ^a …(I)

A is an adsorption group; n is an integer of 2 or more; Pa is a residue of an organic compound having ^a weight average molecular weight of 1000 or more; -(BQ) _m- (II)

B is a repeating unit having an adsorption group; m is an integer of 2 or more; Q is a repeating unit containing an organic compound residue having a weight average molecular weight of 1000 or more.

[10] The etching solution according to any one of [1] to [9], which is applied to a semiconductor substrate including a third layer of silicide containing silicon or germanium, and other than silicon or germanium The second layer of metal species.

[11] The etching liquid according to [10], wherein the second layer is a layer containing titanium.

[12] The etching solution according to any one of [1] to [11], which is applied to a semiconductor substrate including a fourth layer containing TiAlC.

[13] An etching method that applies an etching solution to a semiconductor substrate, the etching solution containing a compound P having a plurality of adsorption groups and having a weight average molecular weight of 1000 or more, or a compound having a plurality of adsorption groups and having a stereoscopic repulsion site P.

[14] The etching method according to [13], wherein the etching solution further contains at least one of a metal-dissolving component, an acid auxiliary agent having a pKa of 4 or less, an organic solvent, and water.

[15] The etching method according to [13] or [14], which is applied to a semiconductor substrate including a third layer of silicide containing silicon or germanium, and a metal type other than silicon or germanium Second floor.

[16] The etching method according to any one of [13] to [15], wherein the second layer is a layer containing titanium.

[17] The etching method according to any one of [13] to [16], which is applied to a semiconductor substrate including a fourth layer containing TiAlC.

[18] A method of manufacturing a semiconductor substrate product, which manufactures a semiconductor substrate product via the etching method according to any one of [13] to [17].

[19] A metal anticorrosive agent or a metal anticorrosive composition containing the same, which comprises a compound P having a plurality of adsorption groups and having a weight average molecular weight of 1000 or more, or a compound P having a plurality of adsorption groups and having a stereoscopic repulsion site.

[20] The metal anticorrosive agent or the metal anticorrosive composition containing the same as described in [19], which is used in an etching solution for semiconductor manufacturing processes.

According to the present invention, the predetermined metal layer can be etched while suppressing damage to the predetermined metal layer.

The above-mentioned and other features and advantages of the present invention can be clarified from the following description with reference to the accompanying drawings.

1‧‧‧Metal layer (second layer)

2‧‧‧Silicon or germanium-containing layer (first layer)

3‧‧‧ Silicide layer (third layer)

11‧‧‧Processing container (processing tank)

12‧‧‧rotating table

13‧‧‧Spray outlet

14‧‧‧Confluence

21‧‧‧Si substrate

22‧‧‧Gate insulating film

23‧‧‧Gate electrode

25‧‧‧Side wall

26‧‧‧Source electrode

26A‧‧‧TiGeSi source electrode part

26B‧‧‧ Annealed silicide source electrode

27‧‧‧ Drain electrode

27A‧‧‧TiSiGe drain electrode part

27B‧‧‧annealed silicide drain electrode

28‧‧‧Ti film

80‧‧‧Lower semiconductor layer

81‧‧‧First work function material layer

82A, 82B‧‧‧Second work function material layer

83A, 83B‧‧‧Metal part

90A, 90B‧‧‧ replacement gate stack

91A、91B‧‧‧Metal semiconductor alloy part

92A, 92B‧‧‧well

93‧‧‧ Ditch and Ditch Structure Department

94A, 94B ‧‧‧ source/drain expansion area

95A, 95B ‧‧‧ gate spacer

96A, 96B ‧‧‧ source/drain region

97A, 97B ‧‧‧ gate insulating film

99‧‧‧flat dielectric layer

A, B‧‧‧ liquid

fc, fd‧‧‧stream

M‧‧‧rotation drive

r‧‧‧Direction

S‧‧‧Substrate

t‧‧‧Movement trajectory

FIG. 1(a), FIG. 1(b) and FIG. 1(c) are schematic A cross-sectional view of an example of the manufacturing process of the semiconductor substrate in the embodiment.

FIG. 2(A), FIG. 2(B), FIG. 2(C), FIG. 2(D), and FIG. 2(E) show a metal oxide semiconductor (MOS) in an embodiment of the present invention. Step diagram of a manufacturing example of a transistor.

3 is a cross-sectional view schematically showing the structure of a substrate according to another embodiment of the present invention.

FIG. 4 is an apparatus configuration diagram showing a part of a wet etching apparatus according to a preferred embodiment of the present invention.

5 is a plan view schematically showing a movement locus of a nozzle relative to a semiconductor substrate in an embodiment of the present invention.

First, the preferred embodiment of the etching step to which the etching solution of the present invention is applied will be described based on FIG. 1(a), FIG. 1(b), and FIG. 1(c) to FIG.

[Etching step]

1(a), 1(b), and 1(c) are diagrams showing semiconductor substrates before and after etching. In the manufacturing example of this embodiment, a metal layer (second layer) 1 is disposed on the upper surface of the silicon or germanium-containing layer (first layer) 2. The silicon or germanium-containing layer (first layer) should be a SiGe epitaxial layer that constitutes the source electrode and the drain electrode. The first layer may include Si, but it is preferably a SiGe or Ge epitaxial layer.

The constituent materials of the metal layer (second layer) 1 include metals such as titanium (Ti), cobalt (Co), nickel (Ni), nickel platinum (NiPt), tantalum (Ta), niobium (Nb), and tungsten (W) Type (single metal or composite metal). The formation of the metal layer can usually use such a metal film The method used for formation specifically includes film formation by chemical vapor deposition (Chemical Vapor Deposition, CVD). At this time, the thickness of the metal layer is not particularly limited, and examples of films of 5 nm or more and 50 nm or less can be cited. In the present invention, when the metal layer is a Ti layer, the removal performance of the etchant can be fully exerted, which is preferable.

In addition to the listed metal atoms, the metal layer may also contain other elements. For example, oxygen or nitrogen inevitably mixed may be present. It is preferable to suppress the amount of inevitable impurities to, for example, about 1 ppt to 10 ppm (mass basis).

In the step (a), after forming the metal layer 1 on the upper side of the silicon or germanium-containing layer 2, annealing (sintering) is performed to form a metal-Si reaction film (third layer: silicide layer) 3 ( Step (b)). The annealing may be performed under conditions generally used in the manufacture of such devices, and for example, treatment at 200°C to 1000°C may be mentioned. The thickness of the silicide layer 3 at this time is not particularly limited, and examples of the layer being 50 nm or less can be cited, and examples of the layer being 10 nm or less can be further cited. The lower limit value is not particularly limited, but is actually 1 nm or more. The silicide layer can be applied as a low-resistance film, and functions as a conductive portion that electrically connects the source electrode and the drain electrode located at the lower portion thereof and the wiring disposed at the upper portion thereof. Therefore, if a defect or corrosion occurs in the silicide layer, its conduction is impeded, which may result in quality deterioration such as device misoperation. In particular, the integrated circuit structure inside the substrate has recently been miniaturized, and even slight damage will have a large impact on the performance of the device. Therefore, it is desirable to prevent such defects or corrosion.

In addition, in this specification, in a broad sense, the silicide layer is included in the first The concept of layers containing silicon or germanium. Therefore, when the second layer is selectively removed relative to the first layer, it means not only that the second layer (metal layer) is preferentially removed relative to the unsilicided silicon-containing or germanium layer, but also includes the relative silicidation. The second layer (metal layer) is preferentially removed. In a narrow sense, when the first layer containing silicon or germanium (except the silicide layer) is distinguished from the third layer of silicide layer, it is called the first layer and the third layer, respectively.

Next, the remaining metal layer 1 is etched (step (b) -> step (c)). In this embodiment, the etching liquid is applied at this time, and the etching liquid is applied from the upper side of the metal layer 1 to be in contact therewith, thereby removing the metal layer 1. The form applied to the etching solution will be described later.

The silicon or germanium-containing layer 2 includes a SiGe epitaxial layer, which is formed by chemical vapor deposition (CVD) method on a silicon substrate having a specific crystallinity by crystal growth. Alternatively, the epitaxial layer formed with the desired crystallinity can be formed by an electron beam epitaxy (Molecular Beam Epitaxy (MBE)) method or the like.

In order to set the silicon- or germanium-containing layer as a P-type layer, it is preferable that boron (B) be doped at a concentration of about 1×10 ¹⁴ cm ⁻³ to 1×10 ²¹ cm ⁻³ . In order to be an N-type layer, it is preferable to dope phosphorus (P) 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 is preferably 20% by mass or more, and 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. In addition, when germanium is 100% by mass, the layer formed by the alloy of the second layer due to its annealing contains germanium and the specific metal element of the second layer, and does not contain silicon. However, in this specification, for convenience, Including it It is called a germanium silicide layer.

(Metal concentration)

In the present invention, the concentration of metals such as germanium is a value measured by the following measuring method. The substrate containing the layer of the specific metal was analyzed to 0nm to 30nm by means of Electron Spectroscopy for Chemical Analysis (ESCA) (Quantera) manufactured by Japan Vacuum (ULVAC-PHI) In the depth direction, the average value of the concentration of the metal (Ge, etc.) in the analysis result of 3 nm to 15 nm is taken as the concentration (mass %) of the metal.

After a salicide step, a silicide layer is formed between the silicon or germanium-containing layer (first layer) and the metal layer (second layer) as silicon-containing or germanium-containing (Ge) and The layer of the composition (the specific metal type) of the second layer. The silicide layer is included in the first layer in a broad sense, and is referred to as the "third layer" when distinguished in a narrow sense. The composition is not particularly limited, and a germanium silicide layer containing germanium is preferred. In the formula of SixGeyMz (M: metal element), if x+y+z=1, it is preferably 0.2≦x+y≦0.8, and more preferably 0.3≦x+y≦0.7. Regarding z, preferably 0.2≦z≦0.8, and more preferably 0.3≦z≦0.7. The preferred range of the ratio of x to y is as stated in the aforementioned regulations. Among them, other elements may also be included in the third layer. This aspect is the same as that described in the metal layer (second layer).

In the semiconductor substrate, in addition to the silicide material, there are sometimes materials that are not desired to be etched. In the etching solution of this embodiment, it is preferable to minimize the corrosion of the material that is not desired to be etched. The material (fourth layer) that is not desired to be etched may include at least one selected from the group consisting of Al, SiO ₂ , SiN, SiOC, HfO, and TiAlC. In particular, the fourth layer such as TiAlC is sometimes used in the gate electrode 23 (FIG. 2(A), FIG. 2(B), FIG. 2(C), FIG. 2(D), and FIG. 2(E)). It is preferable that the material protecting the fourth layer can be etched separately from the protection of the first layer and the third layer or simultaneously with it.

(Processing of MOS transistor)

FIG. 2(A), FIG. 2(B), FIG. 2(C), FIG. 2(D) and FIG. 2(E) are step diagrams showing a manufacturing example of the MOS transistor. Fig. 2(A) is the step of forming the MOS transistor structure, Fig. 2(B) is the sputtering step of the metal film, Fig. 2(C) is the first annealing step, and Fig. 2(D) is the selective removal of the metal film Step 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 silicon substrate 21. Extension regions may be additionally formed on both sides of the gate electrode 23 of the silicon substrate 21. A protective layer (not shown) that prevents contact with the Ti layer may be formed on the upper side of the gate electrode 23. In addition, the side wall 25 including the silicon oxide film or the silicon nitride film is formed, and the source region 26 and the drain region 27 are formed by ion implantation.

Next, as shown in the figure, a Ti film 28 is formed, and annealing treatment is rapidly performed. As a result, the elements in the Ti film 28 are diffused into the silicon substrate to be silicided (in this specification, when germanium is also contained at 100% by mass, alloying by annealing is referred to as silicification for convenience). As a result, the upper portions of the source electrode 26 and the drain electrode 27 are silicided to form the TiGeSi source electrode portion 26A and the TiSiGe drain electrode portion 27A. At this time, if necessary, the second annealing is performed as shown in FIG. 2(E), thereby changing the electrode member to a desired state (the annealed silicide source electrode 26B is subjected to retreat Fired silicide drain electrode 27B). The annealing temperatures of the first and second times are not particularly limited, and may be performed at 300°C to 1100°C, for example.

The Ti film 28 remaining without participating in silicidation can be removed by using the etching solution of this embodiment (FIG. 2(C), FIG. 2(D)). At this time, the person shown in the figure is largely modeled, and the Ti film deposited on the silicided layers (26A, 27A) and remaining is optional. The structure of the semiconductor substrate or its product is also shown in a simplified manner, which can be interpreted as including necessary components as necessary.

If the preferred examples of the constituent materials are listed, the following forms can be exemplified.

The semiconductor substrate to which the etching method of the present invention is applied is as described above, but it is not limited to this specific example, and can also be applied to other semiconductor substrates. For example, a semiconductor substrate including a high-dielectric film/metal gate FinFET with a silicide pattern on the source and/or drain regions can be cited.

In the examples of FIG. 2(A), FIG. 2(B), FIG. 2(C), FIG. 2(D) and FIG. 2(E), the silicide layer (first layer, third layer) Protection was carried out Explanation, but the present invention is not interpreted as being limited thereto. For example, the protection of the fourth layer such as TiAlC can be realized separately from the protection of the silicide, and the etching of the second layer such as Ti can be realized on the one side.

3 is a cross-sectional view schematically showing the structure of a substrate according to another embodiment of the present invention. 90A is the first gate stack located in the first element region. 90B is the second gate stack located in the second element region. Here, the gate stack contains a conductive tantalum alloy layer or TiAlC. If the first gate stack is described, 92A is a well. 94A is the first source/drain expansion region, 96A is the first source/drain region, and 91A is the first metal semiconductor alloy portion. 95A is the first gate spacer. 97A is a first gate insulating film, 81 is a first work function material layer (first work function material layer), and 82A is a second work function material layer (second work function material layer). 83A is a first metal portion that becomes an electrode. 93 is a trench structure part, and 99 is a planarized dielectric layer. 80 is the lower semiconductor layer.

The second gate stack has the same structure, and its 91B, 92B, 94B, 95B, 96B, 97B, 82B, and 83B are the same as those of the first gate stack, 91A, 92A, 94A, 95A, 96A, 97A, 82A, 83A correspondence. If the structural differences between the two are listed, the first work function material layer 81 is present on the first gate stack, but the first work function material layer 81 may not be provided on the second gate stack.

The work function material layer may be any of a p-type work function material layer and an n-type work function material layer. The p-type work function material refers to a material having a work function between the valence level of silicon and the intermediate band gap level. That is, in the energy level of silicon, the energy level of the conduction band and the valence level are equally separated. n-type work function material refers to the energy level of the conduction band of silicon A material with a work function between the intermediate bandgap energy level of silicon.

The material of the work function material layer is preferably a conductive tantalum alloy layer or TiAlC. The conductive tantalum alloy layer may include a material selected from (i) an alloy of tantalum and aluminum, (ii) an alloy of tantalum and carbon, (iii) an alloy of tantalum, aluminum, and carbon. TiAlC is a material containing titanium, aluminum, and carbon.

(i)TaAl

In an alloy of tantalum and aluminum, the atomic concentration of tantalum can be set at 10% to 99%. The atomic concentration of aluminum can be set to 1% to 90%.

(ii) TaC

In an alloy of tantalum and carbon, the atomic concentration of tantalum can be set to 20% to 80%. The atomic concentration of carbon can be set from 20% to 80%.

(iii) TaAlC

In tantalum, aluminum, and carbon alloys, the atomic concentration of tantalum can be set to 15% to 80%. The atomic concentration of aluminum can be set from 1% to 60%. The atomic concentration of carbon can be set from 15% to 80%.

In other embodiments, the work function material layer may be (iv) a titanium nitride layer substantially made of titanium nitride or (v) an alloy layer of titanium and aluminum and carbon.

(iv)TiN

In the titanium nitride layer, the atomic concentration of titanium can be set to 30% to 90%. The atomic concentration of nitrogen can be set at 10% to 70%.

(v)TiAlC

In the alloy layer of titanium and aluminum and carbon, the atomic concentration of titanium can be set to 15% to 45%. The atomic concentration of aluminum can be set at 5% to 40%. The atomic concentration of carbon can be set at 5% to 50%.

The work function material layer may be formed by atomic layer deposition (ALD), physical vapor deposition (PVD), chemical vapor deposition (CVD), or the like. The work function material layer is preferably formed by covering the gate electrode, and its film thickness is preferably 100 nm or less, more preferably 50 nm or less, and still more preferably 1 nm to 10 nm.

Among them, in the present invention, from the viewpoint of appropriately expressing the selectivity of etching, it is preferable to use a substrate using a TiAlC layer.

In the device of this embodiment, the gate dielectric layer contains a high dielectric constant material containing metal and oxygen. A well-known high dielectric constant gate dielectric material can be used. The film can be deposited by the usual method. For example, chemical vapor deposition (CVD), physical vapor deposition (PVD), molecular beam vapor deposition (MBD), pulsed laser vapor deposition (PLD), liquid raw material mist chemical deposition (LSMCD), atomic layer deposition (ALD) )Wait. Typical high dielectric constant dielectric materials include HfO ₂ , ZrO ₂ , La ₂ O ₃ , Al ₂ O ₃ , TiO ₂ , SrTiO ₃ , LaAlO ₃ , Y ₂ O ₃ , HfO _x N _y , ZrO _x N _{y, La 2 O x N y} , Al 2 O x N y, TiO x N y, SrTiO x N y, LaAlO x N y, Y 2 O x N y and the like. x is 0.5~3, y is 0~2. The thickness of the gate dielectric layer is preferably 0.9 nm to 6 nm, and more preferably 1 nm to 3 nm. Among them, it is preferable that the gate dielectric layer contains hafnium oxide (HfO ₂ ).

Other members or structures may be formed by common materials according to common methods. For details, reference may be made to U.S. Publication No. 2013/0214364 and U.S. Publication No. 2013/0341631, incorporated by reference.

With the etching solution of the preferred embodiment of the present invention, even the substrate with the work function material layer (TiAlC) exposed as described above, the damage of the layer can be suppressed. Effectively remove silicide metals (Ni, Pt, Ti, etc.).

[Etching solution]

(Compound P)

The etching solution for a semiconductor process of this embodiment contains the compound P (P1) having a plurality of adsorption groups and a weight average molecular weight of 1000 or more, or the compound P (P2) having a plurality of adsorption groups and a stereoscopic repulsion site. The compound P having a plurality of adsorption groups and having a weight average molecular weight of 1000 or more can suppress the dissolution of the desired metal without reducing the performance of the metal dissolving component in the etching solution. Based on this function, this compound P is sometimes referred to as a "metal corrosion inhibitor", and a composition containing it is referred to as a "metal corrosion inhibitor composition". The reason for obtaining this effect is not yet clear, but it is presumed as follows: when the etching liquid comes into contact with the metal, the adsorption group of the compound P is adsorbed on the predetermined metal. Since there are a plurality of such adsorption groups, the adhesion to the metal can be improved. On the other hand, since there are structures or three-dimensional repulsive sites with a weight average molecular weight of 1,000 or more, these cover the surface of the prescribed metal, hinder the contact of the metal-dissolved component, and suppress the dissolution of the desired metal.

Compound P, especially Al, is excellent in the corrosion prevention effect. The compound P is preferably represented by the following formula (I). The weight average molecular weight is more preferably 3000 or more, and particularly preferably 5000 or more.

(A) _n -P ^a …(I)

A is an adsorption group. n is an integer of 2 or more. Pa is a residue of an organic compound (polymer compound) having ^a weight average molecular weight of 1,000 or more, and may also be a stereorepellent site. As described above, the weight average molecular weight is preferably 5,000 or more, and more preferably 7,000 or more. The upper limit is preferably about 100,000, and more preferably 10,000 or less. If the molecular weight is small, the effect of suppressing the dissolution of the metal tends to be insufficient; if the molecular weight is large, there is a possibility that the etching is not good.

P ^{a is} preferably a residue of a polymer compound defined by P1 described below.

The compound P is also preferably a compound having a partial structure represented by the following formula (II). The weight average molecular weight is more preferably 3000 or more, and particularly preferably 5000 or more.

-(BQ) _m- (II)

B is a repeating unit having an adsorption group. The adsorption group is synonymous with the aforementioned formula (I). m is an integer of 2 or more. Q is a repeating unit containing an organic compound residue having a weight average molecular weight of 1,000 or more. The structure of the polymer compound residue is the same as the formula (I).

Definition of molecular weight (1)

In the present invention, the molecular weight of the polymer means the weight average molecular weight unless otherwise specified, and the weight average molecular weight in terms of standard polystyrene is measured by gel permeation chromatography (Gel Penetration Chromatography, GPC). The weight average molecular weight is measured by the following methods: HPC-8220GPC (manufactured by Tosoh Corporation), protection column: TSKguardcolumn SuperHZ-L, column: TSKgel SuperHZM-M, TSKgel SuperHZ4000, TSKgel SuperHZ3000 and TSKgel SuperHZ2000 are directly connected, and 10 μl of a tetrahydrofuran solution with a sample concentration of 0.1% by mass is injected at a column temperature of 40°C, and tetrahydrofuran is flowed at a flow rate of 0.35 ml per minute as a leaching solvent by an RI detection device Detect the peak value of the sample. The calculation was performed using a calibration curve prepared using standard polystyrene.

Furthermore, in the compound, A may be an adsorption group, n may be an integer of 2 or more, and P may be a hydrophobic group (polymer). The hydrophobic group preferably has a ClogP of 3 or more, more preferably 10 or more, and preferably 100 or less. Particularly preferable as the adsorption group A is the following substituent A ¹ .

The compound P represented by the formula (I) is more preferably a polymer compound represented by the formula (1).

A ¹ represents a group having at least one group selected from an acid group, a group having a basic nitrogen atom, a urea group, a carbamate group, a group having a coordination oxygen atom, a phenol group, an alkyl group , Aryl groups, groups with alkyloxy chains, amide imino groups, alkoxycarbonyl groups, alkylaminocarbonyl groups, carboxylate groups, sulfonamide groups, alkoxysilyl groups, epoxy groups, Isocyanate group, hydroxyl group, and heterocyclic group. A ¹ preferably functions as a base having the ability to adsorb specific metals. A ¹ present in the same compound may be the same or different.

R ¹ represents a (m+n)-valent linking group, and R ² represents a single bond or a divalent linking group.

m is a positive number below 8, n represents 1~9, and m+n satisfies 3~10.

P ¹ represents a polymer chain. The m P ^1s may be the same or different.

A ¹ may include two or more adsorption sites. Examples of its implementation include chain saturated hydrocarbon groups (which may be linear or branched, preferably 1 to 10 carbon atoms), and cyclic saturated hydrocarbon groups (preferably 3 to 10 carbon atoms). ), an aromatic group (preferably having a carbon number of 5 to 10, such as phenylene) and the like, and a group having at least two adsorption sites bonded thereto. Among them, it is preferable to bond two or more adsorption sites via a chain saturated hydrocarbon group. In addition, when the adsorption site itself constitutes a monovalent substituent, the adsorption site itself may be a monovalent substituent represented by A ¹ .

The "acid group" is preferably, for example, a carboxyl group, a sulfonic acid group, a monosulfate group, a phosphoric acid group, a monophosphate group, a phosphonic acid group, a phosphinic acid group, or a boric acid group, more preferably a carboxyl group, a sulfonic acid group Group, monosulfate group, phosphoric acid group, monophosphate group, phosphonic acid group, phosphinic acid group, particularly preferably a carboxyl group.

"Ureido group" include e.g. -NR ^N CONR ^N ₂ as a preferred embodiment, is better -NR ^N CONHR ^N, particularly preferred is -NHCONHR ^N.

The "carbamate group" includes, for example, -NHCOOR ^N , -NR ^N COOR ^N , -OCONHR ^N , -OCONR ^N ₂ and the like as preferred examples, more preferably -NHCOOR ^N , -OCONHR ^N, etc., particularly preferred It is -NHCOOR ^N , -OCONHR ^N and so on. Here, R ^N is the following definition.

The "group having a coordinating oxygen atom" may, for example, be acetone or crown ether.

The "group having a basic nitrogen atom" includes, for example, amine groups (-NH ₂ ), substituted imino groups (-NHR ^N , -NR ^N ₂ ), guanidine groups represented by the following formula (a1), and the following The amidino group represented by the above formula (a2) is a preferred example.

In the formula, R ^N independently represents an alkyl group having 1 to 20 carbon atoms, an aryl group having 6 to 14 carbon atoms, or an aralkyl group having 7 to 15 carbon atoms. Among them, preferred is an alkyl group having 1 to 10 carbon atoms, an aryl group having 6 to 10 carbon atoms, or an aralkyl group having 7 to 11 carbon atoms. More preferably, it is an alkyl group having 1 to 5 carbon atoms, a phenyl group, or a benzyl group.

Among these, more preferred are amine groups (-NH ₂ ), substituted imino groups (-NHR ^N , -NR ^N ₂ ), guanidine groups represented by formula (a1), and those represented by formula (a2) Amidine and so on.

"Alkyl group" may be linear or branched, preferably an alkyl group having a carbon number of 1 to 40, more preferably an alkyl group having a carbon number of 4 to 30, and even more preferably a carbon number It is an alkyl group of 10-18.

The "aryl group" is preferably an aryl group having 6 to 10 carbon atoms.

The "group having an alkyleneoxy chain" preferably forms an alkoxy group or a hydroxyl group at the terminal, and more preferably forms an alkoxy group having 1 to 20 carbon atoms. In addition, the alkyleneoxy chain is not particularly limited as long as it has at least one alkyleneoxy group, and it is preferably an alkyleneoxy group having 1 to 6 carbon atoms. Examples of the alkyleneoxy group include -(R ^C ) _mc -. R ^{C is} preferably an alkylene group having 1 to 3 carbon atoms, and more preferably an alkylene group having 2 or 3 carbon atoms. The mc is preferably 1 to 6, and more preferably 1 to 3.

The alkyl portion in the "alkoxycarbonyl group" is preferably an alkyl group having 1 to 20 carbon atoms.

The alkyl portion in the "alkylaminocarbonyl group" is preferably an alkyl group having 1 to 20 carbon atoms.

The "carboxylate group" includes a group containing an ammonium salt of carboxylic acid and the like.

As the "sulfonylamido group", a hydrogen atom bonded to a nitrogen atom may be substituted with an alkyl group (methyl group, etc.), an acyl group (acetyl group, trifluoroacetyl group, etc.).

The "heterocyclic group" includes, for example, thienyl, furyl, xanthene, pyrrolyl, pyrrolinyl, pyrrolidinyl, dioxolyl, pyrazolyl, pyrazolinyl, pyrazolinyl , Imidazolyl, oxazolyl, thiazolyl, oxadiazolyl, triazolyl, thiadiazolyl, pyranyl, pyridyl, piperidinyl, dioxanyl, morpholinyl, pyridazinyl, pyrimidine Group, piperazinyl, triazinyl, trithianyl, isoindolinyl, isoindolinone, benzimidazolone, benzothiazolyl, succinimido, phthalimido Imidyl groups such as imino groups, naphthalimide groups, hydantoin groups, indolyl groups, quinolinyl groups, carbazolyl groups, acridinyl groups, acridinone groups, and anthraquinone groups are preferred example. In addition, cyclic ketones containing anthraquinone groups are also included in the heterocycle.

Examples of the "acylimidyl group" include succinimide, phthalimide, and naphthalimide.

In addition, the "heterocyclic group" and "acylimino group" may further have a substituent, and examples of the substituent include an alkyl group having 1 to 20 carbon atoms and 6 to 16 carbon atoms. Aryl, hydroxy, amine, carboxyl, sulfonamide, N-sulfonamide, ethoxy, etc. 1 to 6 carbon oxy, methoxy, ethoxy, etc. Alkoxy groups having 1 to 20 carbon atoms, halogen atoms, methoxycarbonyl groups, ethoxycarbonyl groups, cyclohexyloxycarbonyl groups, etc., having 2 to 7 carbon atoms, cyano groups, third butyl carbonate, etc. Carbonate group.

The "alkoxysilane group" may be any of a monoalkoxysilane group, a dialkoxysilane group, and a trialkoxysilane group, preferably a trialkoxysilane group, for example, trimethoxy Silyl, triethoxysilyl, etc.

The "epoxy group" may include substituted or unsubstituted oxetanyl (oxirane).

In particular, A ^{1 is} preferably a monovalent substituent having at least one functional group having a pKa of 5 or more, and more preferably a monovalent substituent having at least one functional group having a pKa of 5 to 14.

At this time, the so-called "pKa" is the definition described in Chemical Handbook (II) (Revised Fourth Edition, 1993, edited by the Chemical Society of Japan, Maruzen Co., Ltd.).

Examples of the functional group having a pKa of 5 or more include a group having a coordinated oxygen atom, a group having a basic nitrogen atom, a phenol group, a urea group, a carbamate group, an alkyl group, an aryl group, and an alkoxy group A carbonyl group, an alkylaminocarbonyl group, a group having an alkyloxy group, an amide imide group, a carboxylate group, a sulfonamide group, a hydroxyl group, a heterocyclic group, and the like.

Alternatively, a value calculated using ACD/Labs (produced by Advanced Chemistry Development) or the like can be used.

The functional group having a pKa of 5 or more specifically includes, for example, a phenol group (pKa is about 8 to 10), an alkyl group (pKa is about 46 to 53), an aryl group (pKa is about 40 to 43), and a urea group (pKa Is about 12 to 14), a carbamate group (pKa is about 11 to 13), -COCH ₂ CO- (pKa is about 8 to 10) as a coordinated oxygen atom, and a sulfonamide group (pKa is 9 to 11), hydroxyl (pKa is about 15 to 17), heterocyclic group (pKa is about 12 to 30) and so on.

In the above, A ^{1 is} preferably a monovalent substituent having at least one group selected from the group consisting of acid groups, hydroxyphenyl groups, alkyl groups, aryl groups, and alkyleneoxy groups Chain group, hydroxyl group, urea group, urethane group, sulfonamide group, amide imine group and group having a coordinated oxygen atom. As A ¹ , an acid group, a hydroxyphenyl group, or a hydroxyl group is more preferable, and an acid group (particularly a carboxyl group) is particularly preferable.

In formula (1), R ² represents a single bond or a divalent linking group. n R ² may be the same or different. The divalent linking group represented by R ² includes 1 to 100 carbon atoms, 0 to 10 nitrogen atoms, 0 to 50 oxygen atoms, 1 to 200 hydrogen atoms, and 0 to 20 atoms The sulfur atom group may be unsubstituted or may further have a substituent.

R ^{2 is} preferably a single bond, or contains 1 to 10 carbon atoms, 0 to 5 nitrogen atoms, 0 to 10 oxygen atoms, 1 to 30 hydrogen atoms, and 0 to 5 sulfur A divalent linking group of atoms.

R ^{2 is more} preferably selected from a chain-like saturated hydrocarbon group (which may be linear or branched, preferably having a carbon number of 1-20), and a cyclic saturated hydrocarbon group (preferably having a carbon number of 3~ 20), an aromatic group (preferably having a carbon number of 5 to 20, such as phenylene), a thioether bond, an ester bond, an amide bond, an ether bond, a nitrogen atom, and a carbonyl group , Or a combination of two or more of these, further preferably selected from the group consisting of a chain saturated hydrocarbon group, a cyclic saturated hydrocarbon group, an aromatic group, a thioether bond, an ester bond, an ether bond, and an amide bond The group constituting the group, or a group formed by combining two or more of these, is particularly preferably selected from the group consisting of a chain saturated hydrocarbon group, a thioether bond, an ester bond, an ether bond, and an amide bond Or a combination of two or more of these.

In the above, when the divalent linking group represented by R ² has a substituent, examples of the substituent include an alkyl group having 1 to 20 carbon atoms, an aryl group having 6 to 16 carbon atoms, a hydroxyl group, and an amine. 1 to 6 carbon alkoxy groups such as carboxyl groups, carboxyl groups, sulfonamide groups, N-sulfonyl amide groups, acetoxy groups, etc. , Such as halogen atoms such as chlorine and bromine, alkoxycarbonyl groups such as methoxycarbonyl group, ethoxycarbonyl group, and cyclohexyloxycarbonyl group, carbonic acid groups such as alkoxycarbonyl groups having 2 to 7 carbon atoms, cyano groups, and third butyl carbonate.

In formula (1), R ¹ represents a (m+n)-valent linking group. m+n satisfies 3~10.

The (m+n)-valent linking group represented by R ¹ includes 1 to 100 carbon atoms, 0 to 10 nitrogen atoms, 0 to 50 oxygen atoms, 1 to 200 hydrogen atoms, and 0 A group of ~20 sulfur atoms may be unsubstituted or may further have a substituent.

The (m+n)-valent linking group represented by R ¹ is preferably a group represented by any of the following formulas.

[Chemical 3]

In the above formula, L represents a 3- to 6-valent group. T represents a single bond or a divalent linking group. There are 3 to 6 Ts that can be the same or different. L is preferably a carbon atom, an aryl linking group (preferably a carbon number of 6-22, more preferably a carbon number of 6-14, particularly preferably a carbon number of 6-10), heterocyclic linking Base (preferably, the carbon number is 2 to 12, more preferably the carbon number is 2 to 6). T represents an alkylene group (preferably, the carbon number is 1 to 12, more preferably, the carbon number is 1 to 6, and particularly preferably, the carbon number is 1 to 3), carbonyl group (CO), oxy group (O) , Imine group (NR ^N ), sulfide group (S), or a combination of these groups. ^RN according to the definition.

The following shows specific examples of (m+n)-valent linking groups represented by R ¹ [specific examples (1) to specific examples (17)]. However, in the present invention, it is not limited to these specific examples.

[Chemical 4]

In the specific examples, the availability of raw materials, the ease of synthesis, and the From the viewpoint of solubility in various solvents, the best (m+n)-valent linking group is the group of (1), (2), (10), (11), (16), (17) .

In formula (1), m represents a positive number of 8 or less. m is preferably 0.5 to 5, more preferably 1 to 4, and particularly preferably 1 to 3. n represents 1~9. n is preferably 2-8, more preferably 2-7, and particularly preferably 3-6. In addition, when m and n are accompanied by decimals, it represents a mixture of compounds having different m and n.

In formula (1), P ¹ represents a polymer chain, and can be selected from known polymers and the like as necessary. The m P ^1s may be the same or different.

Among polymers, in order to constitute a polymer chain, it is preferably selected from polymers or copolymers of vinyl monomers, ester-based polymers, ether-based polymers, carbamate-based polymers, and amide-based polymers Polymers, epoxy-based polymers, silicone-based polymers, modified products of these, or copolymers [for example, polymers containing polyether/polyurethane copolymers, polyether/vinyl monomers At least one of the group consisting of copolymers such as random copolymers, block copolymers, and graft copolymers, more preferably selected from polymers or copolymers of vinyl monomers At least one of the group consisting of compounds, ester-based polymers, ether-based polymers, urethane-based polymers, and modified products or copolymers thereof, particularly preferably vinyl monomer polymers Or copolymer.

It is preferable that the polymer or copolymer of the vinyl monomer, ester-based polymer, and ether-based polymer that the polymer chain P ¹ may have have the following formula (L), formula (M), and formula (N ) The structure represented by any one.

[化6]

In the above formula, X ¹ represents a hydrogen atom or a monovalent organic group. From the viewpoint of synthesis restrictions, a hydrogen atom or an alkyl group having 1 to 12 carbon atoms is preferred, a hydrogen atom or a methyl group is more preferred, and a methyl group is particularly preferred.

R ¹⁰ represents a hydrogen atom or a monovalent organic group. Preferred is a hydrogen atom, alkyl group, aryl group, or heteroaryl group, and more preferred is a hydrogen atom, or alkyl group. In the case where R ¹⁰ is an alkyl group, the alkyl group is preferably a linear alkyl group having 1 to 20 carbon atoms, a branched alkyl group having 3 to 20 carbon atoms, or 5 carbon atoms The cyclic alkyl group of ~20 is more preferably a linear alkyl group having 1 to 20 carbon atoms, and particularly preferably a linear alkyl group having 1 to 6 carbon atoms. In formula (L), it may have two or more types of R ¹⁰ having different structures.

R ¹¹ and R ¹² represent a branched or linear alkylene group (the carbon number is preferably 1-10, more preferably 2-8, and even more preferably 3-6). In each formula, two or more R ¹¹ or R ¹² having different structures may also be present.

k1, k2, and k3 independently represent numbers from 5 to 140, respectively.

It is preferable that the polymer chain P ¹ contains at least one kind of repeating unit.

From the viewpoint of enhancing the dispersion stability by exerting a three-dimensional repulsive force, the repeating number k (k1, k2, k3) of at least one repeating unit in the polymer chain P ¹ is preferably 5 or more, and more preferably 7 or more .

The repeating unit number k of repeating units is preferably 140 or less, more preferably 130 Below, further preferably 60 or less.

In addition, the polymer is preferably soluble in an organic solvent. If the affinity with the organic solvent is low, the affinity with the dispersion medium is weak, and it becomes impossible to secure an adsorption layer with sufficient dispersion stabilization.

The vinyl monomer is not particularly limited, for example, (meth)acrylates, crotonic acid esters, vinyl esters, vinyl monomers having acid groups, maleic diesters, fumaric acid are preferred Diesters, itaconic acid diesters, (meth)acrylamides, styrenes, vinyl ethers, vinyl ketones, olefins, maleimides, (meth)acrylonitrile, etc. More preferred are (meth)acrylates, crotonates, vinyl esters, and vinyl monomers having an acid group, and further preferred are (meth)acrylates and crotonates.

Preferred examples of these vinyl monomers include paragraphs 0089 to 0009, paragraph 0096, and paragraph 0097 of Japanese Patent Laid-Open No. 2007-277514 (paragraphs in the corresponding specification of U.S. Patent Application Publication No. 2010/233595 The vinyl monomers described in paragraphs 0105 to paragraph 0117 and paragraphs 0119 to 0120) are incorporated into the specification of the present application.

In addition to the above compounds, for example, vinyl monomers having functional groups such as carbamate groups, urea groups, sulfonamide groups, hydroxyphenyl groups, and imidate groups can also be used. Such a monomer having a carbamate group or a urea group can be suitably synthesized by, for example, an addition reaction of an isocyanate group and a hydroxyl group or an amine group. Specifically, the addition reaction of a monomer containing an isocyanate group and a compound containing a hydroxyl group or a compound containing a first- or second-stage amine group, or a monomer containing a hydroxyl group or a class 1 or 2 It is suitable for the synthesis reaction such as the addition reaction of the grade amine monomer and monoisocyanate.

The compound represented by formula (1) is preferably represented by the following formula (2).

In formula (2), A ^{2 is} synonymous with A ¹ in formula (1), and the preferred aspect is also the same.

In formula (2), R ⁴ and R ⁵ each independently represent a single bond or a divalent linking group. n R ⁴ may be the same or different. Moreover, m R ⁵ may be the same or different.

The divalent linking groups represented by R ⁴ and R ⁵ can use the same divalent linking groups as those listed as the divalent linking groups represented by R ² in formula (1), and the preferred aspects are also the same .

In formula (2), R ³ represents a (m+n)-valent linking group. m+n satisfies 3~10.

R ³ may use the same linking group as exemplified as the linking group represented by R ¹ , and the preferred aspect is also the same.

In formula (2), m and n are respectively synonymous with m and n in formula (1), and the preferred aspects are also the same.

Furthermore, P ² in formula (2) is synonymous with P ¹ in formula (1), and the preferred aspect is also the same. The m P ² may be the same or different.

Among the polymer compounds represented by formula (2), it is most preferable to satisfy all of R ³ , R ⁴ , R ⁵ , P ² , m, and n shown below.

R ³ : The specific example (1), specific example (2), specific example (10), specific example (11), specific example (16), or specific example (17)

R ⁴ : single bond, or a group selected from the group consisting of a chain saturated hydrocarbon group, a cyclic saturated hydrocarbon group, an aromatic group, an ester bond, an amide bond, an ether bond, a nitrogen atom, and a carbonyl group, or those Combination of 2 or more

R ⁵ : single bond, ethylidene, propylidene, the following group (a), or the following group (b)

In the following groups, R ¹² represents a hydrogen atom or a methyl group, and l represents 1 or 2.

P ² : polymer or copolymer of vinyl monomer, ester polymer, ether polymer, urethane polymer, and modified products thereof

m: 1~3

n: 3~6

The compound P (polymer compound represented by formula (1) or formula (2), etc.) is not particularly limited, and can be based on paragraphs 0114 to 0140 and paragraphs 0266 to 0348 of Japanese Patent Laid-Open No. 2007-277514 Documented synthesis method synthesis. In addition, specific examples of the compound P include those described below.

Compounds disclosed in Examples after paragraph 0265 of Japanese Patent Laid-Open No. 2007-277514 (B-1~B-24, C-1~C-57, D-1~D-12)

Compounds (C-1~C-136) disclosed in the Examples after paragraph 0200 of WO2014/034813A1

Compounds disclosed in the examples after paragraph 0194 of WO2014/034815A1 (C-1~C-199)

In addition, the production method of the compound P can be referred to the aforementioned publications.

The concentration of the compound P is preferably 0.01% by mass or more in the etching solution, more preferably 0.05% by mass or more, and particularly preferably 0.1% by mass or more. The upper limit is preferably 20% by mass or less, more preferably 10% by mass or less, even more preferably 5% by mass or less, and particularly preferably 1% by mass or less. By applying the compound P at the above concentration, good metal layer (second layer) etching can be achieved, and effective protection of the first layer, third layer, and fourth layer can be achieved.

Compound P may be used alone or in combination.

(Metal dissolved component)

The etching solution of the present invention contains a metal dissolved component. The metal dissolved component is preferably a halide ion, and more preferably a fluoride ion. It can be understood that metal-dissolved components (particularly fluoride ions) play a role in the etching solution as a ligand (complexing agent) of the metal (Ti, etc.) of the second layer, thereby promoting dissolution.

The concentration of the dissolved metal component (particularly fluoride ion) is preferably 0.1% by mass or more in the etching solution, more preferably 0.5% by mass or more, and particularly preferably There are more than 1% by mass. 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. By applying metal-dissolved components (especially fluoride ions) at the above concentration, good metal layer etching can be achieved, and effective protection of the layer to be protected can be achieved. Only one type of dissolving component may be used, or a plurality of types may be used in combination.

In addition, in the confirmation of the blending amount, when the component is an ion, the amount of the added salt can also be determined by quantifying the amount of the added salt.

The fluorine ion supply source may include the fluorine compounds in the following table.

(Acids with pKa of 4 or less (acid additives))

It is preferable to include an acid auxiliary agent (acid with pKa of 4 or less) in the etching solution of the present invention. The pKa is more preferably 3 or less, more preferably 2 or less, still more preferably 1.5 or less, still more preferably 1 or less, and particularly preferably 0.5 or less. The lower limit is actually pKa above -20. It can be understood that the acid additive plays the following role in the etching solution: even the formulation with low water content can accelerate the oxidation of the metal (Ti, etc.) of the second layer. From this point of view, if the pKa exceeds the above range, there is a phenomenon that the metal (unoxidized) Ti and the like cannot be dissolved.

The acid assistant is preferably a boric acid compound, a phosphoric acid compound, a phosphonic acid compound, HBF ₄ , HBr, HCl, HI, H ₂ SO ₄ , F ₃ CCOOH, Cl ₃ CCOOH and the like. Among them, inorganic acids are preferred, and inorganic acids containing halogen atoms are more preferred. The reason for the effect of the acid auxiliary agent in the present invention is not clear, but it can be understood that the anion of the acid auxiliary agent exhibits a unique effect due to the relationship with the time dependency of the etching described later.

pKa is synonymous with the definition. The calculation examples of representative substituents are shown below. When the acid adjuvant has a multi-level dissociation constant, it is evaluated by the smallest dissociation constant.

HBF ₄ : -0.4

HBr: -9.0

HCl: -7.0

MSA: -1.8 (methanesulfonic acid)

TSA: -2.8 (p-toluenesulfonic acid)

Examples of the phosphonic acid compounds include alkylphosphonic acids (preferably, the carbon number is 1 to 30, more preferably, the carbon number is 3 to 24, and particularly preferably, the carbon number is 4 to 18), and arylphosphonic acid (compared Preferably, the carbon number is 6~22, more preferably, the carbon number is 6~14, and particularly preferably, the carbon number is 6~10), aralkylphosphonic acid (preferably, the carbon number is 7~23, More preferably, the carbon number is 7~15, and particularly preferable is that the carbon number is 7~11). Or it may be polyvinylphosphonic acid. The weight average molecular weight may be selected as appropriate, and is preferably 3,000 or more and 50,000 or less.

Examples of the acid compound containing boron include boric acid, boric acid, and tetrafluoroboric acid. The boronic acid is preferably boronic acid having 1 to 24 carbon atoms, and more preferably boronic acid having 1 to 12 carbon atoms. Specific examples include phenylboronic acid and methylboronic acid.

When these acids become salts, their counter ions are not particularly limited, and alkali metals can be cited Cation or organic cation, etc.

The concentration of the acid additive is preferably 0.1% by mass or more in the etching solution, 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, even more preferably 5% by mass or less, and particularly preferably 3% by mass or less. With respect to 100 parts by mass of the dissolved component, it is preferably 10 parts by mass or more, more preferably 30 parts by mass or more, and particularly preferably 50 parts by mass or more. The upper limit is preferably 1000 parts by mass or less, more preferably 600 parts by mass or less, and particularly preferably 200 parts by mass or less. In addition, only one kind of acid additive may be used, or two or more kinds may be used in combination.

(Organic solvents)

The etching solution of the present invention may contain an organic solvent. Among them, the organic solvent is preferably a protic polar organic solvent. The protic polar organic solvent is preferably an alcohol compound (including a polyol compound), an ether compound, and a carboxylic acid compound. It can be understood that the organic solvent plays the following role in the etching solution: by reducing the relative amount of water in the chemical solution, the dissolution rate of the metal or the insulating film requiring selective treatment is reduced.

For the organic solvent, for example, it is desirable that the δh (hydrogen bond energy) of the Hansen solubility parameter is 5 or more, and particularly preferably 10 or more. The ideal viscosity is 40mPa. Below s(20℃), 35mPa is more ideal. Below s, 10mPa is particularly ideal. s below.

. Alcohol compounds

Alcohol compounds widely include compounds having carbon and hydrogen in the molecule and having more than one hydroxyl group. Here, even if it is an ether compound, those having a hydroxyl group also serve as an alcohol compound. The carbon number of the alcohol compound may be 1 or more, more preferably 2 or more, and still more preferably It is 3 or more, more preferably 4 or more, still more preferably 5 or more, and particularly preferably 6 or more. The upper limit is preferably 24 or less, more preferably the carbon number is 12 or less, and particularly preferably the carbon number is 8 or less.

For example, methanol, ethanol, 1-propanol, 2-propanol, 2-butanol, ethylene glycol, propylene glycol, glycerin, hexanediol [HG], 1,6-hexanediol, cyclohexane Glycol, sorbitol, xylitol, 2-methyl-2,4-pentanediol, 1,3-butanediol, 1,4-butanediol [14BD], 3-methyl-1- Butanol [3M1B], methylpentanediol, cyclohexanol, ethylhexanol, benzyl alcohol, phenylethanol and other alcohol compounds that do not contain ether groups,

Contains alkyl glycol alkyl ethers (ethylene glycol monomethyl ether, ethylene glycol monobutyl ether, dipropylene glycol, propylene glycol monomethyl ether, diethylene glycol monomethyl ether, triethylene glycol, polyethylene glycol, propylene glycol mono Ether, dipropylene glycol monomethyl ether, tripropylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol monobutyl ether [DEGBE], etc.), phenoxyethanol, methoxymethyl butanol containing ether groups Of alcohol compounds.

Among the alcohol compounds, compounds represented by the following formula (O-1) are preferred.

R ^O1 -(-OR ^O2 -) _nO -OH…(O-1)

. R ^O1

R ^O1 is a hydrogen atom or an alkyl group having a carbon number of 1 to 12 (preferably 1 to 6, more preferably 1 to 3), and an aromatic group having a carbon number of 6 to 14 (preferably 6 to 10) Group, or an aralkyl group having 7 to 15 carbon atoms (preferably 7 to 11).

. R ^O2

R ^O2 is a linear or branched alkylene chain having 1 to 12 carbon atoms. When there are multiple R ^O2 , they may also be different. R ^O2 preferably has a carbon number of 2 to 10, and more preferably has a carbon number of 2 to 6.

. no

no is an integer of 0 or more and 12 or less, preferably 1 or more and 6 or less. When no is 2 or more, a plurality of R ^O2 may be different from each other. However, when no is 0, R ^O1 is not a hydrogen atom.

The alcohol compound is also preferably a compound represented by the following formula (O-2) or formula (O-3).

R ^O3 -L ^O1 -R ^O4 -OH…(O-2)

R ^O3 -(L ^O1 -R ^O4 )no-OH…(O-3)

R ^{O3 is} preferably a cyclic structure which may also have a substituent. The cyclic structural group may be an aromatic ring, an aromatic heterocyclic ring, an aliphatic ring, or an aliphatic heterocyclic ring. Examples of the aromatic ring include aryl groups having 6 to 14 carbon atoms (preferably 6 to 10 carbon atoms, and more preferably phenyl groups). The aliphatic ring may be cyclic alkyl having 3 to 14 carbon atoms (preferably having 3 to 10 carbon atoms, and more preferably cyclohexyl). The heterocyclic ring is preferably a heterocyclic group having 2 to 20 carbon atoms. Among them, a 5-membered ring or 6-membered ring heterocyclic group having at least one oxygen atom, sulfur atom, and nitrogen atom is preferred. Examples include 2-pyridyl, 4-pyridyl, 2-imidazolyl, 2-benzimidazolyl, 2-thiazolyl, and 2-oxazolyl. The cyclic structural group may suitably have any substituent.

L ^O1 is a single ^{bond, O, CO, NR N,} S, or a combination of the plurality. Among them, single bonds, CO, and O are preferred, and single bonds or O are more preferred. ^RN according to the definition.

R ^O4 is an alkylene group (preferably a carbon number of 1 to 12, more preferably a carbon number of 1 to 6, particularly preferably a carbon number of 1 to 3), an aryl group (preferably a carbon The number is 6-14, more preferably the carbon number is 6-10), or the aralkyl group (preferably the carbon number is 7-15, more preferably the carbon number is 7-11).

no is synonymous with the above.

Among them, the ether compound is preferably a compound represented by the following formula (E-1).

R ^E1 -(-OR ^E2 -) _m -R ^E3 …(E-1)

. R ^E1

R ^E1 is an alkyl group having a carbon number of 1 to 12 (preferably 1 to 6, more preferably 1 to 4, and even more preferably 1 to 3), and a carbon number of 6 to 14 (preferably 6-10) aryl groups, or aralkyl groups having 7-15 carbon atoms (preferably 7-11).

. R ^E2 is synonymous with R ^O2 .

. R ^E3 is synonymous with R ^O1 .

. m is an integer of 1 or more and 12 or less, preferably 1 or more and 6 or less. When m is 2 or more, a plurality of R ^E2 may be different from each other.

The concentration of the organic solvent is preferably 20% by mass or more in the etching solution, more preferably 50% by mass or more, and particularly preferably 70% by mass or more. The upper limit is preferably 98% by mass or less, more preferably 95% by mass or less, and particularly preferably 90% by mass or less.

In addition, in the present invention, only one organic solvent may be used, or two or more organic solvents may be used in combination. When two or more types are used in combination, the combination ratio is not particularly limited, and the total amount used is preferably the sum of the two or more types in the concentration range.

(Carboxylic acid compound)

The etching solution of the present invention may contain a carboxylic acid compound. The carboxylic acid compound is preferably an organic compound having a carboxyl group. The carboxylic acid compound may have a low molecular weight if it has a carboxyl group in the molecule. When the carboxylic acid compound is a low-molecular compound, the carbon number is preferably 4 to 48, more preferably the carbon number is 4 to 36, and particularly preferably the carbon number is 6 to 24. It can be understood that the carboxylic acid compound plays the following role in the etching solution: as a complexing agent, it accelerates the dissolution of the metal oxide (titanium oxide, etc.) of the second layer.

The carboxylic acid compound is preferably a compound represented by R ¹ -COOH. R ¹ is an alkyl group (preferably a carbon number of 1 to 48, more preferably a carbon number of 4 to 36, and particularly preferably a carbon number of 6 to 24), alkenyl group (preferably a carbon number of 2~48, more preferably, the carbon number is 4~36, further preferably, the carbon number is 6~24), alkynyl group (preferably, the carbon number is 2~48, more preferably, the carbon number is 4 ~36, further preferably 6 to 24 carbon atoms, aryl (preferably 6 to 22 carbon atoms, more preferably 6 to 14 carbon atoms), or aralkyl (preferably The carbon number is 7~23, more preferably the carbon number is 7~15). When R ¹ is an aryl group, an alkyl group having 1 to 20 carbon atoms, an alkenyl group having 2 to 20 carbon atoms, or an alkynyl group having 2 to 20 carbon atoms may be substituted thereon. When R ¹ is an alkyl group, it may have the following structure.

*-R ² -(R ³ -Y) _n -R ⁴

R ² is a single bond, an alkylene group (preferably the carbon number is 1 to 12, more preferably the carbon number is 1 to 6, particularly preferably the carbon number is 1 to 3), the alkynyl group (preferably The carbon number is 2~12, more preferably the carbon number is 2~6), the alkenyl group (preferably the carbon number is 2~12, more preferably the carbon number is 2~6), stretch aromatic Group (preferably the carbon number is 6-22, more preferably the carbon number is 6-14), or aralkylene group (preferably the carbon number is 7-23, more preferably the carbon number is 7 ~15).

The linking groups of R ³ and R ² are synonymous.

Y is an oxygen atom (O), a sulfur atom (S), a carbonyl group (CO), or an imino group (NR ^N ). R ⁴ is an alkyl group (preferably a carbon number of 1 to 12, more preferably a carbon number of 1 to 6, particularly preferably a carbon number of 1 to 3), an alkenyl group (preferably a carbon number of 2-12, more preferably carbon number 2-6), alkynyl (preferably carbon number 2-12, more preferably carbon number 2-6), aryl group (preferably carbon The number is 6 to 22, more preferably the carbon number is 6 to 14), or the aralkyl group (preferably the carbon number is 7 to 23, more preferably the carbon number is 7 to 15). ^RN according to the definition.

n is an integer from 0 to 8.

R ¹ may further have a substituent, of which sulfonyl (SH), hydroxyl (OH), and amine (NR ^N ₂ ) are preferred. ^RN according to the definition.

The concentration of the carboxylic acid compound is preferably 0.01% by mass or more in the etching solution, more preferably 0.05% by mass or more, and particularly preferably 0.1% by mass or more. The upper limit is preferably 10% by mass or less, more preferably 3% by mass or less, and particularly preferably 1 Mass% or less. With respect to 100 parts by mass of hydrofluoric acid, it is preferably 1 part by mass or more, more preferably 3 parts by mass or more, and particularly preferably 5 parts by mass or more. The upper limit is preferably 50 parts by mass or less, more preferably 30 parts by mass or less, and particularly preferably 20 parts by mass or less.

(oxalic acid)

In the carboxylic acid compound, oxalic acid may be contained in the etchant as another kind of additive. Oxalic acid acts as a complexing agent in the etching solution.

The concentration of oxalic acid is preferably 0.1% by mass or more in the etching solution, 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, even more preferably 5% by mass or less, and particularly preferably 3% by mass or less. With respect to 100 parts by mass of hydrofluoric acid, it is preferably 10 parts by mass or more, more preferably 30 parts by mass or more, and particularly preferably 50 parts by mass or more. The upper limit is preferably 1000 parts by mass or less, more preferably 600 parts by mass or less, and particularly preferably 200 parts by mass or less.

(carbohydrate)

The etching solution of the present invention may contain sugar. It can be understood that the saccharides play a role in preventing corrosion of the desired protective layer in the etching solution.

The sugars are not particularly limited, and may be monosaccharides or polysaccharides, preferably monosaccharides. Monosaccharides include hexose, pentose and the like. Structurally, ketose, aldose, pyranose, and furanose can be mentioned. Examples of hexose include allose, altrose, glucose, mannose, gulose, idose, galactose, talose, allulose, fructose, sorbose, tagatose, and the like. Examples of pentoses include ribose, arabinose, xylose, lyxose, ribulose, Xylulose etc. Examples of furanose include erythrfuranose, furansuaraose, ribofuranose, arabinan furanose, xylofuranose, and lefufuranose. Examples of pyranose include ribofuranose, arabinopyranose, xylanopyranose, lysopyranose, allopyranose, acetopyranose, grape pyranose, pyranulose, gulopyran Sugar, idylpyranose, galactopyranose, talopyranose.

The concentration of sugar is preferably 0.01% by mass or more in the etching solution, more preferably 0.05% by mass or more, and particularly preferably 0.1% by mass or more. The upper limit is preferably 10% by mass or less, more preferably 3% by mass or less, and particularly preferably 1% by mass or less. Relative to 100 parts by mass of the dissolved component, it is preferably 1 part by mass or more, more preferably 3 parts by mass or more, and particularly preferably 5 parts by mass or more. The upper limit is preferably 50 parts by mass or less, more preferably 30 parts by mass or less, and particularly preferably 20 parts by mass or less.

(Polymer containing carboxylic acid)

The etching solution of the present invention may also contain a carboxylic acid-containing polymer. It is understood that the carboxylic acid-containing polymer plays a role of preventing corrosion of the Al or Si-based insulating film in the etchant.

The carboxylic acid-containing polymer is not particularly limited, and various polymers including a structural unit having a carboxyl group can be applied. Examples of the monomer constituting such a polymer include acrylic acid (AA), methacrylic acid (MA), and vinyl benzoic acid (VBA).

The concentration of the carboxylic acid-containing polymer is preferably 0.01% by mass or more in the etching solution, more preferably 0.05% by mass or more, and particularly preferably 0.1% by mass or more. The upper limit is preferably 10% by mass or less, more preferably 3% by mass or less, and particularly preferably 1% by mass or less. Relative to 100 parts by mass of dissolved components, It is preferably 1 part by mass or more, more preferably 3 parts by mass or more, and particularly preferably 5 parts by mass or more. The upper limit is preferably 50 parts by mass or less, more preferably 30 parts by mass or less, and particularly preferably 20 parts by mass or less.

In the present specification, when the compound, substituent/linker, etc. include alkyl/alkylene, alkenyl/alkenyl, alkynyl/alkynyl, etc., these may be cyclic or chain-like, It may be linear or branched, and may be substituted by any group or unsubstituted. At this time, an alkyl / alkylene, alkenyl / alkenylene group, an alkynyl group / insert also extending alkynyl group (e.g. O, S, CO, NR ^N and the like) containing a hetero atom, and also along with this Form a ring structure. In addition, when an aryl group, a heterocyclic group, or the like is included, these may be monocyclic or condensed, and may be substituted or unsubstituted.

In the present specification, various technical matters such as temperature and thickness, including the choice of the substituent or the linking group of the compound, may be described independently in the list, or may be combined with each other.

In the present specification, when the compound is attached to the end of the compound or acid, the meaning of the ion and salt is included in addition to the compound within the scope of the effect of the present invention. Furthermore, the meaning of its derivatives is also included.

(water)

It is preferable that the etching solution of the present invention contains water (aqueous medium). The water (aqueous medium) may be an aqueous medium containing a dissolved component within a range that does not impair the effects of the present invention, or may contain an inevitable trace of a mixed component. Among them, the purified water such as distilled water, ion-exchanged water, or ultrapure water is preferable, and ultrapure water used in semiconductor manufacturing is particularly preferable. The concentration of water is not particularly limited, It is preferably 0.1% by mass or more, more preferably 1% by mass or more, and particularly preferably 5% by mass or more. The upper limit is preferably 50% by mass or less, more preferably 40% by mass or less, and particularly preferably 25% by mass or less.

In the present invention, it is preferable to set the concentration of the etching solution within a predetermined range. In the anhydrous state, there is a phenomenon that the etching effect of the metal layer is not sufficiently exhibited. It is preferably used in this respect, but by suppressing the amount to a small amount, the damage of the metal layer to be protected can be suppressed.

(Specific organic additives)

It is preferable that the etching solution of this embodiment contains a specific organic additive. The organic additive contains an organic compound containing a nitrogen atom, a sulfur atom, a phosphorus atom, or an oxygen atom. Among them, the organic additive preferably has an amine group (-NR ^N ₂ ) or a salt thereof, an imino group (-NR ^N -) or a salt thereof, a sulfanyl group (-SH), a hydroxyl group ( -OH), carbonyl group (-CO-), sulfonic acid group (-SO ₃ H) or its salt, phosphoric acid group (-PO ₄ H ₂ ) or its salt, onium group or its salt, sulfinyl group (-SO -), sulfonyl (SO ₂ ), ether (-O-), amine oxide, and thioether (-S-) substituents or linker compounds. Also preferred are aprotic dissociative organic compounds (alcohol compounds, ether compounds, ester compounds, carbonate compounds), azole compounds, betaine compounds, sulfonic acid compounds, amide compounds, onium compounds, amino acid compounds, Phosphoric acid compounds, sulfonate compounds.

The ^{RN is} according to the definition. The substituent is preferably an alkyl group (preferably, the carbon number is 1 to 24, more preferably, the carbon number is 1 to 12, and even more preferably, the carbon number is 1 to 6, and particularly preferably, the carbon number is 1~3), alkenyl group (preferably, the carbon number is 2~24, more preferably, the carbon number is 2~12, even more preferably, the carbon number is 2~6, and particularly preferably, the carbon number is 2 ~3), alkynyl groups (preferably, the carbon number is 2~24, more preferably, the carbon number is 2~12, even more preferably, the carbon number is 2~6, and particularly preferably, the carbon number is 2~ 3). Aryl groups having 6 to 10 carbon atoms and aralkyl groups having 7 to 11 carbon atoms.

It is particularly preferable that the specific organic additive includes a compound represented by any of the following formula (I) to formula (XIII).

Formula (I):

R ¹¹ and R ¹² are independently a hydrogen atom, an alkyl group (preferably the carbon number is 1-12, more preferably the carbon number is 1-6, and particularly preferably the carbon number is 1-3), alkenyl group (Preferably the carbon number is 2-12, more preferably the carbon number is 2-6), alkynyl (preferably the carbon number is 2-12, more preferably the carbon number is 2-6), Aryl (preferably carbon number 6~22, more preferably carbon number 6-14), aralkyl group (preferably carbon number 7-23, more preferably carbon number 7~ 15), a thio group (SH), a hydroxyl group (OH), or an amine group (-NR ^N ₂ ). Among them, it is preferable that at least one of R ¹¹ and R ¹² is a thio group, a hydroxyl group, or an amine group (preferably, the carbon number is 0 to 6, and more preferably, the carbon number is 0 to 3). ^RN according to the definition. In addition, when the substituent further uses a substituent (alkyl, alkenyl, aryl, etc.), it may further have an arbitrary substituent T. The substituents or linking groups described later are also the same.

X ¹ is a methylene group (CR ^C ₂ ), a sulfur atom (S), or an oxygen atom (O). Among them, a sulfur atom is preferred. R ^C is a hydrogen atom or a substituent (preferably the substituent T described later).

Formula (II):

X ² is a methine group (=CR ^C -) or a nitrogen atom (N). R ²¹ is a substituent (preferably a substituent T described later), and among them, a thio group (SH), a hydroxyl group (OH), and an amine group (NR ^N ₂ ) are preferred. R ^C and R ^{N are} based on the above definition.

n2 is an integer from 0 to 4.

When there are a plurality of R ²¹ , these may be the same or different, or may be bonded or condensed with each other to form a ring. The formed ring is preferably a nitrogen-containing heterocyclic ring, and more preferably an unsaturated 5- or 6-membered nitrogen-containing heterocyclic ring.

Formula (III):

Y ¹ is a methylene group, an imino group (NR ^N ), or a sulfur atom (S). ^RN according to the definition.

Y ² is a hydrogen atom, an alkyl group (preferably a carbon number of 1 to 12, more preferably a carbon number of 1 to 6, particularly preferably a carbon number of 1 to 3), alkenyl group (preferably Carbon number is 2-12, more preferably carbon number 2-6), alkynyl group (preferably carbon number 2-12, more preferably carbon number 2-6), aryl group (preferably Carbon number is 6-22, more preferably carbon number 6-14), aralkyl (preferably carbon number 7-23, more preferably carbon number 7-15), amine group (Preferably, the carbon number is 0~6, more preferably, the carbon number is 0~3), hydroxyl group, and sulfur group.

R ³¹ is a substituent (preferably the substituent T described later). Among them, preferred are a sulfur group (SH), a hydroxyl group (OH), and an amine group (NR ^N ₂ ). ^RN according to the definition.

n3 is an integer from 0 to 2.

When there are a plurality of R ³¹ , these may be the same or different, or may be bonded or condensed with each other to form a ring. The formed ring is preferably a six-membered ring, and a benzene structure or a six-membered heteroaryl structure (among them, a pyridine structure and a pyrimidine structure are preferred).

The formula (III) is preferably the following formula (III-1).

Y ³ and Y ⁴ are each independently a methine group (=CR ^C -) or a nitrogen atom (N). R ^C according to the definition.

Y ¹ , Y ² , R ³¹ and n3 are synonymous with the above. As for the positions of Y ³ and Y ⁴ , they can also be located at other positions in the six-member ring.

Formula (IV):

L ¹ is an alkylene group (preferably a carbon number of 1 to 12, more preferably a carbon number of 1 to 6, particularly preferably a carbon number of 1 to 3), alkynyl group (preferably a carbon The number is 2-12, more preferably the carbon number is 2-6), the alkenyl group (preferably the carbon number is 2-12, more preferably the carbon number is 2-6), the aryl group (more Preferably, the carbon number is 6-22, more preferably, the carbon number is 6-14), or aralkylene (preferably, the carbon number is 7-23, and more preferably, the carbon number is 7-15) .

X ⁴ is a carboxyl group or a hydroxyl group.

The SH group in the formula can also be disulfide to form a dimer.

Formula (V):

R ⁵¹ is an alkyl group (preferably, the carbon number is 1-24, more preferably, the carbon number is 1-12, even more preferably, the carbon number is 1-6, and particularly preferably, the carbon number is 1-3. ), alkenyl (preferably the carbon number is 2 to 24, more preferably the carbon number is 2 to 12, and even more preferably the carbon number is 2 to 6), alkynyl (preferably the carbon number is 2~24, more preferably, the carbon number is 2~12, and even more preferably, the carbon number is 2~6), aryl group (preferably, the carbon number is 6~22, more preferably, the carbon number is 6 ~14), or aralkyl (preferably the carbon number is 7~23, more preferably the carbon number is 7~15).

When R ⁵¹ is an aryl group, it is preferably substituted with an alkyl group having 1 to 20 carbon atoms, an alkenyl group having 2 to 20 carbon atoms, or an alkynyl group having 2 to 20 carbon atoms, and the carbon number It is an alkoxy group of 1-20, an aryl group having 6-14 carbon atoms, and an aryloxy group having 6-14 carbon atoms.

When R ⁵¹ is an alkyl group, it may have the following structure.

*-R ⁵² -(R ⁵³ -Y ⁵³ ) _n5 -R ⁵⁴

R ⁵² is a single bond or a linking group synonymous with L ¹ . R ⁵³ is a linking group synonymous with L ¹ . Y ⁵³ is an oxygen atom (O), a sulfur atom (S), a carbonyl group (CO), or an imino group (NR ^N ). Or it may be a combination of an oxygen atom (O), a sulfur atom (S), a carbonyl group (CO), and an imino group (NR ^N ). For example, (C=O)O, O(C=O), etc. may be mentioned. R ⁵⁴ is an alkyl group (preferably, the carbon number is 1~24, more preferably, the carbon number is 1~12, even more preferably, the carbon number is 1~6, and particularly preferably, the carbon number is 1~3. ), alkenyl (preferably the carbon number is 2~12, more preferably the carbon number is 2~6), alkynyl (preferably the carbon number is 2~12, more preferably the carbon number is 2 ~6), aryl (preferably carbon number 6~22, more preferably carbon number 6-14), or aralkyl group (preferably carbon number 7~23, more preferably Carbon number is 7~15). ^RN according to the definition.

n5 is an integer from 0 to 8.

R ⁵¹ may further have a substituent T, among which a thio group (SH), a hydroxyl group (OH), and an amine group (NR ^N ₂ ) are preferred. ^RN according to the definition.

Z is an amine group (NR ^N ₂ ) (preferably the carbon number is 0~6, more preferably the carbon number is 0~3), sulfonic acid group (SO ₃ H), sulfate group (SO ₄ H), a phosphate group (PO ₄ H _2), carboxy, hydroxy, thio (SH), an onium group (preferably having 3 to 12 carbon atoms), acyl group, or an amine oxide (-NR ^N ₂ ⁺ O ^- ). Here, ^{RN is} according to the definition.

In the present invention, unless otherwise specified, an amine group, a sulfonic acid group, a phosphate group, and a carboxyl group, in the case of their salts or acids, mean that their acid esters (such as alkyl esters, preferably carbon The number is 1~24, more preferably, the carbon number is 1~12, and even more preferably, the carbon number is 1~6). The alkyl group to be a carboxylic acid ester may further have a substituent T. For example, an alkyl group having a hydroxyl group can be mentioned. In this case, the alkyl group may contain heteroatom (e.g. O, S, CO, NR ^N, etc.) form a ring structure. Examples of the alkyl group having a hydroxy ring structure include sorbitan residues. That is, the sorbitan fatty acid ester can be suitably used (preferably the carbon number is 7-40, and more preferably the carbon number is 8-24).

Between R ⁵¹ and Z in formula (V) may also have any linking group within a range that achieves the desired effect. Examples of any linking group include the above-mentioned examples of L ¹ and examples of Y ⁵³ .

When formula (V) is a carboxylic acid, R ^{51 is} preferably an alkyl group. In this case, the carbon number is preferably 1 to 24, more preferably the carbon number is 3 to 20, and still more preferably The carbon number is 6~18, and the carbon number is 8~16. The alkyl group may further have a substituent T, which is the same as in other cases.

The compound having an onium group is preferably a compound having an ammonium group _{^{(R 51 -NR N 3 + M}} -), a compound having a pyridinium group _{^{(C 5 R N 5 N +}} -R 51 .M -), compound _{^{(C 3 R N 3 NR N}} N + -R 51 .M -) or an imidazolinium group. R ^N is synonymous with the above. M ^- is an anion pair (e.g., OH ^-).

If the compound having the onium group is exemplified in further detail, those represented by the following formula can be cited.

[Chem 11]

In the formula, R ^O7 ~ R ^O10 are independently an alkyl group having 1-24 carbon atoms, an alkenyl group having 2-24 carbon atoms, an alkynyl group having 2-24 carbon atoms, and an aryl group having 6-14 carbon atoms. , An aralkyl group having 7 to 14 carbon atoms, and a group represented by the following formula (y). Among them, the carbon number of at least one of R ^O7 to R ^O10 is preferably 6 or more, and more preferably 8 or more.

Y1-(Ry1-Y2)my-Ry2-* (y)

Y1 represents a hydrogen atom, an alkyl group having 1 to 12 carbon atoms, an alkenyl group having 2 to 12 carbon atoms, an alkynyl group having 2 to 12 carbon atoms, an aralkyl group having 7 to 14 carbon atoms, and 6 carbon atoms ~14 aryl, hydroxyl, or alkoxy having 1 to 4 carbons. Y2 represents O, S, CO, NR ^N. Ry1 and Ry2 independently represent an alkylene group having 1 to 6 carbon atoms, an alkenyl group having 2 to 6 carbon atoms, an alkynyl group having 2 to 6 carbon atoms, and an arylene group having 6 to 10 carbon atoms. , Or a combination of these. my represents an integer from 0 to 6. When my is 2 or more, a plurality of Ry1 and Ry2 may be different. Ry1 and Ry2 may further have a substituent T. *It is a combination key. ^RN according to the definition.

R ^O11 is a group synonymous with R ^O7 , and the carbon number is preferably 6 or more, and more preferably 8 or more. R ^O12 is a substituent T. mO is an integer from 0 to 5.

M4 ^-, M5 ^-, and M6 ^- is a counter ion, for example, hydroxide ions.

R ^O13 is synonymous with Y1. R ^O14 and R ^O15 are synonymous with formula (y). It is preferred that at least one Y1 of R ^O14 and R ^O15 is a carboxyl group, constituting betaine.

The compound represented by formula (V) is preferably any of the following formula (V-1) to formula (V-3). In the formula, Z ¹ and Z ² are sulfonic acid groups that sometimes intersect the linking group L. R ⁵⁶ is a substituent T, and the alkyl group exemplified here is preferable. n ⁵¹ and n ⁵⁶ are integers from 0 to 5. n ⁵³ is an integer from 0 to 4. The maximum values of n ⁵¹ , n ⁵³ , and n ⁵⁶ decrease according to the number of Z ¹ or Z ² located in the same ring. n ⁵² is an integer from 1 to 6, preferably 1 or 2. n ⁵⁴ and n ⁵⁵ are independently integers of 0 to 4, and n ⁵⁴ +n ⁵⁵ are 1 or more. n ⁵⁴ +n ^{55 is} preferably 1 or 2. n ⁵⁷ and n ⁵⁸ are independently integers from 0 to 5, and n ⁵⁷ +n ⁵⁸ are 1 or more. n ⁵⁷ +n ^{58 is} preferably 1 or 2. A plurality of R ⁵⁶ may be the same as or different from each other. The linking group L is preferably L ¹ , L ² described below, or a combination thereof, and more preferably L ¹ .

Formula (VI):

R ⁶¹ and R ⁶² are each independently an alkyl group (preferably a carbon number of 1 to 12, more preferably a carbon number of 1 to 6, particularly preferably a carbon number of 1 to 3), an aryl group (preferably The carbon number is 6-22, more preferably the carbon number is 6-14), the alkoxy group (preferably the carbon number is 1-12, more preferably the carbon number is 1~6, particularly good It is a carbon number of 1 to 3), or an alkylamine group (preferably a carbon number of 1 to 12, more preferably a carbon number of 1 to 6, particularly preferably a carbon number of 1 to 3). R ⁶¹ and R ⁶² can also be bonded or condensed to form a ring. When R ⁶¹ or R ⁶² is an alkyl group, the group represented by *-R ⁵² -(R ⁵³ -Y ⁵³ )-R ⁵⁴ may also be used.

L ² is carbonyl, sulfinyl (SO), or sulfonyl (SO ₂ ).

The compound represented by formula (VI) is preferably a compound represented by any of the following formula (VI-1) to formula (VI-3). In the formula, R ⁶¹ and R ^{62 are} synonymous with the above. Q ⁶ is a 3-member ring to 8-member ring, preferably a 5-member ring or a 6-member ring, more preferably a saturated 5-member ring or a 6-member ring, and particularly preferably a saturated hydrocarbon 5-member ring or a 6-member ring ring. Among them, Q ⁶ may have an arbitrary substituent T.

Formula (VII):

R ⁷¹ is an amine group (-NR ^N _2), ammonium groups _{^{(-NR N 3 + .M -)}} , or a carboxyl group. R ^N and M ^- according to the definition.

L ³ is a single bond or a group synonymous with L ¹ . Among them, L ^{3 is} preferably methylene, ethylidene, propylidene, or (-L ³¹ (SR ^S )p-). L ³¹ is an alkylene group having 1 to 6 carbon atoms. R ^S is a hydrogen atom or a disulfide group may be formed at this site to dimerize. p is an integer of 1 or more and 5 or less, preferably 1 or more and 2 or less.

When R ⁷¹ is a carboxyl group, the compound becomes a dicarboxylic acid compound. Examples of the dicarboxylic acid compound include oxalic acid, malonic acid, succinic acid, glutaric acid, adipic acid, pimelic acid, cork acid, azelaic acid, sebacic acid, phthalic acid, isophthalic acid , Terephthalic acid, etc., of which oxalic acid is preferred.

Formula (IIX):

R ⁸¹ and R ⁸² are each independently an alkyl group (preferably a carbon number of 1 to 12, more preferably a carbon number of 1 to 6, particularly preferably a carbon number of 1 to 3), alkenyl (preferably Carbon number is 2-12, more preferably carbon number 2-6), alkynyl (preferably carbon number 2-12, more preferably carbon number 2-6), aryl ( Preferably the carbon number is 6-22, more preferably the carbon number is 6-14), or aralkyl (preferably the carbon number is 7-23, more preferably the carbon number is 7-15) . ^RN according to the definition.

Formula (IX):

L ⁴ is a base synonymous with L ¹ .

R ⁹¹ and R ⁹³ are independently a hydrogen atom, an alkyl group (preferably the carbon number is 1-12, more preferably the carbon number is 1-6, and particularly preferably the carbon number is 1-3), alkenyl group (Preferably the carbon number is 2-12, more preferably the carbon number is 2-6), alkynyl (preferably the carbon number is 2-12, more preferably the carbon number is 2-6), Aryl (preferably the carbon number is 6~22, more preferably the carbon number is 6~14), acetyl group (preferably the carbon number is 2~12, more preferably the carbon number is 2~6 ), or aralkyl (preferably the carbon number is 7~23, and more preferably the carbon number is 7~15). However, when n9 is 0, not all of R ⁹¹ and R ⁹³ become hydrogen atoms.

n9 is an integer from 0 to 100, preferably 0 to 50, more preferably 0 to 25, even more preferably 0 to 15, even more preferably 0 to 10, and particularly preferably 0 to 5.

The compound represented by formula (IX) is more preferably represented by the following formula (IX-1) The compound shown.

R ⁹¹ -(OL ⁴¹ )-(OL ⁴ ) _n91 -OR ⁹³ (IX-1)

L ^{41 is} preferably an alkylene group having a carbon number of 2 or more, and preferably has a carbon number of 2-6. It can be inferred from the setting of the carbon number of the alkylene group that it does not form a unique adsorption state with a metal (for example, Ti), and does not hinder its removal. Furthermore, it can be seen that the bonding component of the metal and the fluorine atom acts hydrophilically or hydrophobically, and it is inferred that the compound having 2 or 3 or more carbon atoms linking the oxygen atom acts appropriately. From this viewpoint, L ⁴¹ further preferably has a carbon number of 3 or more, more preferably has a carbon number of 3 to 6, and particularly preferably has a carbon number of 3 or 4. In addition, as the carbon number of the L ⁴¹ , when it is a branched alkylene group, it is preferable that the carbon atoms contained in the branch are excluded, and the number of linked carbons is 2 or more. For example, the number of connected carbons of 2,2-propanediyl becomes 1. That is, the number of carbon atoms connecting OO is called the number of connecting carbons, and it is preferably two or more. Considering the adsorption effect with the metal, the number of linked carbons is preferably 3 or more, more preferably 3 or more and 6 or less, and particularly preferably 3 or more and 4 or less.

n91 is a number synonymous with n9.

When the present compound is a compound having two or more hydroxyl groups in R ⁹¹ and R ⁹³ , the result is preferably the following formula (IX-2).

[化14]

R ⁹⁴ ~ R ⁹⁷ in the formula are synonymous with R ⁹¹ . R ⁹⁴ to R ⁹⁷ may further have a substituent T, for example, may have a hydroxyl group. L ⁹ is an alkylene group, preferably an alkylene group having 1 to 6 carbon atoms, and more preferably an alkylene group having 1 to 4 carbon atoms. Specific examples of the compound of formula (IX-2) include hexanediol, 1,3-butanediol, 1,4-butanediol, and the like.

From the viewpoint of the hydrophilicity/hydrophobicity, it is preferable that the compound represented by the formula (IX) should use the desired range in its CLogP. The CLogP value of the compound represented by the formula (IX) is preferably -0.4 or more, and more preferably -0.2 or more. The upper limit value is preferably 2 or less, and more preferably 1.5 or less.

. ClogP

The measurement of the octanol-water distribution coefficient (logP value) can generally be carried out by the flask shaking method described in JIS Japanese Industrial Standard Z7260-107 (2000). Moreover, the octanol-water partition coefficient (logP value) can be estimated by computational chemical techniques or empirical methods instead of actual measurement. Known calculation methods can use Crippen's fragmentation method ("J. Chem. Inf. Comput. Sci.", 27, 21 (1987)), Wiswanathan rupture (Viswanadhan's fragmentation) method ("J. Chem. Inf. Comput. Sci.", 29, 163 (1989)), Broto's fragmentation method ("European Medicinal Chemistry-Chemistry The Journal of Therapy (Eur. J. Med. Chem.-Chim. Ther.)", 19, 71 (1984)), etc. For the present invention Crippen's fragmentation method ("J. Chem. Inf. Comput. Sci.", 27, 21 (1987)).

The so-called "ClogP value" is the value of the common logP of the partition coefficient P of 1-octanol and water obtained by calculation. As for the method or software used for calculating the ClogP value, a well-known one can be used, and unless otherwise specified, the system of Daylight Chemical Information Systems (Daylight Chemical Information Systems): ClogP program incorporated in PCModels is used in the present invention .

Formula (X):

R ^A3 is synonymous with R ^N. R ^A1 and R ^A2 are independently a hydrogen atom, an alkyl group (preferably the carbon number is 1-12, more preferably the carbon number is 1-6, particularly preferably the carbon number is 1-3), alkenyl group (Preferably the carbon number is 2-12, more preferably the carbon number is 2-6), alkynyl (preferably the carbon number is 2-12, more preferably the carbon number is 2-6), Aryl (preferably carbon number 6~22, more preferably carbon number 6-14), aralkyl group (preferably carbon number 7-23, more preferably carbon number 7~ 15). Sulfur, hydroxyl or amine groups. Among them, it is preferable that at least one of R ^A1 and R ^A2 is a thio group, a hydroxyl group, or an amine group (preferably the carbon number is 0 to 6, and more preferably the carbon number is 0 to 3).

Formula (XI):

Y ⁷ and Y ⁸ are independently an oxygen atom, a sulfur atom, or an imino group (NR ^N ), and a carbonyl group. R ^B1 is a substituent (preferably a substituent T described later). nB is an integer from 0 to 8. Among them, any of Y ⁷ and Y ⁸ may be a methylene group (CR ^C ₂ ). R ^C and R ^{N are} based on the above definition.

Formula (XII):

Y ⁹ and Y ¹⁰ are independently an oxygen atom, a sulfur atom, a methylene group (CR ^C ₂ ), an imino group (NR ^N ), or a carbonyl group. Y ⁹ and Y ¹⁰ can also be other positions of the six-member ring. R ^C and R ^{N are} based on the above definition.

X ⁵ and X ⁶ are sulfur atoms or oxygen atoms. The dotted line indicates that the bond can be a single bond or a double bond. R ^C1 is a substituent (preferably the substituent T described later). nC is an integer from 0 to 2.

When there are a plurality of R ^C1 , they may be the same as or different from each other, or may be bonded or condensed to form a ring.

Formula (XIII):

X ³ is an oxygen atom, a sulfur atom, and an imino group (NR ^M ). R ^M is a hydrogen atom or an alkyl group having a carbon number of 1-24, preferably an alkyl group having a carbon number of 2-20, more preferably an alkyl group having a carbon number of 4-16, and particularly preferably a carbon number It is an alkyl group of 6-12.

X ⁵ is an oxygen atom, a sulfur atom, an imino group (NR ^M ), or a methylene group (CR ^C ₂ ). R ^C according to the definition.

R ^D1 is a substituent, and a substituent T described later is preferable. Among them, R ^{D1 is} preferably an alkyl group having 1 to 24 carbon atoms, and more preferably an alkyl group having 1 to 12 carbon atoms.

nD is an integer of 0~6, preferably an integer of 0~2, and particularly preferably 1.

Among them, X ³ -CO-X ⁵ in the formula is preferably NR ^N -CO-CR ^C ₂ , O-CO-O, O-CO-CR ^C ₂ . ^RN according to the definition.

It is preferable that the specific organic additive contains a compound selected from the first group or the second group described below.

Among specific organic additives, the concentration of organic additives belonging to the first group Preferably, the etching solution contains 50% by mass or more, more preferably 55% by mass or more, even more preferably 60% by mass or more, and particularly preferably 70% by mass or more. The upper limit is preferably 99% by mass or less, more preferably 95% by mass or less, and particularly preferably 90% by mass or less.

Among the specific organic additives, the concentration of the organic additives belonging to the second group is preferably 0.005 mass% or more in the etching solution, more preferably 0.01 mass% or more, and even more preferably 0.03 mass% or more, It is particularly preferable to contain 0.05% by mass or more. The upper limit is preferably 10% by mass or less, more preferably 7% by mass or less, and particularly preferably 5% by mass or less.

Regarding the difference between the above formulas and the first group and the second group, it is preferred that formula (V) or a part thereof, formula (VI), formula (IIX), formula (IX), formula (XI) Compounds are in the first group, and other compounds of formula or formula (V) or a part thereof are in the second group.

In addition, in this specification, the expression about a compound (for example, when it is attached to the end and is called a compound) is used in the meaning of including the compound itself, its salt, and its ion. In addition, within the scope of achieving the desired effect, it includes the meaning of derivatives in which a part of the substituent is introduced and changed.

In the present specification, substituted and unsubstituted substituents are not explicitly described (the same is true for the linking group), and the meaning of the substituent may be arbitrary in the group. It is also synonymous with the compound which does not clearly describe a substituted or unsubstituted. Preferred substituents include the following substituent T.

Examples of the substituent T include the following.

Alkyl (preferably alkyl having 1 to 20 carbon atoms, such as methyl, ethyl, isopropyl, third butyl, pentyl, heptyl, 1-ethylpentyl, benzyl, 2-ethoxyethyl, 1-carboxymethyl, etc.), alkenyl (preferably alkenyl having 2 to 20 carbon atoms, such as vinyl, allyl, oleyl, etc.), alkynyl (Preferably an alkynyl group having 2 to 20 carbon atoms, such as ethynyl, butadiynyl, phenylethynyl, etc.), cycloalkyl (preferably a cycloalkane having 3 to 20 carbon atoms) Groups, such as cyclopropyl, cyclopentyl, cyclohexyl, 4-methylcyclohexyl, etc.), aryl groups (preferably aryl groups having 6 to 26 carbon atoms, such as phenyl, 1-naphthyl, 4-methoxyphenyl, 2-chlorophenyl, 3-methylphenyl, etc.), heterocyclic group (preferably a heterocyclic group having 2 to 20 carbon atoms, preferably having at least one 5-membered or 6-membered heterocyclic group of oxygen atom, sulfur atom, nitrogen atom, such as 2-pyridyl, 4-pyridyl, 2-imidazolyl, 2-benzimidazolyl, 2-thiazolyl, 2 -Oxazolyl, etc.), alkoxy (preferably C 1-20 alkoxy, such as methoxy, ethoxy, isopropoxy, benzyloxy, etc.), aryloxy (Preferably aryloxy groups having 6 to 26 carbon atoms, such as phenoxy, 1-naphthoxy, 3-methylphenoxy, 4-methoxyphenoxy, etc.), alkoxy Carbonyl (preferably alkoxycarbonyl having 2 to 20 carbon atoms, such as ethoxycarbonyl, 2-ethylhexyloxycarbonyl, etc.), amine (preferably 0 to 20 carbon atoms Amine groups, including alkylamine groups, arylamine groups, such as amine groups, N,N-dimethylamino groups, N,N-diethylamine groups, N-ethylamine groups, aniline groups, etc.) , Sulfamoyl (preferably sulfamoyl with a carbon number of 0~20, such as N,N-dimethylsulfamoyl, N-phenylsulfamoyl, etc.), acetyl ( Preferably, it is an acyl group having 1 to 20 carbon atoms, for example, acetyl group, propyl group, butyl group, benzoyl group, etc.), oxy group (preferably, 1 to 20 carbon group) Oxygen, such as acetoxy Group, benzyloxy group, etc.), carbamoyl group (preferably a carbamoyl group having 1 to 20 carbon atoms, such as N,N-dimethylamine, carbamoyl group, N-phenylamine (Methanyl group, etc.), acylamino group (preferably acylamino group having 1 to 20 carbon atoms, such as acetylamino group, benzylamino group, etc.), sulfonamide group (compared to It is preferably a sulfonamide group having 0 to 20 carbon atoms, for example, mesylate, benzenesulfonamide, N-methyl mesylate, N-ethylbenzenesulfonamide, etc.) , Alkylthio (preferably alkylthio having 1 to 20 carbon atoms, such as methylthio, ethylthio, isopropylthio, benzylthio, etc.), arylthio (preferably carbon Arylthio groups with 6 to 26 atoms, such as phenylthio, 1-naphthylthio, 3-methylphenylthio, 4-methoxyphenylthio, etc.), alkylsulfonyl or arylsulfonyl Acyl (preferably C1-C20 alkylsulfonyl or arylsulfonyl, such as methylsulfonyl, ethylsulfonyl, phenylsulfonyl, etc.), hydroxyl, Cyano group, halogen atom (such as fluorine atom, chlorine atom, bromine atom, iodine atom, etc.), preferably alkyl, alkenyl, aryl, heterocyclic, alkoxy, aryloxy, alkoxycarbonyl , Amine group, acylamino group, phosphonic acid group, sulfonic acid group, phosphoric acid group, carboxyl group, hydroxyl group or halogen atom.

Moreover, each of the groups listed in these substituents T may further replace the substituent T.

(Set)

The etching solution in the present invention can also be made into a kit in which the raw material is divided into multiple parts. For example, a liquid composition prepared to contain the dissolved component in water is prepared as the first liquid, and a liquid composition containing an organic solvent is prepared as the second liquid. At this time, components such as other compounds may be contained in the first liquid, the second liquid, or other third liquids separately or simultaneously.

As an example of its use, it is preferable to mix two liquids to prepare an etching solution, and then apply it to the aspect of the etching process at an appropriate timing. By doing so, the desired etching effect can be effectively exerted without deteriorating the liquid performance caused by the decomposition of each component. Here, the "appropriate timing" after mixing refers to the period after mixing until the desired effect is lost, specifically, it is preferably within 60 minutes, more preferably within 30 minutes, and even more preferably within 10 minutes , The best is within 1 minute. There is nothing special about the lower limit, which is actually more than 1 second.

The method of mixing the first liquid and the second liquid is not particularly limited, and it is preferable to circulate the first liquid and the second liquid in their respective flow paths, and to mix them at the confluence point and mix them. After that, it is preferable to further eject or etch the etching solution obtained by circulating or joining in the flow path from the ejection port to make it contact with the semiconductor substrate. In this embodiment, it is preferable to perform the process of confluence mixing from the confluence point until contact with the semiconductor substrate at the "appropriate timing". 4, the prepared etching liquid is sprayed from the discharge 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 FIG. 4, the two liquids A and B are supplied, merge at the confluence point 14, and then move to the ejection port 13 via the flow path fc. The flow path fd represents a return path for reusing the chemical solution. Preferably, the semiconductor substrate S is placed on the turntable 12 and is rotated together with the turntable by the rotation drive unit M. In addition, the embodiment using such a substrate rotating device is also applied to a process using an etching solution that is not made into a set.

In addition, in view of its use, the etching liquid of the present invention preferably has less impurities, such as metal components, in the liquid. Especially good is that the Na, K, Ca ion concentration in the liquid is in the range of 1ppt~1ppm (mass basis). Furthermore, in the etching solution, the number of coarse particles having an average particle diameter of 0.5 μm or more is preferably in the range of 100 particles/cm ³ or less, and more preferably in the range of 50 particles/cm ³ or less.

(container)

The etching solution of the present invention (regardless of whether it is a set or not) can be stored in any container and stored, transported, and used as long as it does not cause problems such as corrosion. Moreover, for semiconductor applications, a container with high cleanliness and less elution of impurities is preferred. Usable containers include "Clean Bottle" series manufactured by Acelo Chemical Co., Ltd. and "Pure Bottle" manufactured by Kodama Resin Industry Co., Ltd., but are not limited to these .

[Etching condition]

It is preferable to use a monolithic device in the etching method of the present invention. Specifically, the monolithic device preferably includes a processing tank in which the semiconductor substrate is transported or rotated, and the processing tank is provided with (ejection, spray, flow, drip, etc.). The etching liquid brings the etching liquid into contact with the semiconductor substrate.

The advantages of the monolithic device include: (i) the fresh etching solution is always supplied, so the reproducibility is good; (ii) the in-plane uniformity is high. In addition, it is easy to use a kit in which the etching liquid is divided into multiple parts, and for example, a method of mixing and discharging the first liquid and the second liquid in a line can be suitably used. In this case, it is preferable to adjust the temperature of the first liquid and the second liquid together, or adjust the temperature of only one of them, and mix and spray in the line. Among them, the embodiment in which temperature adjustment is performed together is more preferable. The management temperature when adjusting the temperature of the pipeline is preferably set to the processing described later The same temperature range.

The monolithic device preferably includes a nozzle in its processing tank, and preferably a method of swinging the nozzle in the plane direction of the semiconductor substrate to eject the etching solution onto the semiconductor substrate. It is preferable to prevent deterioration of the liquid by performing as described above. In addition, it is preferable to divide into two or more liquids by making a set, which makes it difficult to generate gas or the like.

The processing temperature for etching is preferably 10°C or higher, and more preferably 20°C or higher. The upper limit is preferably 80°C or lower, more preferably 70°C or lower, still more preferably 60°C or lower, still more preferably 50°C or lower, and particularly preferably 40°C or lower. By setting it to the above lower limit or more, it is preferable to ensure a sufficient etching rate for the second layer. By setting it as the said upper limit value or less, the stability of the etching process speed with time can be maintained preferably. Furthermore, the treatment can be carried out near room temperature, which results in a reduction in energy consumption.

In addition, the processing temperature for etching is based on the temperature applied to the substrate in the temperature measurement method shown in the embodiments described below, but it can be set at the storage temperature or managed by batch processing In this case, it can be set at the temperature in the tank, and when it is managed by the circulation system, it can be set at the temperature in the circulation flow path.

The supply rate of the etching solution is not particularly limited, but it is preferably set to 0.05 L/min to 5 L/min, and more preferably set to 0.1 L/min to 3 L/min. By setting it as the above-mentioned lower limit or more, the uniformity in the etched plane can be further satisfactorily maintained, which is preferable. By setting it to the upper limit or less, it is possible to ensure stable performance during continuous processing, which is preferable. When rotating the semiconductor substrate, although it depends on its size, etc., but From the same viewpoint, it is preferable to rotate at 50 rpm to 1000 rpm.

In the monolithic etching according to the preferred embodiment of the present invention, it is preferable to transport or rotate the semiconductor substrate in a predetermined direction, and spray an etching liquid into its space to bring the etching liquid into contact with the semiconductor substrate. The supply speed of the etching solution or the rotation speed of the substrate is the same as described above.

In the configuration of the monolithic device according to the preferred embodiment of the present invention, it is preferable to apply the etching solution while moving the ejection port (nozzle) as shown in FIG. 5. Specifically, in this embodiment, when an etchant is applied to the semiconductor substrate S, the substrate is rotated in the r direction. On the other hand, the ejection port is moved along the movement locus t extending from the center to the end of the semiconductor substrate. As described above, in this embodiment, the rotation direction of the substrate and the movement direction of the ejection port are set to different directions, thereby causing the two to move relative to each other. As a result, the etching liquid can be applied to the entire surface of the semiconductor substrate without omission, and a configuration in which etching uniformity is appropriately ensured.

The moving speed of the ejection port (nozzle) is not particularly limited, preferably 0.1 cm/s or more, and more preferably 1 cm/s or more. On the other hand, the upper limit is preferably 30 cm/s or less, and more preferably 15 cm/s or less. The moving trajectory may be a straight line or a curve (for example, a circular arc shape). In any case, the moving speed can be calculated based on the actual trajectory distance and the time it takes to move. The time required for etching each substrate is preferably in the range of 10 seconds to 300 seconds.

It is preferable to etch the metal layer at a high etching rate. The etching rate [R2] of the second layer (metal layer) is not particularly limited, but considering the production efficiency, It is preferably 50Å/min or more, more preferably 100Å/min or more, and particularly preferably 200Å/min or more. The upper limit is not particularly limited, and is actually 1000 Å/min or less.

The exposed width of the metal layer is not particularly limited, and from the viewpoint that the advantages of the present invention become more prominent, 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, and more preferably 20 nm or less.

The etching rate [R1] of the first layer, the third layer, or the fourth layer is not particularly limited, and it is preferably not removed excessively, more preferably below 40Å/min, and even more preferably 20Å/min Below, particularly preferred is below 10Å/min. The lower limit is not particularly limited, and if the measurement limit is considered, it is actually 0.1 Å/min or more.

In the selective etching of the second layer and the first layer, the third layer, or the fourth layer, the etching rate ratio ([R2]/[R1]) is not particularly limited, preferably 2 or more, more preferably It is 5 or more, and more preferably 10 or more. The upper limit is not particularly specified, and it is preferable that the upper limit is high, but it is actually 10,000 or less.

In addition, according to the etching solution of the preferred embodiment of the present invention, metal electrode layers such as Al and W, HfO, HfSiO, WO, AlO _x , SiO, SiOC, SiON, SiOCN, TiN, SiN, TiAlC and other layers (sometimes referred to collectively as "fourth layers") are damaged, and therefore, it is preferably applied to semiconductor substrates including these. The preferable etching rate of the fourth layer is expressed by the same parameter [R1] as the etching rate of the first layer or the third layer as described above. The preferable range is as described above. The preferred range of the etch rate ratio with the second layer is also synonymous with [R2]/[R1]. In addition, in the present specification, when the composition of the metal compound is described by the combination of elements of the metal compound, the meaning of the arbitrary composition is broadly included. For example, the so-called SiOC (SiON) means that Si and O coexist with C (N), and does not mean that the ratio of the amount is 1:1:1. This notation is common in this specification, and the same is true for other metal compounds.

The time required for etching a substrate is preferably 10 seconds or more, and more preferably 50 seconds or more. The upper limit is preferably 300 seconds or less, and more preferably 200 seconds or less.

[Manufacture of semiconductor substrate products (semiconductor manufacturing process)]

In this embodiment, it is preferable to manufacture a semiconductor substrate product having a desired structure through the following steps: a step of manufacturing a semiconductor substrate on which a silicon layer and a metal layer are formed on a silicon wafer; The step of annealing the substrate; the step of applying an etching solution to the semiconductor substrate, bringing the etching solution into contact with the metal layer, and selectively removing the metal layer. At this time, the specific etchant is used for etching. The order of the steps is not limited, and other steps may be further included between the steps.

The wafer size is not particularly limited, and a wafer with a diameter of 8 inches, a diameter of 12 inches, or a diameter of 14 inches (1 inch = 25.4 mm) can be suitably used.

In addition, when "preparation" is mentioned in this specification, it means that in addition to preparation by synthesizing or blending specific materials, it also includes raising predetermined materials through purchase or the like. In addition, in this specification, the case where the etching liquid which etched each material of a semiconductor substrate was used is called "application", and the embodiment is not specifically limited. For example, it is widely included to make the etching liquid contact with the substrate. Specifically, it can be immersed and etched by a batch-type device, or it can be etched by spraying by a monolithic device.

In this specification, the term “semiconductor substrate” is used to include not only the wafer but also the entire substrate structure to which the circuit structure is applied. The so-called "semiconductor substrate member" refers to a member that constitutes the semiconductor substrate as defined above, and may include one material or multiple materials. In addition, the processed semiconductor substrates are sometimes referred to as "semiconductor substrate products", and if necessary, to further distinguish them, the wafers and their processed products that are processed and diced out are referred to as "semiconductor elements". That is, a semiconductor element or a semiconductor product incorporating it is broadly a semiconductor substrate product.

[Example]

Hereinafter, the present invention will be described in more detail with examples, but the present invention is not limited to the following examples. In addition, "%" and "part" shown as a formula or a blended amount in the examples are quality standards unless otherwise specified.

[Reference Example 1]

(Fabrication of test substrate)

The SiGe epitaxial growth is performed on a commercially available silicon substrate (diameter: 12 inches) and is formed with a thickness of 500Å. In the same manner, a blanket wafer of another film made by CVD or the like is prepared. At this time, the SiGe epitaxial layer contains 50% by mass to 60% by mass of germanium. In the experiments in the table below, the blanket etching wafers were used to calculate the etching rate of each layer.

A Ti layer is further formed on the SiGe epitaxial layer. This was annealed at 800°C for 10 seconds to form a silicide layer to make a test substrate. The thickness of the annealed silicide layer is 15 nm, and the thickness of the metal layer is 5 nm.

(Etching test)

The blanket wafer and the test substrate were etched under the following conditions with a monolithic device (manufactured by SPS-Europe B.V. Co., Ltd., POLOS (trade name)) to perform an evaluation test.

. Processing temperature: 24℃ room temperature

. Spray volume: 1L/min.

. Wafer speed: 500rpm

. Nozzle moving speed: 7cm/S

. Processing time: 60 seconds

In addition, the supply of the etching liquid is performed by one kind of liquid (only the A line in FIG. 4 is used). Each treatment test was performed immediately after preparing the liquid.

(Measurement method of processing temperature)

A radiation thermometer IT-550F (trade name) manufactured by Horiba Manufacturing Co., Ltd. was fixed to a height of 30 cm on the wafer in the monolithic device. Point the thermometer to the wafer surface 2 cm outside from the center of the wafer, and measure the temperature while flowing the chemical solution. The temperature is output from the radiation temperature counter and continuously recorded by a personal computer. Among them, the value obtained by averaging the temperature for 10 seconds at which the temperature is stable is taken as the temperature on the wafer.

(Etching speed [ER])

The etching rate (ER) was calculated by measuring the film thickness before and after the etching process using ellipsometry (spectral ellipsometer, J.A. Woollam Japan Co., Inc., using Vase). Use the average value of 5 points (the measurement condition is the measurement range: 1.2eV ~2.5eV, measuring angle: 70 degrees, 75 degrees).

(TiSiGe damage)

The extent of damage to the germanium silicide layer (TiSiGe) can be determined based on the amount of change in sheet resistance before and after the etching process and the thickness of TiSiGe etched by ESCA. Evaluation A to Evaluation E are defined by the following formula based on how much the thickness of the ESCA TiSiGe layer is lost compared to the initial state.

TiSiGe damage (%) = (thickness of TiSiGe after chemical treatment/thickness of TiSiGe before chemical treatment) × 100

A: More than 80 and under 100

B: More than 60 and below 80

C: more than 40, below 60

D: More than 20 and below 40

E: more than 0, 20 or less

In addition, A ^- is an evaluation which becomes A, but is slightly worse.

<note of table>

ER: etching speed

PAA: Polyacrylic acid

DHC: dehydrocholic acid

LA: Lauric acid

SA: stearic acid

Lib: ribose

DEGBE: Diethylene glycol monobutyl ether

The amount of the next line of each ingredient (mass%)

It can be understood that the case where the etching rate becomes negative is not etched and apparently thickened.

[Example 1]

Except that the oxalic acid of Test No. 101 to No. 112 were changed to the following compounds, respectively, the etching rate [ER] and TiSiGe damage were evaluated in the same manner as Test No. 101 to No. 112. As a result, in any of the examples, TiAlC [ER] was made 1.0 or less without degrading other properties, and a remarkable anti-corrosion effect of TiAlC was obtained.

Compounds disclosed in Examples after paragraph 0265 of Japanese Patent Laid-Open No. 2007-277514 (B-1~B-24, C-1~C-57, D-1~D-12)

Compounds (C-1~C-136) disclosed in the Examples after paragraph 0200 of WO2014/034813A1

Compounds disclosed in the examples after paragraph 0194 of WO2014/034815A1 (C-1~C-199)

Furthermore, the organic solvents in Test No. 101 to No. 112 were reduced, and 0.2% by mass of the compound was added instead of the organic solvent. Except for this, the etching rate was evaluated in the same manner as in Test No. 101 to No. 112 [ER ] Damage with TiSiGe. As a result, in any of the examples, TiAlC [ER] was made 1.0 or less without lowering other properties, and a remarkable anti-corrosion effect of TiAlC was obtained.

[Example 2, Comparative Example 1]

Using an etching solution having the following composition, except that the same manner as in Reference Example 1 confirmed Ti, SiO _2, TiAlC etch rate.

EtOH: ethanol

DEGBE: Diethylene glycol monobutyl ether

PGME: propylene glycol monomethyl ether

Next line: Blending amount (mass %)

The compounds disclosed in the examples after paragraph 0194 of WO2014/034815A1 (C-2 to C-14, C-101 to C-119) were used instead of the C-1, and the examples were carried out 2 The same test. As a result, similar to the results in Table 3 above, it was confirmed that Ti has a good etching selectivity with respect to TiAlC.

The present invention will be described based on this embodiment, but we believe that as long as it is not specifically specified, our invention will not be limited in any details of the description, and should not violate the invention shown in the scope of the accompanying patent application. Explained broadly in spirit and scope.

This application claims priority based on Japanese Patent Application No. 2014-094213 for which a patent application was filed in Japan on April 30, 2014. These contents are referred to in this specification and the contents are incorporated as part of the description of this specification. Incorporated in this manual.

80‧‧‧Lower semiconductor layer

81‧‧‧First work function material layer

82A, 82B‧‧‧Second work function material layer

83A, 83B‧‧‧Metal part

90A, 90B‧‧‧ replacement gate stack

91A、91B‧‧‧Metal semiconductor alloy part

92A, 92B‧‧‧well

93‧‧‧ Ditch and Ditch Structure Department

94A, 94B ‧‧‧ source/drain expansion area

95A, 95B ‧‧‧ gate spacer

96A, 96B ‧‧‧ source/drain region

97A, 97B ‧‧‧ gate insulating film

99‧‧‧flat dielectric layer

Claims (18)

An etching solution is an etching solution for a semiconductor process containing a compound P, and the compound P is a compound having a plurality of adsorption groups and a weight average molecular weight of 1000 or more or having a plurality of adsorption groups and having a stereoscopic repulsion site Compound, the compound P is represented by the following formula (1),

In formula (1), A ¹ represents a group selected from an acid group, a group having a basic nitrogen atom, a urea group, a carbamate group, a group having a coordinated oxygen atom, a phenol group, an alkyl group, and an aryl group , Groups with alkyloxy groups, amide imino groups, alkoxycarbonyl groups, alkylaminocarbonyl groups, carboxylate groups, sulfonamide groups, alkoxysilyl groups, epoxy groups, isocyanate groups, A group of at least one group of a hydroxyl group and a heterocyclic group; R ¹ represents a (m+n)-valent linking group, R ² represents a divalent linking group where the part bonded to R ¹ is -S-; m represents 8 or less Is a positive number, n represents 1~9, and m+n satisfies 3~10; P ¹ represents a polymer chain; m P ¹ may be the same or different. The etching solution according to item 1 of the patent application scope further contains at least one of a metal-dissolving component, an acid auxiliary agent having a pKa of 4 or less, an organic solvent, and water. The etching solution according to item 2 of the patent application range, wherein the acid auxiliary agent is a boric acid compound, a phosphoric acid compound, a phosphonic acid compound, HBF ₄ , HBr, or HCl. The etching solution according to item 2 of the patent application scope, wherein the organic solvent The agent is a protic polar organic solvent. The etching solution according to item 2 of the patent application scope, wherein the concentration of the metal dissolved component is 0.1% by mass or more and 20% by mass or less. The etching solution according to item 2 of the patent application scope, wherein the metal-dissolved component is a halide ion. The etching solution according to item 6 of the patent application scope, wherein the halogen ion is a fluoride ion. Etching liquid as described in item 1 or 2 of the patent scope, which is applied to a semiconductor substrate including a third layer of silicide containing silicon or germanium, and a metal type other than silicon or germanium Second floor. The etching solution according to item 8 of the patent application range, wherein the second layer is a layer containing titanium. The etching solution as described in the first or second patent application scope is applied to a semiconductor substrate including a fourth layer containing TiAlC. An etching method which applies an etching solution to a semiconductor substrate, the etching solution containing a compound P having a plurality of adsorption groups and having a weight average molecular weight of 1000 or more, or a compound P having a plurality of adsorption groups and having a three-dimensional repulsion site, The compound P is represented by the following formula (1),

In formula (1), A ¹ represents a group selected from an acid group, a group having a basic nitrogen atom, a urea group, a carbamate group, a group having a coordinated oxygen atom, a phenol group, an alkyl group, and an aryl group , Groups with alkyloxy groups, amide imino groups, alkoxycarbonyl groups, alkylaminocarbonyl groups, carboxylate groups, sulfonamide groups, alkoxysilyl groups, epoxy groups, isocyanate groups, A group of at least one group of a hydroxyl group and a heterocyclic group; R ¹ represents a (m+n)-valent linking group, R ² represents a divalent linking group where the part bonded to R ¹ is -S-; m represents 8 or less Is a positive number, n represents 1~9, and m+n satisfies 3~10; P ¹ represents a polymer chain; m P ¹ may be the same or different. The etching method according to item 11 of the patent application range, wherein the etching solution further contains at least one of a metal-dissolving component, an acid additive having a pKa of 4 or less, an organic solvent, and water. The etching method as described in item 11 or item 12 of the patent application scope is applied to a semiconductor substrate including a third layer of silicide containing silicon or germanium, and a metal type other than silicon or germanium Second floor. The etching method as described in claim 11 or claim 12, wherein the second layer is a layer containing titanium. The etching method described in item 11 or item 12 of the patent application scope is applied to a semiconductor substrate including a fourth layer containing TiAlC. A method of manufacturing a semiconductor substrate product, which manufactures a semiconductor substrate product via an etching method as described in item 11 or item 12 of the patent application scope. A metal corrosion inhibitor comprising a compound P having a plurality of adsorption groups and having a weight average molecular weight of 1000 or more or a compound P having a plurality of adsorption groups and having a stereoscopic repulsion site, the compound P is represented by the following formula (1 ),

In formula (1), A ¹ represents a group selected from an acid group, a group having a basic nitrogen atom, a urea group, a carbamate group, a group having a coordinated oxygen atom, a phenol group, an alkyl group, and an aryl group , Groups with alkyloxy chain extension, amide imino groups, alkoxycarbonyl groups, alkylaminocarbonyl groups, carboxylate groups, sulfonamide groups, alkoxysilyl groups, epoxy groups, isocyanate groups, A group of at least one group of a hydroxyl group and a heterocyclic group; R ¹ represents a (m+n)-valent linking group, R ² represents a divalent linking group where the part bonded to R ¹ is -S-; m represents 8 or less Is a positive number, n represents 1~9, and m+n satisfies 3~10; P ¹ represents a polymer chain; m P ¹ may be the same or different. The metal corrosion inhibitor as described in item 17 of the patent application scope is used in an etching solution for semiconductor manufacturing processes.

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