WO2015166976A1

WO2015166976A1 - Etching solution, method for etching in which same is used, method for manufacturing semiconductor substrate product, metal corrosion inhibitor, and metal corrosion-inhibiting composition

Info

Publication number: WO2015166976A1
Application number: PCT/JP2015/062947
Authority: WO
Inventors: 智美高橋; 恭平荒山; 篤史水谷; 哲村山
Original assignee: 富士フイルム株式会社
Priority date: 2014-04-30
Filing date: 2015-04-30
Publication date: 2015-11-05
Also published as: TW201542773A; JP6256851B2; TWI682989B; JPWO2015166976A1

Abstract

　A semiconductor processor etching solution, wherein the etching solution has a plurality of adsorbing groups and contains a compound P (P1) that has a weight-average molecular weight of 1,000 or greater, or the etching solution has a plurality of adsorbing groups and contains a compound P (P2) that has a steric repulsion part.

Description

Etching solution, etching method using the same, method for producing semiconductor substrate product, metal anticorrosive and metal anticorrosive composition

The present invention relates to an etching solution, an etching method using the same, a method for producing a semiconductor substrate product, and a metal anticorrosive and a metal anticorrosive composition.

Integrated circuit manufacturing consists of various processing steps in multiple stages. In the manufacturing process, deposition of various materials, lithography, etching, and the like are repeated many times. Among them, etching is an important process. Certain materials must be selectively etched, and other materials must remain without being corroded. In some cases, it is required to remove only a predetermined layer while leaving layers made of similar metal species or layers made of a more corrosive material. The size of wirings and integrated circuits in a semiconductor substrate is becoming increasingly smaller, and the importance of performing etching accurately without corroding the components to be left is increasing.

International Publication No. 2012/125401 Pamphlet

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, a method for manufacturing a semiconductor substrate product, and a metal anticorrosive and a metal anticorrosive composition. It is in the provision of things.

The above problem has been solved by the following means.
[1] An etching solution for a semiconductor process,
An etchant containing a compound P having a plurality of adsorbing groups and having a weight average molecular weight of 1000 or more.
[2] An etching solution for a semiconductor process,
An etching solution containing a compound P having a plurality of adsorbing groups and a steric repulsion site.
[3] The etching solution according to [1] or [2], further comprising at least one of a metal-dissolving component, an acid assistant having a pKa of 4 or less, an organic solvent, and water.
[4] The etching solution according to [3], wherein the acid assistant 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 from 0.1% by mass to 20% by mass.
[7] The etching solution according to any one of [3] to [6], wherein the metal dissolving component is a halogen ion.
[8] The etching solution according to [7], wherein the halogen ion is a fluorine 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 (I) or a compound having a partial structure represented by the following formula (II).
(A) _n- P ^a (I)
A is an adsorbing 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 adsorbing 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 according to any one of [1] to [9], which is applied to a semiconductor substrate having a third layer containing silicon or germanium silicide and a second layer containing a metal species other than silicon or germanium. liquid.
[11] The etching solution 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 including TiAlC.
[13] An etching method in which an 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 a steric repulsion site is applied to a semiconductor substrate.
[14] The etching method according to [13], wherein the etching solution further contains at least one of a metal-dissolving component, an acid assistant 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 having a third layer containing silicon or germanium silicide and a second layer containing a metal species other than silicon or germanium.
[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 including TiAlC.
[18] A semiconductor substrate product manufacturing method for manufacturing a semiconductor substrate product through the etching method according to any one of [13] to [17].
[19] A metal anticorrosive comprising a compound P having a plurality of adsorbing groups and having a weight average molecular weight of 1000 or more, or a compound P having a plurality of adsorbing groups and having a steric repulsion site, or a metal anticorrosive composition containing the same.
[20] The metal anticorrosive agent according to [19] or a metal anticorrosive composition containing the metal anticorrosive agent according to [19], which is used for an etching solution for a semiconductor process.

According to the present invention, a predetermined metal layer can be etched while suppressing damage to the predetermined metal layer.
The above and other features and advantages of the present invention will become more apparent from the following description, with reference where appropriate to the accompanying drawings.

FIG. 1 is a cross-sectional view schematically showing an example of a manufacturing process of a semiconductor substrate in one embodiment of the present invention. FIG. 2 is a process diagram showing an example of manufacturing a MOS transistor according to an embodiment of the present invention. FIG. 3 is a cross-sectional view schematically showing a substrate structure 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. FIG. 5 is a plan view schematically showing the movement trajectory line of the nozzle with respect to the semiconductor substrate in one embodiment of the present invention.

First, a preferred embodiment of an etching process according to application of the etching solution of the present invention will be described with reference to FIGS.

[Etching process]
FIG. 1 shows the semiconductor substrate before and after etching. In the manufacturing example of the present embodiment, a metal layer (second layer) 1 is disposed on the upper surface of a silicon or germanium-containing layer (first layer) 2. As the silicon or germanium-containing layer (first layer), a SiGe epitaxial layer constituting a source electrode and a drain electrode is applied. The first layer may be composed of Si, but is preferably a SiGe or Ge epitaxial layer.
As a constituent material of the metal layer (second layer) 1, titanium (Ti), cobalt (Co), nickel (Ni), nickel platinum (NiPt), tantalum (Ta), niobium (Nb), tungsten (W), etc. Metal species (single metal or composite metal). The metal layer can be formed by a method usually applied to this type of metal film, and specifically, film formation by CVD (Chemical Vapor Deposition) can be mentioned. The thickness of the metal layer at this time is not particularly limited, but examples include a film having a thickness of 5 nm to 50 nm. In the present invention, it is preferable that the metal layer is a Ti layer because the removal performance of the etching solution is sufficiently exhibited.
The metal layer may contain other elements in addition to the metal atoms listed above. For example, oxygen and nitrogen inevitably mixed in may exist. The amount of inevitable impurities is preferably suppressed to, for example, about 1 ppt to 10 ppm (mass basis).

After the metal layer 1 is formed above the silicon or germanium-containing layer 2 in the above step (a), annealing (sintering) is performed, and a metal-Si reaction film (third layer: silicide layer) is formed at the interface. 3 is formed (step (b)). Annealing may be performed under conditions normally applied to the manufacture of this type of device, and for example, treatment at 200 to 1000 ° C. may be mentioned. The thickness of the silicide layer 3 at this time is not particularly limited, but examples include a layer of 50 nm or less, and an example of a layer of 10 nm or less. Although there is no lower limit in particular, it is practical that it is 1 nm or more. This silicide layer is applied as a low-resistance film, and functions as a conductive portion that electrically connects a source electrode and a drain electrode located below the silicide layer and a wiring disposed thereon. Accordingly, when defects or corrosion occur in the silicide layer, this conduction is hindered, which may lead to quality degradation such as device malfunction. In particular, recently, the integrated circuit structure inside the substrate has been miniaturized, and even a minute damage can have a great influence on the performance of the element. Therefore, it is desirable to prevent such defects and corrosion.
In this specification, the silicide layer is a concept included in the first silicon-containing or germanium-containing layer in a broad sense. Therefore, when the second layer is selectively removed with respect to the first layer, not only a mode in which the second layer (metal layer) is preferentially removed with respect to the silicon or germanium-containing layer that is not silicided. This means that the second layer (metal layer) is preferentially removed with respect to the silicide layer. Strictly speaking, when the first silicon or germanium-containing layer (excluding the silicide layer) and the third silicide layer are distinguished from each other, they are referred to as the first layer and the third layer, respectively.

Next, the remaining metal layer 1 is etched (step (b)-> step (c)). In the present embodiment, an etching solution is applied at this time, and the metal layer 1 is removed by applying and contacting the etching solution from the upper side of the metal layer 1. The form of application of the etchant will be described later.
The silicon- or germanium-containing layer 2 is composed of a SiGe epitaxial layer, and can be formed by crystal growth on a silicon substrate having specific crystallinity by a chemical vapor deposition (CVD) method. Alternatively, an epitaxial layer formed with desired crystallinity may be formed by an electron beam epitaxy (MBE) method or the like.
To make the silicon or germanium-containing layer a P-type layer, it is preferable that boron (B) having a concentration of about 1 × 10 ¹⁴ cm ⁻³ to 1 × 10 ²¹ cm ⁻³ is doped. For an N-type layer, phosphorus (P) is preferably doped at a concentration of 1 × 10 ¹⁴ cm ⁻³ to 1 × 10 ²¹ cm ⁻³ .

When the first layer is a SiGe epitaxial layer, the Ge concentration is preferably 20% by mass or more, and more preferably 40% by mass or more. As an upper limit, 100 mass% or less is preferable, and 90 mass% or less is more preferable. In the case of 100% by mass of germanium, the layer formed by annealing with the alloy of the second layer contains germanium and the specific metal element of the second layer, and does not contain silicon. Is referred to as a germanium silicide layer.
(Metal concentration)
In the present invention, the concentration of a metal such as germanium is a value measured by the following measuring method. A substrate of a layer containing a specific metal is analyzed in the depth direction from 0 to 30 nm by etching ESCA (Quanta by ULVAC-PHI), and the average value of the concentration of metal (Ge, etc.) in the analysis result of 3 to 15 nm is calculated for the metal. Concentration (mass%).

Through the salicide process, the silicide layer is formed between the silicon or germanium-containing layer (first layer) and the metal layer (second layer), and silicon (Si) or germanium (Ge) and the components of the second layer (above It is formed as a layer containing a specific metal species). This silicide layer is included in the first layer in a broad sense, but is referred to as a “third layer” when distinguished from this in a narrow sense. Although the composition is not particularly limited, it is preferably a germanium silicide layer containing germanium. In the formula of SixGeyMz (M: metal element), x + y + z = 1 is preferably 0.2 ≦ x + y ≦ 0.8, and more preferably 0.3 ≦ x + y ≦ 0.7. z is preferably 0.2 ≦ z ≦ 0.8, and more preferably 0.3 ≦ z ≦ 0.7. A preferred range of the ratio of x and y is as defined above. However, the third layer may contain other elements. This is the same as described for the metal layer (second layer).

In addition to the above-described silicide materials, there may be materials that are not desired to be etched in the semiconductor substrate. In the etching solution of this embodiment, it is preferable to minimize corrosion of a material that is not desired to be etched. Examples of the material (fourth layer) that is not desired to be etched include at least one selected from the group consisting of Al, SiO ₂ , SiN, SiOC, HfO, and TiAlC. In particular, a fourth layer such as TiAlC may be applied to the gate electrode 23 (FIG. 2) to protect the material of the fourth layer separately from or simultaneously with the protection of the first layer and the third layer. It is preferable that etching is possible.

(Processing of MOS transistors)
FIG. 2 is a process diagram showing an example of manufacturing a MOS transistor. (A) is a MOS transistor structure formation process, (B) is a metal film sputtering process, (C) is a first annealing process, (D) is a metal film selective removal process, and (E) is a second annealing process. It is a process.
As shown in the figure, a gate electrode 23 is formed through a gate insulating film 22 formed on the surface of the silicon substrate 21. Extension regions may be separately formed on both sides of the gate electrode 23 of the silicon substrate 21. A protective layer (not shown) for preventing contact with the Ti layer may be formed on the gate electrode 23. Further, a sidewall 25 made of a silicon oxide film or a silicon nitride film is formed, and a source region 26 and a drain region 27 are formed by ion implantation.
Next, as shown in the figure, a Ti film 28 is formed and subjected to a rapid annealing process. As a result, the elements in the Ti film 28 are diffused into the silicon substrate for silicidation (in this specification, alloying by annealing is referred to as silicidation for the sake of convenience, including when germanium is 100% by mass). 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 electrode member is changed to a desired state (annealed silicide source electrode 26B, annealed silicide drain electrode 27B) by performing the second annealing as shown in FIG. be able to. Although the first and second annealing temperatures are not particularly limited, for example, the annealing can be performed at 300 to 1100 ° C.

The remaining Ti film 28 without contributing to silicidation can be removed by using the etching solution of the present embodiment (FIGS. 2C and 2D). At this time, what is shown in the figure is schematically shown, and there may or may not be a Ti film deposited and left on top of the silicided layers (26A, 27A). The structure of the semiconductor substrate or its product is also shown in a simplified manner, and may be interpreted as having necessary members as necessary.

The following forms can be illustrated if the preferable example of a constituent material is given.
21 Silicon substrate: Si, SiGe, Ge
22 Gate insulating film: HfO ₂ (High-k)
23 Gate electrode: Al, W, TiAlC
25 Side wall: SiOCN, SiN, SiO ₂ (low-k)
26 Source electrode: Si, SiGe, Ge
27 Drain electrode: Si, SiGe, Ge
28 Metal layer: Ti
Not shown Cap: TiN
Although the semiconductor substrate to which the etching method of the present invention is applied has been described above, the present invention is not limited to this specific example and can be applied to other semiconductor substrates. For example, a semiconductor substrate including a high dielectric film / metal gate FinFET having a silicide pattern on the source and / or drain region may be used.
In the example of FIG. 2 described above, the description mainly focuses on the protection of the silicide layers (first layer and third layer), but the present invention is not construed as being limited thereto. For example, separately from the protection of the silicide layer, the etching of the second layer such as Ti may be realized while the protection of the fourth layer such as TiAlC is realized.

FIG. 3 is a cross-sectional view schematically showing a substrate structure according to another embodiment of the present invention. 90A is a first gate stack located in the first device region. Reference numeral 90B denotes a second gate stack located in the second element region. Here, the gate stack contains a conductive tantalum alloy layer or TiAlC. The first gate stack will be described. 92A is a well. 94A is a first source / drain extension region, 96A is a first source / drain region, and 91A is a first metal semiconductor alloy portion. Reference numeral 95A denotes a first gate spacer. 97A is a first gate insulating film, 81 is a first work function material layer (81), and 82A is a second work function material layer (second work function material layer). Reference numeral 83A denotes a first metal portion that serves as an electrode. 93 is a trench structure, and 99 is a planarizing dielectric layer. Reference numeral 80 denotes a lower semiconductor layer.
The first gate stack has the same structure, and 91B, 92B, 94B, 95B, 96B, 97B, 82B, 83B are 91A, 92A, 94A, 95A, 96A, 97A, 82A of the first gate stack, respectively. , 83A. As a structural difference between the two, the first gate stack has a first work function material layer 81, but the second gate stack is not provided with it.
The work function material layer may be either a p-type work function material layer or an n-type work function material layer. A p-type work function material refers to a material having a work function between the valence band energy level and the mid band gap energy level of silicon. That is, in the energy level of silicon, the energy level of the conduction band and the valence band energy level are equivalently separated. An n-type work function material refers to a material having a work function between the energy level of the conduction band of silicon and the mid band gap 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 can comprise 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 10% to 99%. The atomic concentration of aluminum can be 1% to 90%.
(Ii) TaC
In an alloy of tantalum and carbon, the atomic concentration of tantalum can be 20% to 80%. The atomic concentration of carbon can be 20% to 80%.
(Iii) TaAlC
In an alloy of tantalum, aluminum, and carbon, the atomic concentration of tantalum can be 15% to 80%. The atomic concentration of aluminum can be 1% to 60%. The atomic concentration of carbon can be 15% to 80%.
In another embodiment, the work function material layer can be (iv) a titanium nitride layer consisting essentially of titanium nitride or (v) a layer of titanium, aluminum and carbon alloy.
(Iv) TiN
In the titanium nitride layer, the atomic concentration of titanium can be 30% to 90%. The atomic concentration of nitrogen can be 10% to 70%.
(V) TiAlC
In the titanium / aluminum / carbon alloy layer, the atomic concentration of titanium can be 15% to 45%. The atomic concentration of aluminum can be 5% to 40%. The atomic concentration of carbon can be 5% to 50%.
The work function material layer can 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 so as to cover the gate electrode, and the film thickness is preferably 100 nm or less, more preferably 50 nm or less, and further preferably 1 nm to 10 nm.
Among them, in the present invention, it is preferable to apply a substrate in which a TiAlC layer is employed from the viewpoint of suitably exhibiting etching selectivity.

In the device of the present embodiment, the gate dielectric layer is made of a high-k material containing a metal and oxygen. As the high-k gate dielectric material, known materials can be used. The film can be deposited by conventional methods. Examples include chemical vapor deposition (CVD), physical vapor deposition (PVD), molecular beam vapor deposition (MBD), pulsed laser vapor deposition (PLD, liquid source mist chemical deposition (LSMCD), atomic layer deposition (ALD), and the like. Examples of high-k 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, etc., where x is 0.5-3. y is 0 to 2. The thickness of the gate dielectric layer is preferably 0.9 to 6 nm, more preferably 1 to 3 nm, and in particular, the gate dielectric layer is made of hafnium oxide (HfO 2). It is preferable Ranaru.
Other members and structures can be appropriately formed by ordinary methods using ordinary materials. For details thereof, reference can be made to US Publication No. 2013/0214364 and US Publication No. 2013/0341631, which are incorporated herein by reference.

According to the etching solution according to a preferred embodiment of the present invention, even if the work function material layer (TiAlC) as described above is exposed, the silicide metal (Ni) is effectively suppressed while suppressing damage to the layer. , Pt, Ti, etc.) can be removed.

[Etching solution]
(Compound P)
The etching solution for the semiconductor process of this embodiment includes a compound P (P1) having a plurality of adsorbing groups and a weight average molecular weight of 1000 or more, or a compound P (P2) having a plurality of adsorbing groups and a steric repulsion site. contains. The compound P having a plurality of adsorbing groups and having a weight average molecular weight of 1000 or more suppresses the dissolution of a desired metal without degrading the performance of the metal-dissolving component in the etching solution. Based on this function, the compound P is sometimes referred to as a metal anticorrosive and a composition containing the compound P is sometimes referred to as a metal anticorrosive composition. The reason why such an effect is obtained is not clear, but when the etching solution comes into contact with the metal, the adsorption group of the compound P is adsorbed on the predetermined metal. The presence of a plurality of these adsorbing groups improves the adhesion with the metal. On the other hand, it is presumed that the presence of a structure having a weight average molecular weight of 1000 or more or a steric repulsion site covers the surface of a predetermined metal, prevents contact with a metal-dissolving component, and suppresses dissolution of a desired metal.
Compound P is particularly excellent in the anticorrosive effect of Al. As the compound P, those represented by the following formula (I) are preferable. 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 adsorbing 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 is also a steric repulsion 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, but 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, and if the molecular weight is large, there is a concern of causing etching defects.
P ^a is preferably a residue of a polymer compound as defined in P1 below.

As the compound P, a compound having a partial structure represented by the following formula (II) is also preferable. 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 adsorbing group. The adsorbing group has the same meaning as in the above 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 1000 or more. The structure of the polymer compound residue is the same as in 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 (GPC). The weight average molecular weight was measured by HPC-8220GPC (manufactured by Tosoh Corporation), guard column: TSKguardcolumn SuperHZ-L, column: TSKgel SuperHZM-M, TSKgel SuperHZ4000, TSKgel SuperHZ3000, TSKgel Z 10 μl of a 1 mass% tetrahydrofuran solution was injected, tetrahydrofuran as an elution solvent was allowed to flow at a flow rate of 0.35 ml / min, and the sample peak was detected with an RI detector. Calculation was performed using a calibration curve prepared using standard polystyrene.
In the above compound, A may be an adsorption group, n may be an integer of 2 or more, and P may be a hydrophobic group (polymer). As the hydrophobic group, those having ClogP of 3 or more are preferable, those having 10 or more are more preferable, and those having 100 or less are preferable. Adsorptive group A is particularly preferably the following substituent A ^1.

More preferably, the compound P represented by the above formula (I) is preferably a polymer compound represented by the formula (1).

A ¹ is an acid group, a group having a basic nitrogen atom, a urea group, a urethane group, a group having a coordinating oxygen atom, a phenol group, an alkyl group, an aryl group, a group having an alkyleneoxy chain, an imide group, an alkyl group This represents a group having at least one group selected from an oxycarbonyl group, an alkylaminocarbonyl group, a carboxylate group, a sulfonamide group, an alkoxysilyl group, an epoxy group, an isocyanate group, a hydroxyl group, and a heterocyclic group. A ¹ preferably functions as a group having an adsorption ability for a specific metal. 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 represents a positive number of 8 or less, n represents 1 to 9, and m + n satisfies 3 to 10.
P ¹ represents a polymer chain. The m P ¹ may be the same or different.

It may contain two or more adsorption sites within the A ^1. As embodiments thereof, a linear saturated hydrocarbon group (which may be linear or branched and preferably having 1 to 10 carbon atoms), a cyclic saturated hydrocarbon group (having 3 to 10 carbon atoms) And a group in which two or more adsorption sites are bonded via an aromatic group (preferably having 5 to 10 carbon atoms, for example, a phenylene group) or the like. Among these, an embodiment in which two or more adsorption sites are bonded via a chain saturated hydrocarbon group is preferable. In the case where adsorption sites themselves constitute a monovalent substituent, adsorption sites themselves may also be a monovalent substituent represented by A ^1.

As the “acid group”, 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, and a boric acid group are preferable. Group, monosulfate group, phosphoric acid group, monophosphate group, phosphonic acid group and phosphinic acid group are more preferred, and carboxyl group is particularly preferred.
As the “urea group”, for example, —NR ^N CONR ^N ₂ is mentioned as a preferred example, —NR ^N CONHR ^N is more preferred, and —NHCONHR ^N is particularly preferred.
Examples of the “urethane group” include —NHCOOR ^N , —NR ^N COOR ^N , —OCONHR ^N , —OCONR ^N _{2 and the} like, and —NHCOOR ^N and —OCONHR ^N are more preferable, and —NHCOOR ^N , —OCONHR ^{N and the} like are particularly preferable. Here, ^RN is defined as follows.
Examples of the “group having a coordinating oxygen atom” include an acetylacetonato group and a crown ether.
Examples of the “group having a basic nitrogen atom” include an amino group (—NH ₂ ), a substituted imino group (—NHR ^N , —NR ^N ₂ ), a guanidyl group represented by the following formula (a1), Preferred examples include an amidinyl group represented by (a2).

Wherein, ^{R N} are each independently 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. Of these, 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 is preferable. An alkyl group having 1 to 5 carbon atoms, a phenyl group, or a benzyl group is more preferable.

Among these, an amino group (—NH ₂ ), a substituted imino group (—NHR ^N , —NR ^N ₂ ), a guanidyl group represented by the formula (a1), an amidinyl group represented by the formula (a2) and the like are more preferable. preferable.

The “alkyl group” may be linear or branched and is preferably an alkyl group having 1 to 40 carbon atoms, more preferably an alkyl group having 4 to 30 carbon atoms. An alkyl group having 10 to 18 carbon atoms is more preferable.
The “aryl group” is preferably an aryl group having 6 to 10 carbon atoms.
As the “group having an alkyleneoxy chain”, the terminal preferably forms an alkyloxy group or a hydroxyl group, and more preferably an alkyloxy group having 1 to 20 carbon atoms. The alkyleneoxy chain is not particularly limited as long as it has at least one alkyleneoxy group, but 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, an alkylene group having 2 or 3 is more preferable. mc is preferably 1 to 6, and more preferably 1 to 3.
The alkyl group moiety in the “alkyloxycarbonyl group” is preferably an alkyl group having 1 to 20 carbon atoms.
The alkyl group moiety in the “alkylaminocarbonyl group” is preferably an alkyl group having 1 to 20 carbon atoms.
Examples of the “carboxylic acid group” include groups composed of ammonium salts of carboxylic acids.
In the “sulfonamide group”, a hydrogen atom bonded to a nitrogen atom may be substituted with an alkyl group (such as a methyl group), an acyl group (such as an acetyl group or a trifluoroacetyl group), and the like.

Examples of the “heterocyclic group” include thiophene group, furan group, xanthene group, pyrrole group, pyrroline group, pyrrolidine group, dioxolane group, pyrazole group, pyrazoline group, pyrazolidine group, imidazole group, oxazole group, thiazole group, oxalate group. Diazole, triazole, thiadiazole, pyran, pyridine, piperidine, dioxane, morpholine, pyridazine, pyrimidine, piperazine, triazine, trithiane, isoindoline, isoindolinone, benz Preferred examples include imidazolone groups, benzothiazole groups, succinimide groups, phthalimide groups, naphthalimide groups and other imide groups, hydantoin groups, indole groups, quinoline groups, carbazole groups, acridine groups, acridone groups, and anthraquinone groups. It is. In addition, the cyclic ketone containing an anthraquinone group shall be contained in a heterocyclic ring.
Examples of the “imide group” include succinimide, phthalimide, naphthalimide and the like.

The “heterocyclic group” and the “imide group” may further have a substituent. Examples of the substituent include an alkyl group having 1 to 20 carbon atoms and an aryl group having 6 to 16 carbon atoms. An acyloxy group having 1 to 6 carbon atoms such as a hydroxyl group, amino group, carboxyl group, sulfonamido group, N-sulfonylamide group and acetoxy group, an alkoxy group having 1 to 20 carbon atoms such as methoxy group and ethoxy group, halogen Examples thereof include C2-C7 alkoxycarbonyl groups such as atoms, methoxycarbonyl groups, ethoxycarbonyl groups, and cyclohexyloxycarbonyl groups, cyano groups, and carbonate ester groups such as t-butyl carbonate.

The “alkoxysilyl group” may be any of monoalkoxysilyl group, dialkoxysilyl group, trialkoxysilyl group, but is preferably trialkoxysilyl group, such as trimethoxysilyl group, triethoxysilyl group, etc. Is mentioned.
Examples of the “epoxy group” include a substituted or unsubstituted oxiranyl group (ethylene oxide group).

In particular, A ¹ is preferably a monovalent substituent having at least one functional group of pKa5 or higher, and more preferably a monovalent substituent having at least one functional group of pKa5 to 14.
Here, “pKa” has the definition described in Chemical Handbook (II) (4th revised edition, 1993, edited by The Chemical Society of Japan, Maruzen Co., Ltd.).
The functional group having a pKa of 5 or more includes a group having a coordinating oxygen atom, a group having a basic nitrogen atom, a phenol group, a urea group, a urethane group, an alkyl group, an aryl group, an alkyloxycarbonyl group, and an alkylaminocarbonyl group. A group having an alkyleneoxy chain, an imide group, a carboxylate group, a sulfonamide group, a hydroxyl group, a heterocyclic group, and the like.
Alternatively, a value calculated using ACD / Labs (manufactured by Advanced Chemistry Development) or the like can be used.
Specific examples of the functional group having a pKa of 5 or more include, for example, a phenol group (about pKa 8 to 10), an alkyl group (about pKa 46 to 53), an aryl group (about pKa 40 to 43), and a urea group (pKa 12 to 14). About), urethane group (about pKa 11 to 13), —COCH ₂ CO— as a coordinating oxygen atom (about pKa 8 to 10), sulfonamide group (about pKa 9 to 11), hydroxyl group (pKa 15 to 17), a heterocyclic group (pKa 12-30), and the like.

Among the above, as A ^1, group, hydroxyphenyl group, an alkyl group, an aryl group, an alkyleneoxy chain groups having a hydroxyl group, a urea group, a urethane group, a sulfonamido group, an imido group and coordinating oxygen atom It is preferable that it is a monovalent substituent having at least one group selected from the group consisting of groups containing Among them as A ^1, group, hydroxyphenyl group or more preferably a hydroxyl group, an acid group (in particular carboxyl groups) it is particularly preferred.

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, and 1 to 200 carbon atoms. A group consisting of a hydrogen atom and 0 to 20 sulfur atoms is included, which may be unsubstituted or may further have a substituent.

R ² is a single bond or 1 to 10 carbon atoms, 0 to 5 nitrogen atoms, 0 to 10 oxygen atoms, 1 to 30 hydrogen atoms, and A divalent linking group consisting of 0 to 5 sulfur atoms is preferred.
R ² includes a chain saturated hydrocarbon group (which may be linear or branched, preferably having 1 to 20 carbon atoms), or a cyclic saturated hydrocarbon group (having 3 to 20 carbon atoms). Selected from the group consisting of an aromatic group (preferably having 5 to 20 carbon atoms, such as a phenylene group), a thioether bond, an ester bond, an amide bond, an ether bond, a nitrogen atom, and a carbonyl group. More preferably a group or a combination of two or more of these, 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 Or a combination of two or more of these, a chain saturated hydrocarbon group, a thioether bond, an ester bond, an ether bond, and an amide A group selected from the group consisting of a bond, or a group obtained by combining two or more of these is particularly preferable.

Among 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, C1-C6 acyloxy groups such as amino groups, carboxyl groups, sulfonamido groups, N-sulfonylamide groups, acetoxy groups, etc., C1-C6 alkoxy groups such as methoxy groups, ethoxy groups, chlorine, bromine, etc. Examples thereof include a C2-C7 alkoxycarbonyl group such as a halogen atom, a methoxycarbonyl group, an ethoxycarbonyl group, and a cyclohexyloxycarbonyl group, a cyano group, and a carbonate group such as t-butyl carbonate.

In formula (1), R ¹ represents a (m + n) -valent linking group. m + n satisfies 3 to 10.
Examples of the (m + n) -valent linking group represented by R ¹ include 1 to 100 carbon atoms, 0 to 10 nitrogen atoms, 0 to 50 oxygen atoms, and 1 to 200. A group consisting of up to 20 hydrogen atoms and 0 to 20 sulfur atoms, which may be unsubstituted or further substituted.

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

In the above formula,
L represents a trivalent to hexavalent group. T represents a single bond or a divalent linking group. 3 to 6 Ts may be the same as or different from each other. L is a carbon atom, an aryl linking group (preferably having 6 to 22 carbon atoms, more preferably 6 to 14 and particularly preferably 6 to 10), and a heterocyclic linking group (preferably having 2 to 12 carbon atoms and more preferably having 2 to 6 carbon atoms). Preferred). T is an alkylene group (preferably having 1 to 12 carbon atoms, more preferably 1 to 6 carbon atoms, particularly preferably 1 to 3 carbon atoms), a carbonyl group (CO), an oxy group (O), an imino group (NR ^N ), a sulfide group ( S) or a group related to these combinations. ^RN is as defined above.

Specific examples (specific examples (1) to (17)) of the (m + n) -valent linking group represented by R ¹ are shown below. However, the present invention is not limited to these.

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

In the 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 to 9. n is preferably 2 to 8, more preferably 2 to 7, and particularly preferably 3 to 6. In addition, when m and n have a decimal, it means that it is 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 according to the purpose and the like. The m P ¹ may be the same or different.
Among the polymers, a vinyl monomer polymer or copolymer, an ester polymer, an ether polymer, a urethane polymer, an amide polymer, an epoxy polymer, a silicone polymer, and modifications thereof are used to form a polymer chain. Or copolymer [for example, polyether / polyurethane copolymer, copolymer of polyether / vinyl monomer polymer, etc. (any of random copolymer, block copolymer, graft copolymer, etc. May also be included). At least one selected from the group consisting of vinyl monomers, selected from the group consisting of polymers or copolymers of vinyl monomers, ester polymers, ether polymers, urethane polymers, and modified products or copolymers thereof. At least one kind is more preferred, and a polymer or copolymer of vinyl monomers is particularly preferred.
Polymers or copolymers of vinyl monomers the polymer chain P ¹ may have, ester-based polymer, Examples of the ether-based polymer, respectively, the following formula (L), (M), represented by any one of (N) It preferably has a structure.

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 preferable, a hydrogen atom or a methyl group is more preferable, and a methyl group is particularly preferable.
R ¹⁰ represents a hydrogen atom or a monovalent organic group. Preferably, they are a hydrogen atom, an alkyl group, an aryl group, or a heteroaryl group, More preferably, they are a hydrogen atom or an alkyl group. When R ¹⁰ is an alkyl group, the alkyl group may be a linear alkyl group having 1 to 20 carbon atoms, a branched alkyl group having 3 to 20 carbon atoms, or a cyclic alkyl group having 5 to 20 carbon atoms. Preferably, a linear alkyl group having 1 to 20 carbon atoms is more preferable, and a linear alkyl group having 1 to 6 carbon atoms is particularly preferable. The different R ¹⁰ structurally or may have two or more in the formula (L).
R ¹¹ and R ^{12 each} represent a branched or straight chain alkylene group (the number of carbon atoms is preferably 1 to 10, more preferably 2 to 8, and still more preferably 3 to 6). Different R ¹¹ or R ¹² of the structure may have two or more in each formula.
k1, k2, and k3 each independently represents a number of 5 to 140.

The polymer chain P ¹ preferably contains at least one repeating unit.
The number k (k1, k2, k3) of at least one repeating unit in the polymer chain P ¹ is preferably 5 or more from the viewpoint of exhibiting steric repulsion and improving dispersion stability, and 7 or more. It is more preferable that
The number k of repeating units is preferably 140 or less, more preferably 130 or less, and still more preferably 60 or less.

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 weakened, and it may be impossible to secure an adsorption layer sufficient for stabilizing the dispersion.
Although it does not restrict | limit especially as a vinyl monomer, For example, (meth) acrylic acid esters, crotonic acid esters, vinyl esters, vinyl monomers having an acid group, maleic acid diesters, fumaric acid diesters, itaconic acid diesters , (Meth) acrylamides, styrenes, vinyl ethers, vinyl ketones, olefins, maleimides, (meth) acrylonitrile, etc. are preferred, (meth) acrylic acid esters, crotonic acid esters, vinyl esters, acid groups The vinyl monomer is more preferably, and (meth) acrylic acid esters and crotonic acid esters are more preferable.
Preferable examples of these vinyl monomers include paragraphs 0089 to 0094, 0096 and 0097 of JP-A-2007-277514 (paragraphs 0105 to 0117 and 0119 to 0120 in the corresponding US 2010/233595). ), The contents of which are incorporated herein.

In addition to the above compounds, for example, vinyl monomers having a functional group such as a urethane group, a urea group, a sulfonamide group, a hydroxyphenyl group, and an imide group can also be used. Such a monomer having a urethane group or a urea group can be appropriately synthesized using, for example, an addition reaction between an isocyanate group and a hydroxyl group or an amino group. Specifically, an addition reaction between an isocyanate group-containing monomer and a compound containing one hydroxyl group or a compound containing one primary or secondary amino group, or a hydroxyl group-containing monomer or primary or secondary amino group It can be appropriately synthesized by an addition reaction between the containing monomer and monoisocyanate.

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

In the formula (2), ^{A 2} has the same meaning as ^{A 1} in formula (1), a preferable embodiment thereof is also the same.
In the formula (2), R ⁴ and R ⁵ each independently represents a single bond or a divalent linking group. The n R ^{4 s} may be the same or different. The m R ^{5 s} may be the same or different.
As the divalent linking group represented by R ⁴ or R ⁵ , the same divalent linking groups as those represented by R ² in the formula (1) are used, and the preferred embodiments are also the same. It is.

In Formula (2), R ³ represents a (m + n) -valent linking group. m + n satisfies 3 to 10.
As R < ³ >, the thing similar to what was mentioned as a coupling group represented by R < ¹ > is used, and its preferable aspect is also the same.
In formula (2), m and n have the same meanings as m and n in formula (1), respectively, and the preferred embodiments are also the same.
Further, ^{P 2} in the formula (2) has the same meaning as ^{P 1} in formula (1), a preferable embodiment thereof is also the same. the m P ² can be the same or different.

Of the polymer compounds represented by the formula (2), those satisfying all of R ³ , R ⁴ , R ⁵ , P ² , m, and n shown below are most preferable.
R ³ : Specific example (1), (2), (10), (11), (16), or (17) above
R ⁴ : a 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 these two or more combined group R ^5: a single bond, an ethylene group, a propylene group, 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 to 3
n: 3-6

Compound P (a polymer compound represented by the formula (1) or (2)) is not particularly limited, but conforms to the synthesis method described in paragraphs 0114 to 0140 and 0266 to 0348 of JP-A-2007-277514. Can be synthesized. Furthermore, specific examples of the compound P include those described below.
Compounds disclosed in Examples after paragraph 0265 of JP-A-2007-277514 (B-1 to B-24, C-1 to C-57, D-1 to D-12)
WO2014 / 034813A1 Compounds disclosed in Examples after paragraph 0200 (C-1 to C-136)
WO2014 / 034815A1 Compounds disclosed in Examples after paragraph 0194 (C-1 to C-199)
The above-mentioned publications can be referred to for the method for producing compound P.

The concentration of the compound P is preferably 0.01% by mass or more, more preferably 0.05% by mass or more, and particularly preferably 0.1% by mass or more in the etching solution. As an upper limit, 20 mass% or less is preferable, 10 mass% or less is more preferable, 5 mass% or less is further more preferable, and 1 mass% or less is especially preferable. By applying the compound P at the above concentration, it is possible to achieve effective protection of the first layer, the third layer, and the fourth layer while realizing good etching of the metal layer (second layer). .
Compound P may be used alone or in combination of two or more.

(Metal dissolved component)
In the etching solution of the present invention, a metal dissolving component is contained. As the metal dissolving component, halogen ions are preferable, and fluorine ions are more preferable. It is understood that the metal-dissolving component (particularly fluorine ions) serves as a ligand (complexing agent) for the metal (Ti, etc.) of the second layer and promotes dissolution in the etching solution.
The concentration of the metal-soluble component (particularly fluorine ions) is preferably 0.1% by mass or more, more preferably 0.5% by mass or more, and particularly preferably 1% by mass or more in the etching solution. As an upper limit, 20 mass% or less is preferable, 10 mass% or less is more preferable, 5 mass% or less is further more preferable, and 2 mass% or less is especially preferable. By applying the metal-dissolved component (particularly fluorine ions) at the above concentration, effective protection of the layer to be protected can be realized while realizing good etching of the metal layer. A melt | dissolution component may use only 1 type, or may use it combining several things.
In the confirmation of the blending amount, when the component is ion, the amount may be specified by quantifying the amount of salt to be added.
Examples of the fluorine ion supply source include the fluorine compounds shown in the table below.

(PKa 4 or lower acid (acid assistant))
The etching solution according to the present invention preferably contains an acid assistant (pKa4 or lower acid is preferred). The pKa is further preferably 3 or less, more preferably 2 or less, further preferably 1.5 or less, further preferably 1 or less, and particularly preferably 0.5 or less. preferable. It is practical that the lower limit is pKa-20 or more. It is understood that the acid assistant plays a role of accelerating the oxidation of the second layer metal (such as Ti) even in a prescription with a small amount of water in the etching solution. In this respect, when pKa exceeds the above range, dissolution of metal (not oxidized) Ti or the like may not proceed.
As the acid assistant, boric acid compounds, phosphoric acid compounds, phosphonic acid compounds, HBF ₄ , HBr, HCl, HI, H ₂ SO ₄ , F ₃ CCOOH, Cl ₃ CCOOH and the like are preferable. Among these, an inorganic acid is preferable, and an inorganic acid containing a halogen atom is more preferable. Although the reason why the acid assistant is effective in the present invention is not clear, it is understood that the anion of the acid assistant exerts a specific effect in relation to the etching time dependency described later.
pKa has the same definition as above. Below, the calculation example of a typical substituent is shown. When the acid assistant has a multi-stage dissociation constant, the evaluation is performed based on 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 compound include alkylphosphonic acid (preferably having 1 to 30 carbon atoms, more preferably 3 to 24, and particularly preferably 4 to 18), and arylphosphonic acid (preferably having 6 to 22 carbon atoms, more preferably 6 to 14 carbon atoms). 6 to 10 are particularly preferred) and aralkylphosphonic acid (preferably 7 to 23 carbon atoms, more preferably 7 to 15 carbon atoms, and particularly preferably 7 to 11 carbon atoms). Alternatively, it may be polyvinyl phosphonic acid. The weight average molecular weight may be appropriately selected, but is preferably 3000 or more and 50000 or less.

Examples of the boron-containing acid compound include boric acid, boronic acid, and tetrafluoroboric acid. The boronic acid is preferably a boronic acid having 1 to 24 carbon atoms, more preferably a boronic acid having 1 to 12 carbon atoms. Specific examples include phenylboronic acid and methylboronic acid.
When these acids form a salt, the counter ion is not particularly limited, and examples thereof include alkali metal cations and organic cations.

The concentration of the acid assistant is preferably 0.1% by mass or more, more preferably 0.5% by mass or more, and particularly preferably 1% by mass or more in the etching solution. As an upper limit, 20 mass% or less is preferable, 10 mass% or less is more preferable, 5 mass% or less is further more preferable, and 3 mass% or less is especially preferable. 10 mass parts or more are preferable with respect to 100 mass parts of melt | dissolution components, 30 mass parts or more are more preferable, and 50 mass parts or more are especially preferable. As an upper limit, 1000 mass parts or less are preferable, 600 mass parts or less are more preferable, and 200 mass parts or less are especially preferable. In addition, an acid adjuvant may use only 1 type and may use 2 or more types together.

(Organic solvent)
The etching solution according to the present invention may contain an organic solvent. Among them, a protic polar organic solvent is preferable. As the protic polar organic solvent, alcohol compounds (including polyol compounds), ether compounds, and carboxylic acid compounds are preferable. It is understood that the organic solvent plays a role of reducing the dissolution rate of the metal or insulating film that requires selective treatment by relatively reducing the amount of water in the chemical solution in the etching solution.
For example, the organic solvent preferably has a Hansen parameter δh (hydrogen bond energy) of 5 or more, and particularly preferably of 10 or more. The viscosity is desirably 40 mPa · s (20 ° C.) or less, more desirably 35 mPa · s or less, and particularly desirably 10 mPa · s or less.

-Alcohol compounds Alcohol compounds widely include compounds having carbon and hydrogen in the molecule and having one or more hydroxyl groups. Here, even an ether compound having a hydroxyl group is an alcohol compound. The alcohol compound may have 1 or more carbon atoms, more preferably 2 or more, further preferably 3 or more, further preferably 4 or more, further preferably 5 or more, and particularly preferably 6 or more. The upper limit is preferably 24 or less, more preferably 12 or less, and particularly preferably 8 or less.
For example, methyl alcohol, ethyl alcohol, 1-propyl alcohol, 2-propyl alcohol, 2-butanol, ethylene glycol, propylene glycol, glycerin, hexylene glycol [HG], 1,6-hexanediol, cyclohexanediol, sorbitol, xylitol 2-methyl-2,4-pentanediol, 1,3-butanediol, 1,4-butanediol [14BD], 3-methyl-1-butanol [3M1B], methylpentanediol, cyclohexanol, ethylhexanol, Ether group-free alcohol compounds such as benzyl alcohol and phenylethanol,
Alkylene glycol alkyl ether (ethylene glycol monomethyl ether, ethylene glycol monobutyl ether, dipropylene glycol, propylene glycol monomethyl ether, diethylene glycol monomethyl ether, triethylene glycol, polyethylene glycol, propylene glycol monoethyl ether, dipropylene glycol monomethyl ether, tripropylene glycol Monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol monobutyl ether [DEGBE], etc.), phenoxyethanol, and ether group-containing alcohol compounds including methoxymethylbutanol.

Among them, the alcohol compound is preferably a compound represented by the following formula (O-1).
R ^O1 — (— O—R ^O2 —) _nO —OH (O-1)
・ R ^O1
R ^O1 represents a hydrogen atom, an alkyl group having 1 to 12 (preferably 1 to 6, more preferably 1 to 3) carbon atoms, an aryl group having 6 to 14 (preferably 6 to 10) carbon atoms, or 7 to 7 carbon atoms. 15 (preferably 7 to 11) aralkyl groups.
・ R ^O2
R ^O2 is a linear or branched alkylene chain having 1 to 12 carbon atoms. When a plurality of R ^O2 are present, each of them may be different. R ^O2 preferably has 2 to 10 carbon atoms, and more preferably 2 to 6 carbon atoms.
・ No
no is an integer from 0 to 12, preferably from 1 to 6. When no is 2 or more, the 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 (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 structural group which may have a substituent. The cyclic structural group may be an aromatic ring, a heteroaromatic ring, an aliphatic ring, or a heteroaliphatic ring. Examples of the aromatic ring include aryl groups having 6 to 14 carbon atoms (preferably 6 to 10 carbon atoms, more preferably phenyl groups). Examples of the aliphatic ring include cyclic alkyl groups having 3 to 14 carbon atoms (preferably having 3 to 10 carbon atoms, and more preferably a cyclohexyl group). The heterocyclic ring is preferably a heterocyclic group having 2 to 20 carbon atoms, preferably a 5- or 6-membered heterocyclic group having at least one oxygen atom, sulfur atom or nitrogen atom. Examples include 2-pyridyl, 4-pyridyl, 2-imidazolyl, 2-benzimidazolyl, 2-thiazolyl and 2-oxazolyl. The cyclic structure group may have an arbitrary substituent as appropriate.
L ^O1 represents a single bond, O, CO, is ^NR N, S or combinations thereof. Of these, a single bond, CO, and O are preferable, and a single bond or O is more preferable. ^RN is as defined above.
R ^O4 is an alkylene group (preferably having 1 to 12 carbon atoms, more preferably having 1 to 6 carbon atoms, and particularly preferably having 1 to 3 carbon atoms), or an arylene group (preferably having 6 to 14 carbon atoms, having 6 to 10 carbon atoms). More preferably), or an aralkylene group (preferably having 7 to 15 carbon atoms, more preferably 7 to 11 carbon atoms).
no is as defined above.

In particular, the ether compound is preferably a compound represented by the following formula (E-1).
R ^E1 — (— O—R ^E2 —) _m —R ^E3 (E-1)
・ R ^E1
R ^E1 represents an alkyl group having 1 to 12 carbon atoms (preferably 1 to 6, more preferably 1 to 4, more preferably 1 to 3), an aryl group having 6 to 14 carbon atoms (preferably 6 to 10), or An aralkyl group having 7 to 15 carbon atoms (preferably 7 to 11 carbon atoms).
-R ^E2 is synonymous with R ^O2 .
-R ^E3 is synonymous with R ^O1 .
M is an integer of 1 to 12, and preferably 1 to 6. When m is 2 or more, the plurality of R ^E2 may be different from each other.

The concentration of the organic solvent is preferably 20% by mass or more, more preferably 50% by mass or more, and particularly preferably 70% by mass or more in the etching solution. As an upper limit, 98 mass% or less is preferable, 95 mass% or less is more preferable, and 90 mass% or less is especially preferable.
In the present invention, the organic solvent may be used alone or in combination of two or more. When using 2 or more types together, the combined use ratio is not particularly limited, but the total use amount is preferably within the above-mentioned concentration range as a total of 2 or more types.

(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 only needs to have a carboxyl group in the molecule, and is a low molecular weight compound. When the carboxylic acid compound is a low molecular weight compound, it preferably has 4 to 48 carbon atoms, more preferably 4 to 36 carbon atoms, and particularly preferably 6 to 24 carbon atoms. It is understood that the carboxylic acid compound plays a role of accelerating dissolution of the second layer metal oxide (such as titanium oxide) as a complexing agent in the etching solution.

The carboxylic acid compound is preferably a compound represented by R ¹ —COOH. R ¹ is an alkyl group (preferably 1 to 48 carbon atoms, more preferably 4 to 36 carbon atoms, more preferably 6 to 24 carbon atoms), an alkenyl group (preferably 2 to 48 carbon atoms, more preferably 4 to 36 carbon atoms). 6 to 24 are more preferable), an alkynyl group (preferably having 2 to 48 carbon atoms, more preferably 4 to 36 carbon atoms, still more preferably 6 to 24 carbon atoms), an aryl group (preferably having 6 to 22 carbon atoms, 6 To 14), or an aralkyl group (preferably having 7 to 23 carbon atoms, more preferably 7 to 15 carbon atoms). When R ¹ is an aryl group, it may be 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. 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 having 1 to 12 carbon atoms, more preferably 1 to 6 carbon atoms, particularly preferably 1 to 3 carbon atoms), an alkynylene group (preferably having 2 to 12 carbon atoms, more preferably 2 to 6 carbon atoms). An alkenylene group (preferably having 2 to 12 carbon atoms, more preferably 2 to 6 carbon atoms), an arylene group (preferably having 6 to 22 carbon atoms, more preferably 6 to 14 carbon atoms), or an aralkylene group (preferably having 7 to 23 carbon atoms). 7 to 15 are more preferable.
R ³ has the same meaning as the linking group for R ² .
Y is an oxygen atom (O), a sulfur atom (S), a carbonyl group (CO), or an imino group (NR ^N ). R ⁴ represents an alkyl group (preferably having 1 to 12 carbon atoms, more preferably 1 to 6 carbon atoms, particularly preferably 1 to 3 carbon atoms), an alkenyl group (preferably having 2 to 12 carbon atoms, more preferably 2 to 6 carbon atoms), an alkynyl group. (Preferably 2 to 12 carbon atoms, more preferably 2 to 6 carbon atoms), aryl group (preferably 6 to 22 carbon atoms, more preferably 6 to 14 carbon atoms), or aralkyl group (preferably 7 to 23 carbon atoms, preferably 7 to 7 carbon atoms). 15 is more preferable). ^RN is as defined above.
n is an integer of 0 to 8.
R ¹ may further have a substituent, and among them, a sulfanyl group (SH), a hydroxyl group (OH), and an amino group (NR ^N ₂ ) are preferable. ^RN is as defined above.
The concentration of the carboxylic acid compound is preferably 0.01% by mass or more, more preferably 0.05% by mass or more, and particularly preferably 0.1% by mass or more in the etching solution. As an upper limit, 10 mass% or less is preferable, 3 mass% or less is more preferable, and 1 mass% or less is especially preferable. 1 mass part or more is preferable with respect to 100 mass parts of hydrofluoric acid, 3 mass parts or more are more preferable, and 5 mass parts or more are especially preferable. As an upper limit, 50 mass parts or less are preferable, 30 mass parts or less are more preferable, and 20 mass parts or less are especially preferable.

(Oxalic acid)
Among the above carboxylic acid compounds, oxalic acid may be contained in the etching solution as another type of additive. Oxalic acid plays a role of a complexing agent in the etching solution.

The concentration of oxalic acid is preferably 0.1% by mass or more, more preferably 0.5% by mass or more, and particularly preferably 1% by mass or more in the etching solution. As an upper limit, 20 mass% or less is preferable, 10 mass% or less is more preferable, 5 mass% or less is further more preferable, and 3 mass% or less is especially preferable. With respect to 100 parts by mass of hydrofluoric acid, 10 parts by mass or more is preferable, 30 parts by mass or more is more preferable, and 50 parts by mass or more is particularly preferable. As an upper limit, 1000 mass parts or less are preferable, 600 mass parts or less are more preferable, and 200 mass parts or less are especially preferable.

(Sugar)
The etching solution of the present invention may contain saccharides. It is understood that the acid of pKa2 or higher plays a role of preventing corrosion of the layer to be protected in the etching solution.
The saccharide is not particularly limited and may be a monosaccharide or a polysaccharide, but is preferably a monosaccharide. Examples of monosaccharides include hexose and pentose. In terms of structure, ketose, aldose, pyranose and furanose can be mentioned. Examples of hexose include allose, altrose, glucose, mannose, gulose, idose, galactose, talose, psicose, fructose, sorbose, tagatose and the like. Examples of pentose include ribose, arabinose, xylose, lyxose, ribulose, xylulose and the like. Examples of furanose include trofuranose, treofuranose, ribofuranose, arabinofuranose, xylofuranose, and loxofuranose. Examples of the pyranose include ribopyranose, arabinopyranose, xylopyranose, loxopyranose, allopyranose, arthropyranose, glucopyranose, mannopyranose, gropyranose, idopyranose, galactopyranose, and talopyranose.

The concentration of saccharide is preferably 0.01% by mass or more, more preferably 0.05% by mass or more, and particularly preferably 0.1% by mass or more in the etching solution. As an upper limit, 10 mass% or less is preferable, 3 mass% or less is more preferable, and 1 mass% or less is especially preferable. 1 mass part or more is preferable with respect to 100 mass parts of melt | dissolution components, 3 mass parts or more are more preferable, and 5 mass parts or more are especially preferable. As an upper limit, 50 mass parts or less are preferable, 30 mass parts or less are more preferable, and 20 mass parts or less are especially preferable.

(Carboxylic acid-containing polymer)
The etching solution of the present invention may contain a carboxylic acid-containing polymer. It is understood that the carboxylic acid-containing polymer plays a role of preventing corrosion of Al or Si-based insulating films in the etching solution.
The carboxylic acid-containing polymer is not particularly limited, and various polymers having 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), vinyl benzoic acid (VBA), and the like.

The concentration of the carboxylic acid-containing polymer is preferably 0.01% by mass or more, more preferably 0.05% by mass or more, and particularly preferably 0.1% by mass or more in the etching solution. As an upper limit, 10 mass% or less is preferable, 3 mass% or less is more preferable, and 1 mass% or less is especially preferable. 1 mass part or more is preferable with respect to 100 mass parts of melt | dissolution components, 3 mass parts or more are more preferable, and 5 mass parts or more are especially preferable. As an upper limit, 50 mass parts or less are preferable, 30 mass parts or less are more preferable, and 20 mass parts or less are especially preferable.

In the present specification, when a compound or a substituent / linking group includes an alkyl group / alkylene group, an alkenyl group / alkenylene group, an alkynyl group / alkynylene group, etc., these may be cyclic or linear, and may be linear or branched. It may be substituted with any group or unsubstituted. In this case, an alkyl group, an alkylene group, an alkenyl group, an alkenylene group, an alkynyl group, an alkynylene group is a group containing a hetero atom (e.g., O, S, CO, NR ^N and the like) may be separated by a, with this To form a ring structure. Moreover, when an aryl group, a heterocyclic group, etc. are included, they may be monocyclic or condensed and may be similarly substituted or unsubstituted.
In the present specification, the technical matters such as temperature and thickness, as well as the choices of substituents and linking groups of the compounds, can be combined with each other even if the list is described independently.
In the present specification, when a compound is specified by adding a compound or an acid to the end, it means that in addition to the above compound, its ion and salt are included within the range where the effects of the present invention are exhibited. Similarly, it is meant to include derivatives thereof.

(water)
The etching solution of the present invention preferably contains water (aqueous medium). The water (aqueous medium) may be an aqueous medium containing a dissolved component as long as the effects of the present invention are not impaired, or may contain an unavoidable trace mixed component. Among these, water that has been subjected to purification treatment such as distilled water, ion-exchanged water, or ultrapure water is preferable, and ultrapure water that is used for semiconductor manufacturing is particularly preferable. The concentration of water is not particularly limited, but is preferably 0.1% by mass or more, more preferably 1% by mass or more, and particularly preferably 5% by mass or more. As an upper limit, it is preferable that it is 50 mass% or less, It is more preferable that it is 40 mass% or less, It is especially preferable that it is 25 mass% or less.
In the present invention, it is preferable to regulate the concentration of the etching solution within a predetermined range. In the absence of water, the metal layer may not be sufficiently etched. Although it is preferable to apply in this respect, damage to the metal layer to be protected can be suppressed by suppressing this amount to a small amount.

(Specific organic additives)
The etchant according to this embodiment preferably contains a specific organic additive. This organic additive consists of an organic compound containing a nitrogen atom, a sulfur atom, a phosphorus atom, or an oxygen atom. Among these, the organic additives include amino groups (—NR ^N ₂ ) or salts thereof, imino groups (—NR ^N —) or salts thereof, sulfanyl groups (—SH), hydroxyl groups (—OH), carbonyl groups (— CO—), sulfonic acid group (—SO ₃ H) or a salt thereof, phosphoric acid group (—PO ₄ H ₂ ) or a salt thereof, onium group or a salt thereof, sulfinyl group (—SO—), sulfonyl group (SO ₂ ), An ether group (—O—), an amine oxide group, and a thioether group (—S—), a compound having a substituent or a linking group is preferable. Furthermore, it must be an aprotic dissociative organic compound (alcohol compound, ether compound, ester compound, carbonate compound), azole compound, betaine compound, sulfonic acid compound, amide compound, onium compound, amino acid compound, phosphoric acid compound, sulfoxide compound. Is also preferable.
The above ^RN is as defined above. Examples of the substituent include an alkyl group (preferably having 1 to 24 carbon atoms, more preferably 1 to 12 carbon atoms, further preferably 1 to 6 carbon atoms, and particularly preferably 1 to 3 carbon atoms), and an alkenyl group (preferably having 2 to 24 carbon atoms and 2 carbon atoms). To 12 is more preferable, 2 to 6 is more preferable, and 2 to 3 is particularly preferable, and an alkynyl group (2 to 24 carbon atoms is preferable, 2 to 12 is more preferable, 2 to 6 is more preferable, and 2 to 3 is Especially preferred are aryl groups having 6 to 10 carbon atoms and aralkyl groups having 7 to 11 carbon atoms.

The specific organic additive is particularly preferably composed of a compound represented by any of the following formulas (I) to (XIII).

Formula (I):
R ¹¹ and R ¹² are each independently a hydrogen atom, an alkyl group (preferably having 1 to 12 carbon atoms, more preferably 1 to 6 carbon atoms, particularly preferably 1 to 3 carbon atoms), and an alkenyl group (preferably having 2 to 12 carbon atoms). 2 to 6 are more preferred), an alkynyl group (preferably having 2 to 12 carbon atoms, more preferably 2 to 6), an aryl group (preferably having 6 to 22 carbon atoms, more preferably 6 to 14), an aralkyl group ( 7 to 23 carbon atoms are preferred, and 7 to 15 carbon atoms are more preferred), a sulfanyl group (SH), a hydroxyl group (OH), or an amino group (—NR ^N ₂ ). However, at least one of R ¹¹ and R ¹² is preferably a sulfanyl group, a hydroxyl group, or an amino group (preferably having a carbon number of 0 to 6, more preferably 0 to 3). ^RN is as defined above. In addition, when said substituent further takes a substituent (an alkyl group, an alkenyl group, an aryl group, etc.), you may have arbitrary substituent T. The same applies to the substituents and linking groups described below.

X ¹ is a methylene group (CR ^C ₂ ), a sulfur atom (S), or an oxygen atom (O). Of these, a sulfur atom is preferable. R ^C represents a hydrogen atom or a substituent (substituent T described below is preferred).

Formula (II):
X ² is a methine group (═CR ^C —) or a nitrogen atom (N). R ²¹ is a substituent (substituent T described below is preferred), and among them, a sulfanyl group (SH), a hydroxyl group (OH), and an amino group (NR ^N ₂ ) are preferred. R ^C and R ^N are as defined above.
n2 is an integer of 0-4.
When there are a plurality of R ^{21 s} , they may be the same or different, and may be bonded to each other or condensed to form a ring. The ring to be formed is preferably a nitrogen-containing heterocycle, and more preferably an unsaturated 5-membered or 6-membered nitrogen-containing heterocycle.

Formula (III):
Y ¹ is a methylene group, an imino group (NR ^N ), or a sulfur atom (S). ^RN is as defined above.
Y ² represents a hydrogen atom, an alkyl group (preferably 1 to 12 carbon atoms, more preferably 1 to 6 carbon atoms, particularly preferably 1 to 3 carbon atoms), an alkenyl group (preferably 2 to 12 carbon atoms, more preferably 2 to 6 carbon atoms). An alkynyl group (preferably 2 to 12 carbon atoms, more preferably 2 to 6 carbon atoms), an aryl group (preferably 6 to 22 carbon atoms, more preferably 6 to 14 carbon atoms), an aralkyl group (preferably 7 to 23 carbon atoms, 7 to 15 are more preferable), an amino group (preferably having 0 to 6 carbon atoms, more preferably 0 to 3), a hydroxyl group, and a sulfanyl group.
R ³¹ is a substituent (substituent T described below is preferred). Of these, a sulfanyl group (SH), a hydroxyl group (OH), and an amino group (NR ^N ₂ ) are preferable. ^RN is as defined above.
n3 is an integer of 0-2.
When there are a plurality of R ^{31 s} , they may be the same or different and may be bonded to each other or condensed to form a ring. The ring to be formed is preferably a 6-membered ring, and examples thereof include a benzene structure or a 6-membered heteroaryl structure (in particular, a pyridine structure or a pyrimidine structure is preferable).

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 is as defined above.
Y ¹ , Y ² , R ³¹ and n3 are as defined above. The positions of Y ³ and Y ⁴ may be at different positions in the six-membered ring.

Formula (IV):
L ¹ is an alkylene group (preferably having 1 to 12 carbon atoms, more preferably 1 to 6 carbon atoms, particularly preferably 1 to 3 carbon atoms), an alkynylene group (preferably having 2 to 12 carbon atoms, more preferably 2 to 6 carbon atoms), an alkenylene group. (Preferably 2 to 12 carbon atoms, more preferably 2 to 6 carbon atoms), arylene group (preferably 6 to 22 carbon atoms, more preferably 6 to 14 carbon atoms), or aralkylene group (preferably 7 to 23 carbon atoms, preferably 7 to 7 carbon atoms). 15 is more preferable).
X ⁴ is a carboxyl group or a hydroxyl group.
The SH group in the formula may be disulfide to form a dimer.

Formula (V):
R ⁵¹ is an alkyl group (preferably having 1 to 24 carbon atoms, more preferably 1 to 12 carbon atoms, still more preferably 1 to 6 carbon atoms, particularly preferably 1 to 3 carbon atoms), an alkenyl group (preferably having 2 to 24 carbon atoms, More preferably 2 to 12 carbon atoms, still more preferably 2 to 6 carbon atoms, an alkynyl group (preferably 2 to 24 carbon atoms, more preferably 2 to 12 carbon atoms, still more preferably 2 to 6 carbon atoms), an aryl group (carbon number 6 to 22 is preferable, and 6 to 14 is more preferable), or an aralkyl group (C 7 to 23 is preferable, and 7 to 15 is more preferable).
When R ⁵¹ is an aryl group, it includes an alkyl group having 1 to 20 carbon atoms, an alkenyl group having 2 to 20 carbon atoms, an alkynyl group having 2 to 20 carbon atoms, an alkoxy group having 1 to 20 carbon atoms, carbon An aryl group having 6 to 14 carbon atoms and an aryloxy group having 6 to 14 carbon atoms are preferably substituted.
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 having the same meaning as L ¹ . R ⁵³ is a linking group having the same meaning as L ¹ . Y ⁵³ is an oxygen atom (O), a sulfur atom (S), a carbonyl group (CO), or an imino group (NR ^N ). Alternatively, a combination of an oxygen atom (O), a sulfur atom (S), a carbonyl group (CO), and an imino group (NR ^N ) may be used, and examples thereof include (C═O) O and O (C═O). . R ⁵⁴ is an alkyl group (preferably having 1 to 24 carbon atoms, preferably 1 to 12, more preferably 1 to 6, more preferably 1 to 3), or an alkenyl group (preferably having 2 to 12 carbon atoms, preferably having 2 to 6 carbon atoms). More preferably), an alkynyl group (preferably 2 to 12 carbon atoms, more preferably 2 to 6 carbon atoms), an aryl group (preferably 6 to 22 carbon atoms, more preferably 6 to 14 carbon atoms), or an aralkyl group (7 to 7 carbon atoms). 23 is preferable, and 7 to 15 is more preferable. ^RN is as defined above.
n5 is an integer of 0 to 8.
R ⁵¹ may further have a substituent T, and among them, a sulfanyl group (SH), a hydroxyl group (OH), and an amino group (NR ^N ₂ ) are preferable. ^RN is as defined above.
Z is an amino group (NR ^N ₂ ) (preferably having 0 to 6 carbon atoms, more preferably 0 to 3), a sulfonic acid group (SO ₃ H), a sulfuric acid group (SO ₄ H), a phosphoric acid group (PO ₄ H ₂ ), a carboxyl group, a hydroxyl group, a sulfanyl group (SH), an onium group (preferably having 3 to 12 carbon atoms), an acyloxy group, or an amine oxide group (—NR ^N ₂ ⁺ O ⁻ ). Here, ^RN is as defined above.
In the present invention, an amino group, a sulfonic acid group, a phosphoric acid group, and a carboxyl group are acid esters (for example, alkyl esters, preferably having 1 to 24 carbon atoms, in the case of salts or acids thereof, unless otherwise specified. The number 1 to 12 is more preferable, and 1 to 6 is more preferable. The alkyl group forming the carboxylic acid ester may further have a substituent T. For example, the alkyl group which has a hydroxyl group is mentioned. In this case, the alkyl group is a group containing a hetero atom (e.g., O, S, CO, NR ^N, etc.) may form a ring structure with a. A sorbitan residue is mentioned as an alkyl group of a ring structure having a hydroxyl group. That is, sorbitan fatty acid esters (preferably having 7 to 40 carbon atoms, more preferably 8 to 24 carbon atoms) can be suitably used.

Between R ⁵¹ and Z in Formula (V), you may have arbitrary coupling groups in the range which has a desired effect. The optional linking group, examples of the examples or Y ⁵³ in the L ¹ and the like.
When Formula (V) is a carboxylic acid, R ⁵¹ is preferably an alkyl group, and in this case, 1 to 24 carbon atoms are preferable, 3 to 20 are more preferable, 6 to 18 are more preferable, and 8 to 16 is particularly preferred. The fact that this alkyl group may further have a substituent T is the same as the others.

Examples of the compound having an onium group include 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 ⁻ ), or an imidazoli sulfonium group _{^{_{^{^{(C 3 R N 3 NR N}}}}} N + -R 51 · M -) is preferred. ^RN is as defined above. M ⁻ is a paired anion (for example, OH ⁻ ).

When the compound which has the said onium group is illustrated in more detail, what is represented by the following formula | equation will be mentioned.

In the formula, R ^O7 to R ^O10 are each independently an alkyl group having 1 to 24 carbon atoms, an alkenyl group having 2 to 24 carbon atoms, an alkynyl group having 2 to 24 carbon atoms, an aryl group having 6 to 14 carbon atoms, 7 to 14 aralkyl groups, groups represented by the following formula (y). However, at least one carbon number of R ^O7 to R ^O10 is preferably 6 or more, 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, or an aryl group having 6 to 14 carbon atoms. Represents a hydroxyl group or an alkoxy group having 1 to 4 carbon atoms. Y2 represents O, S, CO, and NR ^N. Ry1 and Ry2 each independently represents an alkylene group having 1 to 6 carbon atoms, an alkenylene group having 2 to 6 carbon atoms, an alkynylene group having 2 to 6 carbon atoms, an arylene group having 6 to 10 carbon atoms, or a combination thereof. my represents an integer of 0 to 6. When my is 2 or more, the plurality of Ry1 and Y2 may be different from each other. Ry1 and Ry2 may further have a substituent T. * Is a bond. ^RN is as defined above.
R ^O11 is a group having the same ^meaning as R ^O7 , but the carbon number is preferably 6 or more, and more preferably 8 or more. R ^O12 is a substituent T. mO is an integer of 0-5.
M4 ⁻ , M5 ⁻ and M6 ⁻ are counter ions, and examples thereof include hydroxide ions.
R ^O13 is a group having the same ^meaning as Y1. R ^O14 and R ^O15 are the same groups as those in the formula (y). At least one Y1 of R ^O14 and R ^O15 is a carboxyl group, and preferably constitutes betaine.

The compound represented by the formula (V) is preferably any one of the following formulas (V-1) to (V-3). In formula, Z < ¹ >, Z < ² > is a sulfonic acid group which may pass through the coupling group L. In FIG. R ⁵⁶ is a substituent T, and among them, an alkyl group exemplified therein is preferable. n ⁵¹ and n ⁵⁶ are integers of 0 to 5. n ⁵³ is an integer of 0 to 4. The maximum value of n ⁵¹ , n ⁵³ , and n ⁵⁶ decreases with the number of Z ¹ or Z ^{2 in} the same ring. n ⁵² is an integer of 1 to 6, preferably 1 or 2. n ⁵⁴ and n ⁵⁵ are each independently an integer of 0 to 4, and n ⁵⁴ + n ⁵⁵ is 1 or more. n ⁵⁴ + n ⁵⁵ is preferably 1 or 2. n ⁵⁷ and n ⁵⁸ are each independently an integer of 0 to 5, and n ⁵⁷ + n ⁵⁸ is 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. Linking group L above L ^1, is preferably below L ^2, or a combination ^thereof, and more preferably L ^1.

Formula (VI):
R ⁶¹ and R ⁶² each independently represents an alkyl group (preferably having 1 to 12 carbon atoms, more preferably 1 to 6 carbon atoms, and particularly preferably 1 to 3 carbon atoms) or an aryl group (preferably having 6 to 22 carbon atoms, preferably 6 to 6 carbon atoms). 14 is more preferable), an alkoxy group (preferably having 1 to 12 carbon atoms, more preferably 1 to 6 carbon atoms, particularly preferably 1 to 3 carbon atoms), or an alkylamino group (preferably having 1 to 12 carbon atoms and more preferably 1 to 6 carbon atoms). 1 to 3 are preferred). R ⁶¹ and R ⁶² may be bonded or condensed to form a ring. When R ⁶¹ or R ⁶² is an alkyl group, it may be a group represented by the above * —R ⁵² — (R ⁵³ —Y ⁵³ ) —R ⁵⁴ .
L ² is a carbonyl group, a sulfinyl group (SO), or a sulfonyl group (SO ₂ ).
The compound represented by the formula (VI) is preferably a compound represented by any one of the following formulas (VI-1) to (VI-3). In the formula, R ⁶¹ and R ⁶² are as defined above. Q ⁶ is a 3- to 8-membered ring, preferably a 5- or 6-membered ring, more preferably a saturated 5- or 6-membered ring, and particularly preferably a saturated hydrocarbon 5- or 6-membered ring. However, Q ⁶ may have an arbitrary substituent T.

Formula (VII):
R ⁷¹ is an amino group (—NR ^N ₂ ), an ammonium group (—NR ^N ₃ ⁺ · M ⁻ ), or a carboxyl group. R ^N and M ^- it is according to the foregoing definition.
L ³ is a single bond or a group having the same meaning as L ¹ . Among them, L ³ is preferably a methylene group, an ethylene group, a propylene group, or (—L ³¹ (SR ^S ) p—). L ³¹ is an alkylene group having 1 to 6 carbon atoms. R ^S may be dimerized by forming a hydrogen atom or a disulfide group at this site. p is an integer of 1 to 5, preferably 1 to 2.
When R ⁷¹ is a carboxyl group, this compound becomes a dicarboxylic acid compound. Examples of dicarboxylic acid compounds include oxalic acid, malonic acid, succinic acid, glutaric acid, adipic acid, pimelic acid, suberic acid, xeraic acid, sebacic acid, phthalic acid, isophthalic acid, terephthalic acid, among others. Oxalic acid is preferred.

Formula (IIX):
R ⁸¹ and R ⁸² each independently represents an alkyl group (preferably having 1 to 12 carbon atoms, more preferably 1 to 6 carbon atoms, and particularly preferably 1 to 3 carbon atoms) or an alkenyl group (preferably having 2 to 12 carbon atoms). 6 is more preferable), an alkynyl group (preferably having 2 to 12 carbon atoms, more preferably 2 to 6 carbon atoms), an aryl group (preferably having 6 to 22 carbon atoms, more preferably 6 to 14 carbon atoms), or an aralkyl group (having carbon numbers). 7 to 23 are preferable, and 7 to 15 are more preferable. ^RN is as defined above.

Formula (IX):
L ⁴ is a group having the same meaning as L ¹ .
R ⁹¹ and R ⁹³ each independently represent a hydrogen atom, an alkyl group (preferably having 1 to 12 carbon atoms, more preferably 1 to 6 carbon atoms, and particularly preferably 1 to 3 carbon atoms), or an alkenyl group (preferably having 2 to 12 carbon atoms; To 6), alkynyl groups (preferably having 2 to 12 carbon atoms, more preferably 2 to 6 carbon atoms), aryl groups (preferably having 6 to 22 carbon atoms, more preferably 6 to 14 carbon atoms), acyl groups (having carbon numbers) 2 to 12 are preferred, and 2 to 6 are more preferred), or an aralkyl group (preferably having a carbon number of 7 to 23, more preferably 7 to 15). However, when n9 is 0, R ⁹¹ and R ⁹³ are not both hydrogen atoms.
n9 is an integer of 0 to 100, preferably 0 to 50, more preferably 0 to 25, still more preferably 0 to 15, further preferably 0 to 10, and particularly preferably 0 to 5.

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

^{^{^{_{R 91 - (OL 41) -}}}} (OL 4) n91 -OR 93 (IX-1)

L ⁴¹ is preferably an alkylene group having 2 or more carbon atoms, preferably 2 to 6 carbon atoms. By setting the number of carbon atoms of the alkylene group, it is presumed that a specific adsorption state with a metal (for example, Ti) is not formed and the removal thereof is not hindered. In addition, the binding component between the metal and the fluorine atom is considered to behave in a hydrophilic or hydrophobic manner, and it is presumed that a compound having 2 or 3 or more carbon atoms connecting the oxygen atoms acts suitably. From this viewpoint, L ⁴¹ preferably further has 3 or more carbon atoms, more preferably 3 to 6 carbon atoms, and particularly preferably 3 or 4 carbon atoms. The number of carbon atoms in the L ^41, when an alkylene group of branches, except the carbon atoms contained in the branch, it is preferred that the linking carbon number of 2 or more. For example, a 2,2-propanediyl group has a linking carbon number of 1. That is, the number of carbon atoms connecting OO is called the number of connected carbons, and it is preferable that the number is 2 or more. Considering the adsorption action with the above metal, the number of connected 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 the same number as n9.

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

R ⁹⁴ to R ⁹⁷ in the formula have the same ^meaning as R ⁹¹ . R ⁹⁴ to R ⁹⁷ may further have a substituent T, for example, 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 hexylene glycol, 1,3-butanediol, 1,4-butanediol and the like.

From the viewpoint of the hydrophilicity / hydrophobicity, the compound represented by the formula (IX) is preferably used in a desired range in the 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 is preferably 2 or less, and more preferably 1.5 or less.

・ ClogP
The measurement of the octanol-water partition coefficient (log P value) can be generally carried out by a flask soaking method described in JIS Japanese Industrial Standard Z7260-107 (2000). Further, the octanol-water partition coefficient (log P value) can be estimated by a computational chemical method or an empirical method instead of the actual measurement. As the calculation method, Crippen's fragmentation method (J. Chem. Inf. Comput. Sci., 27, 21 (1987)), Viswanadhan's fragmentation method (J. Chem. Inf. Comput. Sci., 29, 163 (1989)), Broto's It is known to use a fragmentation method (Eur. J. Med. Chem.-Chim. Theor., 19, 71 (1984)). In the present invention, the Crippen's fragmentation method (J. Chem. Inf. Comput. Sci., 27, 21 (1987)) is used.
The ClogP value is a value obtained by calculating the common logarithm logP of the distribution coefficient P between 1-octanol and water. Known methods and software can be used for calculating the ClogP value. Unless otherwise specified, the present invention uses a ClogP program incorporated in the system: PCModels of Daylight Chemical Information Systems.

Formula (X):
R ^A3 has the same ^meaning as RN. R ^A1 and R ^A2 each independently represent a hydrogen atom, an alkyl group (preferably having 1 to 12 carbon atoms, more preferably 1 to 6 carbon atoms, and particularly preferably 1 to 3 carbon atoms), or an alkenyl group (preferably having 2 to 12 carbon atoms). 2 to 6 are more preferred), an alkynyl group (preferably having 2 to 12 carbon atoms, more preferably 2 to 6), an aryl group (preferably having 6 to 22 carbon atoms, more preferably 6 to 14), an aralkyl group ( 7 to 23 carbon atoms, more preferably 7 to 15 carbon atoms), a sulfanyl group, a hydroxyl group, or an amino group. However, at least one of R ^A1 and R ^A2 is preferably a sulfanyl group, a hydroxyl group, or an amino group (preferably having 0 to 6 carbon atoms, more preferably 0 to 3 carbon atoms).

Formula (XI):
Y ⁷ and Y ⁸ are each independently an oxygen atom, a sulfur atom, an imino group (NR ^N ) or a carbonyl group. R ^B1 is a substituent (the substituent T described below is preferred). nB is an integer of 0-8. However, either one of Y ⁷ and Y ⁸ may be a methylene group (CR ^C ₂ ). R ^C and R ^N are as defined above.

Formula (XII):
Y ⁹ and Y ¹⁰ are each 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 may be another position of the six-membered ring. R ^C and R ^N are as defined above.
X ⁵ and X ⁶ are a sulfur atom or an oxygen atom. A broken line means that the bond may be a single bond or a double bond. R ^C1 is a substituent (the substituent T described later is preferred). nC is an integer of 0-2.
When there are a plurality of R ^{C1 s} , they may be the same as or different from each other, and may be bonded or condensed to form a ring.

Formula (XIII):
X ³ is an oxygen atom, a sulfur atom, or an imino group (NR ^M ). R ^M is a hydrogen atom or an alkyl group having 1 to 24 carbon atoms, preferably an alkyl group having 2 to 20 carbon atoms, more preferably an alkyl group having 4 to 16 carbon atoms, and an alkyl group having 6 to 12 carbon atoms. It is particularly preferred.
X ⁵ is an oxygen atom, a sulfur atom, an imino group (NR ^M ), or a methylene group (CR ^C ₂ ). R ^C is as defined above.
R ^D1 is a substituent, and the substituent T described later is preferable. R ^D1 is preferably an alkyl group of 1 to 24, more preferably an alkyl group of 1 to 12.
nD is an integer of 0 to 6, preferably an integer of 0 to 2, and particularly preferably 1.
Of these, X ³ —CO—X ⁵ in the formula is preferably NR ^N —CO—CR ^C ₂ , O—CO—O, or O—CO—CR ^C ₂ . ^RN is as defined above.

The specific organic additive is preferably composed of a compound selected from the following first group or second group.

Among the specific organic additives, the concentration of those belonging to the first group is preferably 50% by mass or more, more preferably 55% by mass or more, still more preferably 60% by mass or more, in the etching solution, 70 It is particularly preferable to contain at least mass%. As an upper limit, 99 mass% or less is preferable, 95 mass% or less is more preferable, and 90 mass% or less is especially preferable.
Among the specific organic additives, the concentration of those belonging to the second group is preferably 0.005% by mass or more, more preferably 0.01% by mass or more, and 0.03% by mass in the etching solution. The above is more preferable, and 0.05% by mass or more is particularly preferable. As an upper limit, 10 mass% or less is preferable, 7 mass% or less is more preferable, and 5 mass% or less is especially preferable.

Regarding the distinction between the above formulas and the first group and the second group, the compounds according to the formula (V) or a part thereof, (VI), (IIX), (IX), (XI) are the first group. In addition, it is preferable that the compound according to the other formula or formula (V) or a part thereof is the second group.
In addition, in this specification, it uses for the meaning containing the salt and its ion besides the compound itself about the display of a compound (for example, when calling it attaching | subjecting to a compound and an end). In addition, it is meant to include derivatives in which a part thereof is changed, such as introduction of a substituent, within a range where a desired effect is exhibited.

In the present specification, a substituent that does not specify substitution / non-substitution (the same applies to a linking group) means that the group may have an arbitrary substituent. This is also synonymous for compounds that do not specify substitution / non-substitution. Preferred substituents include the following substituent T.
Examples of the substituent T include the following.
An alkyl group (preferably an alkyl group having 1 to 20 carbon atoms, such as methyl, ethyl, isopropyl, t-butyl, pentyl, heptyl, 1-ethylpentyl, benzyl, 2-ethoxyethyl, 1-carboxymethyl, etc.), alkenyl A group (preferably an alkenyl group having 2 to 20 carbon atoms such as vinyl, allyl, oleyl and the like), an alkynyl group (preferably an alkynyl group having 2 to 20 carbon atoms such as ethynyl, butadiynyl, phenylethynyl and the like), A cycloalkyl group (preferably a cycloalkyl group having 3 to 20 carbon atoms, such as cyclopropyl, cyclopentyl, cyclohexyl, 4-methylcyclohexyl, etc.), an aryl group (preferably an aryl group having 6 to 26 carbon atoms, for example, Phenyl, 1-naphthyl, 4-methoxyphenyl, -Chlorophenyl, 3-methylphenyl, etc.), heterocyclic groups (preferably heterocyclic groups of 2 to 20 carbon atoms, preferably 5- or 6-membered heterocycles having at least one oxygen atom, sulfur atom, nitrogen atom) A cyclic group is preferred, for example, 2-pyridyl, 4-pyridyl, 2-imidazolyl, 2-benzimidazolyl, 2-thiazolyl, 2-oxazolyl, etc.), an alkoxy group (preferably an alkoxy group having 1 to 20 carbon atoms, for example, Methoxy, ethoxy, isopropyloxy, benzyloxy, etc.), aryloxy groups (preferably aryloxy groups having 6 to 26 carbon atoms, such as phenoxy, 1-naphthyloxy, 3-methylphenoxy, 4-methoxyphenoxy, etc.), An alkoxycarbonyl group (preferably an alkoxycarbonyl group having 2 to 20 carbon atoms) Nyl groups such as ethoxycarbonyl, 2-ethylhexyloxycarbonyl and the like, amino groups (preferably containing an amino group having 0 to 20 carbon atoms, alkylamino group, arylamino group, such as amino, N, N-dimethyl) Amino, N, N-diethylamino, N-ethylamino, anilino, etc.), sulfamoyl groups (preferably sulfamoyl groups having 0 to 20 carbon atoms, such as N, N-dimethylsulfamoyl, N-phenylsulfamoyl, etc.) ), An acyl group (preferably an acyl group having 1 to 20 carbon atoms, such as acetyl, propionyl, butyryl, benzoyl, etc.), an acyloxy group (preferably an acyloxy group having 1 to 20 carbon atoms, such as acetyloxy, benzoyl) Oxy, etc.), a carbamoyl group (preferably a C 1-20 carbon Rubamoyl groups such as N, N-dimethylcarbamoyl and N-phenylcarbamoyl), acylamino groups (preferably acylamino groups having 1 to 20 carbon atoms such as acetylamino and benzoylamino), sulfonamide groups (preferably A sulfamoyl group having 0 to 20 carbon atoms, such as methanesulfonamide, benzenesulfonamide, N-methylmethanesulfonamide, N-ethylbenzenesulfonamide, etc., an alkylthio group (preferably an alkylthio group having 1 to 20 carbon atoms, For example, methylthio, ethylthio, isopropylthio, benzylthio, etc.), arylthio groups (preferably arylthio groups having 6 to 26 carbon atoms, such as phenylthio, 1-naphthylthio, 3-methylphenylthio, 4-methoxyphenylthio, etc.), Alkyl group or arylsulfonyl group (preferably an alkyl or arylsulfonyl group having 1 to 20 carbon atoms, such as methylsulfonyl, ethylsulfonyl, benzenesulfonyl, etc.), hydroxyl group, cyano group, halogen atom (for example, fluorine atom, chlorine atom, Bromine atom, iodine atom, etc.), more preferably alkyl group, alkenyl group, aryl group, heterocyclic group, alkoxy group, aryloxy group, alkoxycarbonyl group, amino group, acylamino group, phosphonic acid group, sulfonic acid group , Phosphoric acid group, carboxyl group, hydroxyl group or halogen atom.
In addition, each of the groups listed as the substituent T may be further substituted with the substituent T described above.

(kit)
The etching solution in the present invention may be a kit in which the raw material is divided into a plurality. For example, the liquid composition which contains the said melt | dissolution component in water as a 1st liquid is prepared, and the aspect which prepares the liquid composition containing an organic solvent as a 2nd liquid is mentioned. At this time, components such as other compounds can be contained separately or together in the first liquid, the second liquid, or the other third liquid.
As an example of its use, a mode in which both solutions are mixed to prepare an etching solution, and then applied to the etching treatment at an appropriate time is preferable. By doing in this way, it does not cause deterioration of the liquid performance by decomposition | disassembly of each component, and a desired etching effect | action can be exhibited effectively. Here, “timely” after mixing refers to the time until the desired action is lost after mixing, specifically within 60 minutes, more preferably within 30 minutes, and more preferably within 10 minutes. Is more preferably within 1 minute, and particularly preferably within 1 minute. Although there is no lower limit in particular, it is practical that it is 1 second or more.
The method of mixing the first liquid and the second liquid is not particularly limited, but it is preferable that the first liquid and the second liquid are circulated through the respective flow paths, and both are merged at the merging point and mixed. After that, it is preferable that the flow path is further circulated, and the etching solution obtained by joining is discharged or jetted from the discharge port and brought into contact with the semiconductor substrate. In this embodiment, it is preferable that the process from the merging and mixing at the merging point to the contact with the semiconductor substrate is performed at the “timely”. This will be described with reference to FIG. 4. The prepared etching solution 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 the figure, the two liquids A and B are supplied, merge at the junction 14, and then move to the discharge port 13 via the flow path fc. A flow path fd indicates a return path for reusing the chemical solution. The semiconductor substrate S is on the turntable 12 and is preferably rotated together with the turntable by the rotation drive unit M. Note that an embodiment using such a substrate rotation type apparatus can be similarly applied to a process using an etching solution that is not used as a kit.
In addition, the etching liquid of this invention has few impurities, for example, a metal content, etc. in a liquid in view of the use use. In particular, the Na, K, and Ca ion concentration in the liquid is preferably in the range of 1 ppt to 1 ppm (mass basis). In the etching solution, the number of coarse particles having an average particle size of 0.5 μm or more is preferably in the range of 100 particles / cm ³ or less, and is preferably in the range of 50 particles / cm ³ or less.

(container)
The etching solution of the present invention can be stored, transported and used in any container as long as corrosivity or the like is not a problem (regardless of whether it is a kit or not). For semiconductor applications, a container having a high cleanliness and a low impurity elution is preferable. Examples of the containers that can be used include, but are not limited to, “Clean Bottle” series manufactured by Aicero Chemical Co., Ltd., “Pure Bottle” manufactured by Kodama Resin Co., Ltd., and the like.

[Etching conditions]
In the etching method of the present invention, it is preferable to use a single wafer type apparatus. Specifically, the single wafer type apparatus has a processing tank, and the semiconductor substrate is transported or rotated in the processing tank, and the etching solution is applied (discharge, jetting, flowing down, dropping, etc.) into the processing tank. The etching solution is preferably brought into contact with the semiconductor substrate.
Advantages of the single wafer type apparatus include (i) a fresh etching solution is always supplied, so that reproducibility is good, and (ii) in-plane uniformity is high. Furthermore, it is easy to use a kit in which the etching liquid is divided into a plurality of parts. For example, a method in which the first liquid and the second liquid are mixed in-line and discharged is suitably employed. At this time, it is preferable to adjust the temperature of both the first liquid and the second liquid, or to adjust the temperature of only one of them and mix and discharge them in-line. Among these, an embodiment in which the temperature is controlled together is more preferable. The management temperature when adjusting the line temperature is preferably in the same range as the processing temperature described later.
The single wafer type apparatus is preferably provided with a nozzle in its processing tank, and a method of discharging the etching liquid onto the semiconductor substrate by swinging the nozzle in the surface direction of the semiconductor substrate is preferable. By doing so, the deterioration of the liquid can be prevented, which is preferable. In addition, it is preferable that a kit is divided into two or more liquids so that it is difficult to generate gas or the like.

The processing temperature at which etching is performed 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, further preferably 60 ° C. or lower, further preferably 50 ° C. or lower, and preferably 40 ° C. or lower. Particularly preferred. By setting it to the above lower limit value or more, a sufficient etching rate for the second layer can be secured, which is preferable. By setting it to the upper limit value or less, it is preferable because the temporal stability of the etching processing rate can be maintained. In addition, the ability to process near room temperature leads to a reduction in energy consumption.
The etching processing temperature is based on the temperature applied to the substrate in the temperature measurement method shown in the examples described later. However, when the temperature is controlled by the storage temperature or batch processing, the temperature in the tank is controlled by the circulation system. In some cases, the temperature may be set in the circulation flow path.
The supply rate of the etching solution is not particularly limited, but is preferably 0.05 to 5 L / min, and more preferably 0.1 to 3 L / min. By setting it to the above lower limit value or more, it is preferable because uniformity in the etching plane can be ensured. By setting it to the upper limit value or less, it is preferable because stable performance can be secured during continuous processing. When the semiconductor substrate is rotated, although it depends on its size and the like, it is preferably rotated at 50 to 1000 rpm from the same viewpoint as described above.

In the single-wafer etching according to a preferred embodiment of the present invention, it is preferable that the semiconductor substrate is transported or rotated in a predetermined direction, an etching solution is sprayed into the space, and the etching solution is brought into contact with the semiconductor substrate. . The supply rate of the etching solution and the rotation speed of the substrate are the same as those already described.
In the single-wafer type apparatus configuration according to a preferred embodiment of the present invention, as shown in FIG. 5, it is preferable to apply the etching solution while moving the discharge port (nozzle). Specifically, in the present embodiment, when the etching solution is applied to the semiconductor substrate S, the substrate is rotated in the r direction. On the other hand, the discharge port is adapted to move along a movement trajectory line t extending from the center portion to the end portion of the semiconductor substrate. As described above, in this embodiment, the direction of rotation of the substrate and the direction of movement of the discharge port are set to be different from each other. As a result, the etching solution can be applied evenly over the entire surface of the semiconductor substrate, and the etching uniformity is suitably ensured.
The moving speed of the discharge port (nozzle) is not particularly limited, but is preferably 0.1 cm / s or more, and more preferably 1 cm / s or more. On the other hand, the upper limit is preferably 30 cm / s or less, and more preferably 15 cm / s or less. The movement trajectory line may be a straight line or a curved line (for example, an arc shape). In either case, the moving speed can be calculated from the actual distance of the trajectory line and the time spent for the movement. The time required for etching one substrate is preferably in the range of 10 to 300 seconds.

The metal layer is preferably etched at a high etching rate. The etching rate [R2] of the second layer (metal layer) is not particularly limited, but is preferably 50 Å / min or more, more preferably 100 Å / min or more, and 200 Å / min or more in consideration of production efficiency. It is particularly preferred. Although there is no upper limit in particular, it is practical that it is 1000 kg / min or less.

Although the exposed width of the metal layer is not particularly limited, it is preferably 2 nm or more, more preferably 4 nm or more from the viewpoint that the advantages of the present invention become more prominent. Similarly, from the viewpoint of conspicuous effect, the upper limit is practically 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, but is preferably not excessively removed, more preferably 40 Å / min or less, and 20 Å / min or less. More preferably, it is 10 Å / min or less. There is no particular lower limit, but considering the measurement limit, it is practical that it is 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, but is preferably 2 or more, It is more preferably 5 or more, and further preferably 10 or more. The upper limit is not particularly defined and is preferably as high as possible, but is practically 10,000 or less.

Furthermore, in the etching solution according to a preferred embodiment of the present invention, a metal electrode layer such as Al or W, a layer such as HfO, HfSiO, WO, AlO _x , SiO, SiOC, SiON, SiOCN, TiN, SiN, or TiAlC (these layers) (Sometimes collectively referred to as a fourth layer) can be suitably suppressed, and therefore, it is also preferably applied to a semiconductor substrate including these. The preferable etching rate of the fourth layer is indicated by the same parameter [R1] as the etching rate of the first layer to the third layer as described above. The preferred range is as described above. The preferable range of the etching rate ratio with the second layer is also synonymous with [R2] / [R1]. In addition, in this specification, when the composition of a metal compound is expressed by a combination of elements, it means that a composition having an arbitrary composition is widely included. For example, SiOC (SiON) means that Si, O, and C (N) coexist, and does not mean that the ratio of the amounts is 1: 1: 1. This is common in this specification, and the same applies to other metal compounds.

The time required for etching one substrate is preferably 10 seconds or more, and more preferably 50 seconds or more. As an upper limit, it is preferable that it is 300 seconds or less, and it is more preferable that it is 200 seconds or less.

[Manufacture of semiconductor substrate products (semiconductor process)]
In this embodiment, a step of forming a semiconductor substrate on which a silicon layer and a metal layer are formed on a silicon wafer, a step of annealing the semiconductor substrate, an etchant is applied to the semiconductor substrate, and the etchant and the metal layer It is preferable to manufacture a semiconductor substrate product having a desired structure through a step of selectively removing the metal layer by bringing the metal layer into contact with each other. At this time, the specific etching solution is used for etching. The order of the above steps is not construed as being limited, and further steps may be included between the steps.
The wafer size is not particularly limited, but a wafer having a diameter of 8 inches, a diameter of 12 inches, or a diameter of 14 inches can be suitably used (1 inch = 25.4 mm).
In this specification, the term “preparation” means that a specific material is synthesized or blended, and a predetermined item is procured by purchase or the like. In this specification, using an etchant so as to etch each material of a semiconductor substrate is referred to as “application”, but the embodiment is not particularly limited. For example, the method widely includes contacting the etching solution with the substrate. Specifically, the etching solution may be immersed and etched in a batch type or may be etched by discharge in a single wafer type.
In this specification, the term “semiconductor substrate” is used to mean not only a wafer but also the entire substrate structure having a circuit structure formed thereon. A semiconductor substrate member refers to the member which comprises the semiconductor substrate defined above, and may consist of one material or may consist of several materials. A processed semiconductor substrate is sometimes referred to as a semiconductor substrate product, and is further distinguished as necessary, and a chip that has been processed and diced out and processed product thereof is referred to as a semiconductor element. That is, in a broad sense, a semiconductor element or a semiconductor product incorporating the semiconductor element belongs to a semiconductor substrate product.

Hereinafter, the present invention will be described in more detail with reference to examples. However, the present invention is not limited to the following examples. In addition, unless otherwise indicated,% and part shown as prescription and compounding quantity in an Example are mass references | standards.

[Reference Example 1]
(Production of test substrate)
SiGe was epitaxially grown on a commercially available silicon substrate (diameter: 12 inches) and formed to a thickness of 500 mm. Similarly, blanket wafers in which other films were formed by CVD or the like were prepared. At this time, the SiGe epitaxial layer contained 50 to 60% by mass of germanium. In the tests shown in the table below, the etching rate of each layer was calculated using these blanket wafers.
Further, a Ti layer was formed on the SiGe epitaxial layer. This was annealed at 800 ° C. for 10 seconds to form a silicide layer to obtain a test substrate. The thickness of the silicide layer after annealing was 15 nm, and the thickness of the metal layer was 5 nm.

(Etching test)
The blank wafer and the test substrate were etched by the single wafer type apparatus (manufactured by SPS-Europe B.V., POLOS (trade name)) under the following conditions, and an evaluation test was performed.
・ Processing temperature: 24 ° C. Room temperature ・ Discharge rate: 1 L / min.
-Wafer rotation speed: 500 rpm
・ Nozzle moving speed: 7cm / S
Treatment time: 60 seconds Note that the etching solution was supplied in one solution (only the A line in FIG. 4 was used). Each treatment test was performed immediately after preparation.

(Measurement method of processing temperature)
A radiation thermometer IT-550F (trade name) manufactured by HORIBA, Ltd. was fixed at a height of 30 cm above the wafer in the single wafer type apparatus. A thermometer was directed onto the wafer surface 2 cm outside from the wafer center, and the temperature was measured while flowing a chemical solution. The temperature was digitally output from the radiation thermometer and recorded continuously with a personal computer. Among these, the value obtained by averaging the temperature for 10 seconds at which the temperature was stabilized was defined as the temperature on the wafer.

(Etching rate [ER])
About the etching rate (ER), it computed by measuring the film thickness before and behind an etching process using ellipsometry (a spectroscopic ellipsometer, JA Woolum Japan Co., Ltd. Vase was used). An average value of 5 points was adopted (measurement condition measurement range: 1.2-2.5 eV, measurement angle: 70, 75 degrees).
(TiSiGe damage)
The degree of damage to the germanium silicide layer (TiSiGe) was judged from the amount of change in sheet resistance before and after the etching process and the thickness of TiSiGe by etching ESCA. Evaluations A to E were defined by the following equations depending on how much the thickness of the TiSiGe layer in ESCA was lost compared to the initial state.
TiSiGe damage (%) =
(TiSiGe thickness after chemical treatment / TiSiGe thickness before chemical treatment) × 100
A: 80 super 100 or less B: 60 super 80 or less C: 40 super 60 or less D: 20 super 40 the following E: 0 Ultra 20 below Incidentally, A ^- but became evaluation of A, it was slightly inferior.

(A) HF
(B) Water
(C) Organic solvent protic polar solvent with high δh
(D) Acid aid
(E)-(G) Carboxylic acid

<Table notes>
ER: etching rate PAA: polyacrylic acid DHC: dehydrocholic acid LA: lauric acid SA: stearic acid Lib: ribose DEGBE: diethylene glycol monobutyl ether
Those that become negative at the etching rate are understood to have become thicker without being etched.

[Example 1]
Test No. Except that the oxalic acids 101 to 112 were changed to the following compounds, The etching rate [ER] and TiSiGe damage were evaluated in the same manner as in 101-112. As a result, in any of the Examples, TiAlC [ER] was 1.0 or less without deteriorating other performances, and a significant TiAlC anticorrosive effect was obtained.
Compounds disclosed in Examples after paragraph 0265 of JP-A-2007-277514 (B-1 to B-24, C-1 to C-57, D-1 to D-12)
WO2014 / 034813A1 Compounds disclosed in Examples after paragraph 0200 (C-1 to C-136)
WO2014 / 034815A1 Compounds disclosed in Examples after paragraph 0194 (C-1 to C-199)
In addition, the etching rate [ER] and TiSiGe damage were evaluated in the same manner as in Test Nos. 101 to 112 except that the organic solvent in Test Nos. 101 to 112 was reduced and 0.2 mass% of the above compound was added instead. did. As a result, in any of the Examples, TiAlC [ER] was 1.0 or less without deteriorating other performances, and a remarkable anticorrosive effect of TiAlC was obtained.

[Example 2 and Comparative Example 1]
Etching rates of Ti, SiO ₂ and TiAlC were confirmed in the same manner as in Reference Example 1 except that an etching solution having the following composition was used.

(A) HF
(B) Water
(C) Organic solvent protic polar solvent with high δh
(D) Acid aid
(E) Carboxylic acid (oxalic acid)
(F) Compound P

EtOH: Ethanol DEGBE: Diethylene glycol monobutyl ether PGME: Propylene glycol monomethyl ether Lower row: Blending amount (% by mass)

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

While this invention has been described in conjunction with its embodiments, we do not intend to limit our invention in any detail of the description unless otherwise specified and are contrary to the spirit and scope of the invention as set forth in the appended claims. I think it should be interpreted widely.

This application claims priority based on Japanese Patent Application No. 2014-094213 filed in Japan on April 30, 2014, the contents of which are hereby incorporated by reference. Capture as.

1 Metal layer (second layer)
2 Silicon or germanium-containing layer (first layer)
3 Silicide layer (third layer)
11 Processing container (processing tank)
12 Turntable 13 Discharge port 14 Junction point S Substrate 21 Silicon substrate 22 Gate insulating film 23 Gate electrode 25 Side wall 26 Source electrode 27 Drain electrode 28

Ti film

90A, 90B

Replacement gate stack

92A,

92B Well

94A, 94B Source /

drain extension Regions

96A, 96B source /

drain regions

91A, 91B metal

semiconductor alloy portions

95A,

95B gate spacers

97A, 97B gate insulating film 81 first work function material layers 82A, 82B second work function material layers 83A, 83B metal portions 93 trench structure Part 99 Planarized dielectric layer

Claims

An etching solution for a semiconductor process,
An etchant containing a compound P having a plurality of adsorbing groups and having a weight average molecular weight of 1000 or more.
An etching solution for a semiconductor process,
An etching solution containing a compound P having a plurality of adsorbing groups and a steric repulsion site.
The etching solution according to claim 1 or 2, further comprising at least one of a metal-dissolving component, an acid assistant having a pKa of 4 or less, an organic solvent, and water.
The etching solution according to claim 3, wherein the acid assistant is a boric acid compound, a phosphoric acid compound, a phosphonic acid compound, HBF 4 , HBr, or HCl.
The etching solution according to claim 3 or 4, wherein the organic solvent is a protic polar organic solvent.
6. The etching solution according to claim 3, 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 any one of claims 3 to 6, wherein the metal dissolving component is a halogen ion.
The etching solution according to claim 7, wherein the halogen ions are fluorine ions.
The etching solution according to any one of claims 1 to 8, wherein the compound P is a compound represented by the following formula (I) or a compound having a partial structure represented by the following formula (II).
(A) n- P a (I)
A is an adsorbing 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 adsorbing 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.
The etching solution according to any one of claims 1 to 9, which is applied to a semiconductor substrate having a third layer containing a silicon or germanium silicide and a second layer containing a metal species other than silicon or germanium.
The etching solution according to claim 10, wherein the second layer is a layer containing titanium.
The etching solution according to any one of claims 1 to 11, which is applied to a semiconductor substrate including a fourth layer containing TiAlC.
Etching method in which an etching solution containing a compound P having a plurality of adsorbing groups and a weight average molecular weight of 1000 or more or a compound P having a plurality of adsorbing groups and a steric repulsion site is applied to a semiconductor substrate.
The etching method according to claim 13, wherein the etching solution further contains at least one of a metal-dissolving component, an acid assistant having a pKa of 4 or less, an organic solvent, and water.
The etching method according to claim 13 or 14, which is applied to a semiconductor substrate having a third layer containing silicon or germanium silicide and a second layer containing a metal species other than silicon or germanium.
The etching method according to any one of claims 13 to 15, wherein the second layer is a layer containing titanium.
The etching method according to any one of claims 13 to 16, which is applied to a semiconductor substrate including a fourth layer including TiAlC.
A semiconductor substrate product manufacturing method for manufacturing a semiconductor substrate product via the etching method according to any one of claims 13 to 17.
A metal anticorrosive comprising compound P having a plurality of adsorbing groups and a weight average molecular weight of 1000 or more, or compound P having a plurality of adsorbing groups and having a steric repulsion site, or a metal anticorrosion composition containing the same.
The metal anticorrosive agent according to claim 19 or a metal anticorrosive composition containing the metal anticorrosive agent according to claim 19, which is used for an etching solution for a semiconductor process.