JP2002020787A - Detergent for copper wiring semiconductor substrate - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain a detergent capable of effectively removing impurities on the surface of a semiconductor having a copper wiring on the surface without causing corrosion and oxidation of the copper wiring and surface roughness and to provide a method for cleaning. SOLUTION: This detergent for the surface of a semiconductor having a copper wiring on the surface comprises a nonionic surfactant containing a group of formula (1) in the molecule, for example, a nonionic surfactant of general formula 7 (p+q+p'+q' is 1-20). This method for cleaning the surface of a semiconductor uses the detergent. This semiconductor having a copper wiring on the surface is obtained by treating the surface a semiconductor with the detergent.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a cleaning agent and a cleaning method for a semiconductor surface, particularly for a semiconductor surface having copper wiring on the surface.

[0002]

2. Description of the Related Art In recent years, the structure of an LSI has been miniaturized in accordance with high integration, and has a multilayer structure in which metal wirings and the like are stacked on a semiconductor surface in many stages. Further, it has been proposed to change the wiring used from conventional aluminum to copper (Cu) having lower electric resistance.

[0003] In the process of manufacturing a semiconductor having a multilayer structure in which copper wiring is provided in multiple layers on the surface, a so-called chemical-physical method in which a semiconductor substrate is physically polished and flattened while oxidizing metal Cu. Polishing technology (Cu-CMP) is used.

On the other hand, after the Cu-CMP process, the semiconductor surface
The insulating film (silicon oxide) that separates the wiring and each Cu wiring is exposed, and the wafer surface after the Cu-CMP process is contaminated with a large amount of impurity metals and particles. The impurity metal contamination is caused by Cu removed by CMP adsorbed on the insulating film and remaining as copper oxide, and the particle contamination is caused by slurry used for polishing in the CMP process.

[0005] When copper oxide remains on the insulating film as described above, copper elements diffuse into the insulating film by a heat treatment in a later step, and the insulating properties are reduced, thereby deteriorating the characteristics of the device and contaminating the device. In a remarkable case, the isolated wirings are connected to each other, that is, a short circuit is caused, so that the device is destroyed. Therefore, it is necessary to remove copper oxide before proceeding to the next step. In addition, particle contamination similarly has an adverse effect on the next process, and therefore, it is necessary to remove as much as possible.

For the above reasons, a cleaning step after the Cu-CMP step is indispensable in order to remove the impurities and particles as described above.

[0007] In the cleaning process after the Cu-CMP process, conventionally,
When an acidic cleaning liquid (hydrochloric acid, hydrofluoric acid, or the like) that is generally used as a cleaning liquid for a semiconductor is used, not only copper oxide adhering to the insulating film but also metal copper of the wiring is dissolved, resulting in corrosion of the wiring. The use of the acidic cleaning solution is not preferable because it causes disconnection or disconnection. Furthermore, when an acidic solution is used, the semiconductor surface and the particles are attracted electrostatically,
There is a problem that not only particles cannot be removed but also reverse adsorption is caused. An alkaline cleaning solution that electrostatically repels the semiconductor surface and the particles is generally considered to be effective in removing the particles. However, sodium hydroxide or potassium hydroxide containing metal ions as an alkali source is used. When such a cleaning liquid is used, these metals are adsorbed on the surface of the insulating film (silicon oxide) and deteriorate the insulating characteristics. Further, among the alkaline cleaning liquids, a cleaning liquid of an inorganic alkali (aqueous ammonia or the like) containing no metal ion has a strong copper dissolving power and cannot be used.

On the other hand, a cleaning solution containing quaternary ammonium
Although it has the advantage of not corroding the copper wiring and having a high particle removal effect, quaternary ammonium is strongly alkaline, so it has a strong etching power on the insulating film and roughens the surface planarized by the CMP process. There is a disadvantage that. By adding hydrogen peroxide to quaternary ammonium to eliminate such disadvantages,
It is known that the etching rate can be reduced. However, in this case, there is a problem that the surface of the copper wiring is oxidized by the oxidizing power of hydrogen peroxide, and the conductivity is deteriorated.

As described above, the semiconductor substrate provided with the copper wiring is
Until now, there has been no cleaning solution capable of removing surface impurities without causing corrosion or oxidation of copper wiring and without causing surface roughness.

[0010]

SUMMARY OF THE INVENTION The present invention has been made in view of the above-mentioned circumstances, and has been developed in order to prevent the corrosion and oxidation of copper wiring on a semiconductor surface, especially a semiconductor surface having copper wiring on the surface. Another object of the present invention is to provide a cleaning agent and a cleaning method capable of effectively removing impurities on the surface without causing surface roughness.

[0011]

The present invention has the following constitution.

(1) A cleaning agent for a semiconductor surface having a copper wiring on the surface, comprising a nonionic surfactant.

(2) Cleaning a semiconductor surface having a copper wiring provided thereon, the semiconductor surface having a copper wiring provided thereon is treated with a cleaning agent containing a nonionic surfactant. Method.

(3) A semiconductor provided with copper wiring on the surface, obtained by treating the surface of the semiconductor having copper wiring on the surface with a cleaning agent containing a nonionic surfactant.

The present inventors have conducted intensive studies to achieve the above object. As a result, the semiconductor surface on which the copper wiring has been formed is cleaned by using a cleaning agent containing a nonionic surfactant. It can control the etching rate of the film and effectively remove impurities such as copper oxide and particles adsorbed on the insulating film and copper wiring without causing corrosion or oxidation of the copper wiring and without causing surface roughness. This effect can be further improved by using a nonionic surfactant in the molecule.

[0016]

Embedded image

Particularly preferred are those having an acetylene group represented by the following formula, and such a surfactant is used together with a nitrogen-containing alkaline compound such as ammonia, primary to tertiary amine or quaternary ammonium, especially quaternary ammonium. It has been found that the effect is further promoted by the combined use of, and the present invention has been completed based on these series of findings.

As the nonionic surfactant in the present invention, any of the conventionally known nonionic surfactants can be used.

[0019]

Embedded image

A compound having a group (acetylene group) represented by

[0021]

Embedded image

Those having a group represented by the formula (acetylene group) and a polyoxyalkylene group are preferred.

Examples of the polyoxyalkylene group include those represented by the following general formula [1].

[0024]

Embedded image

(Wherein, X represents an alkylene group and y represents a positive integer).

In the general formula [1], the alkylene group represented by X is preferably, for example, a linear, branched or cyclic lower alkylene group having 1 to 6 carbon atoms, for example, a methylene group, an ethylene group , Propylene group, butylene group,
Examples include a methylmethylene group, an ethylethylene group, a methylethylene group, a methylpropylene group, an ethylpropylene group, a pentylene group, a hexylene group, a cyclopentylene group, and a cyclohexylene group. Particularly preferred. Further, y represents a positive integer and is usually 1 to 10, preferably 1 to 8. Among them, those having y of 2 to 8 have low air bubbles and foam even when used in combination with physical cleaning. It is particularly preferable because it is suppressed and troubles due to bubbles hardly occur. The y oxyalkylene groups may be all the same, or may be two or more. In the general formula [1],-(X-
Among the oxyalkylene groups represented by O)-, for example, an oxyethylene group, an oxypropylene group and the like are preferable, and the polyoxyalkylene group represented by-(X-O) y- is composed of, for example, only an oxyethylene group And those composed only of oxypropylene groups, those composed of a combination of oxyethylene groups and oxypropylene groups, and the like are particularly preferred. In the case of a combination of an oxyethylene group and an oxypropylene group, the ratio of the two is usually 50% or more, preferably 70% or more.

As described above, in the molecule:

[0028]

Embedded image

Specific examples of the nonionic surfactant having the group represented by the general formula [1] and the polyoxyalkylene group represented by the general formula [1] include those represented by the following general formula [2]. .

[0030]

Embedded image

[Where X is₁Represents a lower alkylene group,
n represents a positive integer;₁And R_TwoAre independent hydrogen sources
Represents a hydroxyl group, a hydroxyl group, an alkyl group or a hydroxyalkyl group.
Then R _FiveRepresents a hydrogen atom, a hydroxyl group, an alkyl group,
It represents an alkyl group or a group represented by the following general formula [3].

[0032]

Embedded image

(In the formula, R ₃ and R ₄ each independently represent a hydrogen atom, a hydroxyl group, an alkyl group or a hydroxyalkyl group, X ₂ represents a lower alkylene group, and m represents a positive integer.)

In the above general formulas [2] and [3], X ₁
And the lower alkylene group represented by X ₂ is the same as X in the general formula [1] as described above. Also, m and n
Is also the same as y in the general formula [1] as described above. When R ₅ in the general formula [2] is the general formula [3], the sum of m and n is usually 2 to 20, preferably 2 to 16, and especially 4 to 16. Is particularly preferable since it has low bubble properties, suppresses foaming even when used in combination with physical cleaning, and hardly causes troubles due to foaming.

Among the nonionic surfactants represented by the general formula [2], those in which X ₁ and X ₂ are ethylene groups and / or propylene groups are preferred. Preferred examples thereof include those represented by the following general formula [2 ′].

[0036]

Embedded image

[Wherein R ₁ and R ₂ are the same as described above;
r and s each independently represent 0 or a positive integer, and R _{5 ′} represents a hydrogen atom, a hydroxyl group, an alkyl group, a hydroxyalkyl group or a group represented by the following general formula [3 ′].

[0038]

Embedded image

(Wherein R ₃ and R ₄ are the same as described above;
r ′ and s ′ each independently represent 0 or a positive integer. ) Except that r, s, r 'and s' are simultaneously 0. ]

Among them, those in which the group represented by R _{5 ′} in the general formula [2 ′] is the general formula [3 ′], that is, those represented by the following general formula [2 ″] are particularly preferable. .

[0041]

Embedded image

(Wherein R ₁ , R ₂ , R ₃ , R ₄ , R ₅ , r,
r ', s and s' are the same as above. )

In the general formulas [2 '] and [2 "],

[0044]

Embedded image

The compound consisting of r blocks of oxyethylene groups and s blocks of oxypropylene groups (a so-called block copolymer) and oxyethylene groups and oxypropylene groups bonded in no particular order, Is r and the total number of the latter is s (so-called random copolymer). In the above general formulas [3 ′] and [2 ″]

[0046]

Embedded image

The same applies to the case.

The nonionic surfactant according to the present invention can be easily prepared by a method known per se. That is, for example, to prepare a compound in which the group represented by R ₅ in the general formula [2] is the general formula [3], for example, US Pat. No. 3,291,607
And a glycol compound represented by the following general formula [2-1]:

[0049]

Embedded image

(Wherein, R _{1 to} R ₄ are the same as described above). An alkylene oxide corresponding to the following general formula [2-2] or / and [3-1] may be reacted.

[0051]

Embedded image

And

[0053]

Embedded image

(Wherein X ₁ , X ₂ , n and m are the same as described above)

The above formulas [2], [3], [2 '], [3']
And [2 ″], the alkyl group represented by R _{1 to} R ₅ and R _{5 ′} may be saturated or unsaturated, and may have a linear or
Branched or cyclic C 1-10, preferably 1-C
6, more preferably 1-3. Specifically, for example, methyl group, ethyl group, n-propyl group, n-butyl group, n-pentyl group, n-hexyl group, n-octyl group, n-nonyl group,
Saturated linear alkyl group such as n-decanyl group, for example, iso-propyl group, iso-butyl group, sec-butyl group, tert-butyl group, iso-pentyl group, sec-pentyl group, tert-pentyl group, neopentyl group , Iso-hexyl group, sec-hexyl group, saturated branched alkyl group such as tert-hexyl group, for example, cyclopentyl group, cyclic alkyl group such as cyclohexyl group, for example, vinyl group, n-propenyl group, n-butenyl group and the like Unsaturated linear alkyl groups such as iso-propenyl group, is
and unsaturated branched alkyl groups such as o-butenyl group, sec-butenyl group, tert-butenyl group and the like. Examples of the hydroxyalkyl group include those in which one or more, preferably 1 to 3, and more preferably only the terminal hydrogen atom of any hydrogen atom of these alkyl groups has been substituted with a hydroxyl group.

The sum of r, s, r 'and s' is usually 1
-20, preferably 1-16, and especially 4-16 are particularly preferable since they have low air bubble properties, suppress foaming even when used in combination with physical cleaning, and hardly cause troubles due to foaming. Among them, those in which s and s ′ are each independently 0 to 2, and r and r ′ are each independently 4 to 6 are more preferable.

Specific examples of the nonionic surfactant having an acetylene group in the molecule in the present invention include, for example, diisobutyldimethylbutynediol polyoxyethylene glycol ether (1,2) represented by the following general formula [6]:
4-diisobutyl-1,4-dimethylbut-2-yn diol polyoxyethy
lene glycol ether)

[0058]

Embedded image

[Wherein the total number of p and p ′ (p + p ′) is usually 1 to 20, preferably 1 to 16, more preferably 4 to
Sixteen. ],

For example, diisobutyldimethylbutynediol polyoxyethylene / polyoxypropylene glycol ether (1,4-diisobutane) represented by the following general formula [7]:
yl-1,4-dimethylbut-2-yn diol polyoxyethylene-polyo
xypropylene glycol ether)

[0061]

Embedded image

[Wherein the total number of p, q, p ′ and q ′ (p +
q + p ′ + q ′) is usually 1 to 20, preferably 1 to 1
6, more preferably 4-16. ],

For example, diisobutyldimethylbutynediol polyoxypropylene glycol ether (1,4-diisobutyl-1,4-dimethylbut-2) represented by the following general formula [8]
-yn diol polyoxypropylene glycol ether)

[0064]

Embedded image

[Wherein the total number of q and q ′ (q + q ′) is usually 1 to 20, preferably 1 to 16, more preferably 4 to
Sixteen. And the like.

The nonionic surfactant used in the present invention may be one prepared by the method described above or a commercial product. The nonionic surfactants as described above may be used alone or in combination of two or more.

The amount of the nonionic surfactant used may be at least the critical micelle concentration, and if it is less than that, the etching rate is increased and the effect is reduced. The specific amount cannot be specified unconditionally because it differs depending on the type of the surfactant, but it is, for example, usually 1 ppm or more, and there is no particular upper limit. However, in consideration of economy and the like, the content is preferably from 1 to 10,000 ppm, more preferably from 10 to 1000 ppm.

Examples of the ammonia and primary to tertiary amines in the present invention include those represented by the following general formula [4].

[0069]

Embedded image

(Wherein, R ₁₁ , R ₁₂ and R ₁₃ each independently represent a hydrogen atom, a lower alkyl group, or a hydroxy lower alkyl group.)

The lower alkyl group represented by R _{11 to} R ₁₃ in the general formula [4] includes, for example, a linear, branched or cyclic one having 1 to 6 carbon atoms. Is, for example, methyl group, ethyl group, n-propyl group, iso-propyl group, n-butyl group, iso-butyl group, sec-butyl group,
tert-butyl group, n-pentyl group, iso-pentyl group, sec-
Examples include a pentyl group, a tert-pentyl group, a neopentyl group, an n-hexyl group, an iso-hexyl group, a sec-hexyl group, a tert-hexyl group, a cyclopentyl group, and a cyclohexyl group. In the general formula [4], the hydroxy lower alkyl group represented by R _{11 to} R ₁₃ may be one or more of any hydrogen atoms of the lower alkyl group as described above, preferably a terminal hydrogen atom is a hydroxyl group. And specifically, for example, a hydroxymethyl group,
Hydroxyethyl group, 3-hydroxy-n-propyl group, 4-
Hydroxy-n-butyl group, 1-methyl-2-hydroxyethyl group, 2-methyl-3-hydroxypropyl group, 1,1-dimethyl-
And a 2-hydroxyethyl group.

Specific examples of the compound represented by the general formula [4] include, for example, ammonia, for example, primary amines such as methylamine, ethylamine, n-propylamine, and n-butylamine, for example, dimethylamine, diethylamine, methylethylamine, and di-amine. Secondary amines such as n-propylamine and di-n-butylamine, for example, tertiary amines such as trimethylamine, triethylamine, methyldiethylamine, tri-n-propylamine, and tri-n-butylamine, for example, primary hydroxyls such as monoethanolamine Examples of the amine include secondary hydroxylamines such as diethanolamine, and tertiary hydroxyamines such as triethanolamine.

Examples of the quaternary ammonium in the present invention include those represented by the following general formula [5].

[0074]

Embedded image

(In the formula, R _{6 to} R ₉ each independently represent a hydrocarbon residue which may have a hydroxyl group, and M ⁻ represents an anion.)

In the general formula [5], the hydrocarbon residue of the hydrocarbon residue represented by R _{6 to} R ₉ which may have a hydroxyl group is aliphatic, aromatic, araliphatic, or Any of alicyclic groups may be used, and the aliphatic group in the aliphatic group and the araliphatic group may be saturated or unsaturated, and may be linear or branched. Representative examples of these include linear, branched, or cyclic saturated or unsaturated alkyl, aralkyl, and aryl groups. As the alkyl group, a lower alkyl group having 1 to 6 carbon atoms, particularly a lower alkyl group having 1 to 4 carbon atoms is preferable, and specifically, for example, a methyl group, an ethyl group, an n-propyl group, an iso-propyl Group, n-butyl group, iso-butyl group,
sec-butyl, tert-butyl, n-pentyl, iso-pentyl, sec-pentyl, tert-pentyl, neopentyl, n-hexyl, iso-hexyl, sec-hexyl, tert-butyl Hexyl group, cyclopentyl group, cyclohexyl group, vinyl group, n-propenyl group, iso-propenyl group, n-butenyl group, iso-butenyl group, sec-butenyl group,
tert-butenyl group and the like. Examples of the aralkyl group include those having usually 7 to 12 carbon atoms, and specifically, for example, benzyl group, phenethyl group, phenylpropyl group, phenylbutyl group, phenylhexyl group, methylbenzyl group, methylphenethyl group, ethyl And a benzyl group. The aryl group usually has 6 to 1 carbon atoms.
4, specifically, for example, a phenyl group,
o-tolyl group, m-tolyl group, p-tolyl group, 2,3-
Xylyl, 2,4-xylyl, 2,5-xylyl, 2,6-xylyl, 3,5-xylyl, naphthyl, anthryl and the like. The aromatic ring of the aryl group or the aralkyl group as described above may have, for example, a lower alkyl group such as a methyl group or an ethyl group, a halogen atom, a nitro group, an amino group, or the like as a substituent.
Examples of the hydrocarbon residue having a hydroxyl group include those in which a hydrogen atom of the above-described hydrocarbon residue is substituted with a hydroxyl group. In the general formula [5], examples of the anion represented by M ⁻ include OH ^{− and the} like.

Specific examples of the quaternary ammonium as described above include the following. Tetramethyl ammonium hydroxide (TMAH), trimethyl-2-hydroxyethyl ammonium hydroxide (choline), tetraethyl ammonium hydroxide, tetrapropyl ammonium hydroxide, tetrabutyl ammonium hydroxide, monomethyl triethyl ammonium hydroxide, dimethyl diethyl ammonium hydroxide , Trimethyl monoethyl ammonium hydroxide, monomethyl tripropyl ammonium hydroxide, dimethyl dipropyl ammonium hydroxide, trimethyl monopropyl ammonium hydroxide, monomethyl tributyl ammonium hydroxide, dimethyl dibutyl ammonium hydroxide, trimethyl monobutyl ammonium hydroxide, hydroxide Monoethyltripropylammonium, diethyldipropylammonium hydroxide, triethylmonopropylammonium hydroxide Monoethyltributylammonium hydroxide, diethyldibutylammonium hydroxide, triethylmonobutylammonium hydroxide, monopropyltributylammonium hydroxide, dipropyldibutylammonium hydroxide, tripropylmonobutylammonium hydroxide, triethyl-2-hydroxyethyl hydroxide Ammonium, tripropyl-2-hydroxyethylammonium hydroxide, tributyl-2-hydroxyethylammonium hydroxide, trimethyl-3-hydroxypropylammonium hydroxide, triethyl-3-hydroxypropylammonium hydroxide, tripropyl-3-hydroxide Hydroxypropyl ammonium, tributyl-3-hydroxypropylammonium hydroxide, trimethyl-4-hydroxybutylammonium hydroxide, triethyl-4-hydroxybutyrate Ammonium, tripropyl-4-hydroxybutylammonium hydroxide, tributyl-4-hydroxybutylammonium hydroxide, trimethyl-3-hydroxybutylammonium hydroxide, triethyl-3-hydroxybutylammonium hydroxide, tripropyl-3 hydroxide -Hydroxybutylammonium, tributyl-3-hydroxybutylammonium hydroxide, dimethylethyl-2-hydroxyethylammonium hydroxide, methyldiethyl-2-hydroxyethylammonium hydroxide, dimethylethyl-3hydroxide
-Hydroxypropylammonium, methyldiethyl-3-hydroxypropylammonium hydroxide, dimethylethyl-4-hydroxybutylammonium hydroxide, methyldiethyl-4-hydroxybutylammonium hydroxide, dimethylethyl-3-hydroxybutylammonium hydroxide, water Methyl diethyl-3-hydroxybutyl ammonium oxide, dimethyl di (2-hydroxyethyl) ammonium hydroxide, dimethyl di (3-hydroxypropyl) ammonium hydroxide, dimethyl di (3-hydroxybutyl) ammonium hydroxide, dimethyl di (4-hydroxy Butyl) ammonium, diethyldi (2-hydroxyethyl) ammonium hydroxide, diethyldi (3-hydroxypropyl) ammonium hydroxide, diethyldi (3-hydroxybutyl) ammonium hydroxide, diethyldi (4-hydroxyhydroxide) (Butyl) ammonium, methylethyldi (2-hydroxyethyl) ammonium hydroxide, methylethyldi (3-hydroxypropyl) ammonium hydroxide, diethyldi (3-hydroxybutyl) ammonium hydroxide, methylethyldi (4-hydroxybutyl) ammonium hydroxide, hydroxide Methyl tri (2-hydroxyethyl) ammonium, ethyl tri (2-hydroxyethyl) ammonium hydroxide, propyl tri (2-hydroxyethyl) ammonium hydroxide, butyl tri (2-hydroxyethyl) ammonium hydroxide, methyl tri (3-hydroxyethyl) hydroxide Propyl) ammonium, ethyl hydroxide tri (3-
Hydroxybutyl) ammonium hydroxide
Hydroxybutyl) ammonium, ethyl hydroxide tri (4-
Hydroxybutyl) ammonium hydroxide
Hydroxybutyl) ammonium, ethyl hydroxide tri (3-
Hydroxybutyl) ammonium. Among them, tetramethylammonium hydroxide (TMAH), trimethyl-2-hydroxyethylammonium hydroxide (choline) and the like are particularly preferable.

The compound represented by the general formula [4] or the quaternary ammonium represented by the general formula [5] may be used alone or in combination of two or more.

The amount of the compound represented by the general formula [4] or the quaternary ammonium represented by the general formula [5] to be used in the present invention varies depending on the kind, and cannot be specified unconditionally. In this case, the etching rate is slowed down, and the effect is reduced. For example, the etching rate is usually 0.003% (w / v) or more. Although there is no particular upper limit, it is preferably 0.003 to 10% (w / v), more preferably 0.
01 to 6% (w / v), more preferably 0.05 to 1% (w / v).

(1) Preferred embodiments of the cleaning agent of the present invention include, for example, the following. (a) As the nitrogen-containing alkaline compound, ammonia represented by the general formula [4], a primary to tertiary amine or a quaternary ammonium represented by the general formula [5]

[0081]

Embedded image

(Wherein R ₆ , R ₇ , R ₈ , R ₉ , R ₁₁ ,
R ₁₂ , R ₁₃ and M ⁻ are the same as above. ), (B) a nonionic surfactant represented by the general formula [2]:

[0083]

Embedded image

(Wherein R ₁ , R ₂ , R ₅ , X ₁ and n are the same as described above), a semiconductor cleaning agent as a main component.

(2) More preferred embodiments of the cleaning agent of the present invention are as follows, for example. (a ′) a quaternary ammonium represented by the general formula [5]:

[0086]

Embedded image

(Wherein R ₆ , R ₇ , R ₈ , R ₉ and M ⁻ are the same as described above), (b ′) a nonionic surfactant represented by the general formula [2 ′]

[0088]

Embedded image

(Wherein R ₁ , R ₂ , R _{5 ′} , r and s are the same as described above), a semiconductor cleaning agent as a main component.

(3) More preferred embodiments of the cleaning agent of the present invention are as follows, for example. (a '') a quaternary ammonium represented by the general formula [5 ']

[0091]

Embedded image

(Wherein R ₆ , R ₇ , R ₈ and R ₉ are the same as described above), (b ″) a nonionic surfactant represented by the general formula [2 ″]

[0093]

Embedded image

(Wherein R ₁ , R ₂ , R ₃ , R ₄ , r, s,
r 'and s' are the same as above. ), A cleaning agent for semiconductors which is a main component.

In the above embodiment, R ₁ and R _{3 in} the general formula [2 ″] are methyl groups, R ₂ and R ₄ are isobutyl groups, and in the general formula [5 ′] It is particularly preferred that all of R _{6 to} R _{9 in} the formula (I) are methyl groups, or three of them are methyl groups and the remaining one is a 2-hydroxyethyl group.

The cleaning agent of the present invention can be used not only as a cleaning agent for semiconductors but also as a cleaning agent for printed circuit boards, LCD substrates and the like. In particular, the above-described embodiment is used for cleaning semiconductor surfaces having copper wiring on the surface. Useful for

The cleaning agent of the present invention is usually in the form of an aqueous solution, and is prepared by adding and dissolving the above-mentioned nonionic surfactant or a nonionic surfactant and a nitrogen-containing alkaline compound in water. .

It is preferable that the cleaning agent of the present invention thus prepared is subjected to a filtration treatment or the like before use. In addition, the water used here may be any water that has been purified by distillation, ion exchange treatment, or the like, and so-called ultrapure water used in this field is more preferable.

The detergent of the present invention is preferably alkaline, and usually has a pH of 9 or more, preferably pH 9 to 12, more preferably pH 9.5 to 10.5. By setting the pH in such a range, the risk of etching the interlayer insulating film of SiO ₂ is further reduced, and furthermore, the electric repulsion between the semiconductor surface and the particles is increased.
The cleaning effect of O improves.

In order to adjust the pH of the cleaning agent of the present invention to the above-mentioned pH range, if necessary, p-type compounds generally used in this field may be used.
H regulators, for example, carboxylic acids such as citric acid, oxalic acid, phthalic acid, tartaric acid, derivatives thereof, or salts thereof, phosphoric acid, phosphoric acid derivatives or salts, and the like may be used.

Further, the cleaning agent of the present invention comprises p
Those having a buffering ability in the H range are particularly preferred.
In order to impart a buffering capacity to the detergent of the present invention, among the above-mentioned pH adjusting agents, those having a buffering capacity within the above-mentioned pH range alone or in combination of two or more, or It may be used in combination with a pH adjuster other than the above, and does not itself have a buffering ability, but can provide a buffering ability to the detergent of the present invention by using two or more kinds in combination, or A cleaning agent of the present invention that can impart buffering ability by using in combination with a nitrogen-containing alkaline compound may be used. It should be noted that, in the case where the detergent of the present invention can impart a buffering ability only with the above-described nitrogen-containing alkaline compound, it is needless to say that a pH adjuster need not be particularly used.

The amount of use of these pH adjusters cannot be unconditionally determined because they vary depending on the type of pH adjuster used, but when added to the cleaning agent of the present invention, the pH of the cleaning agent is as described above. Any amount that falls within the range may be used,
For example, it is usually 0.0001 to 10% (w / v), preferably 0.001 to 1% (w / v) of the total amount of the detergent.

Further, a chelating agent having no ability to dissolve copper wiring may be added to the cleaning agent of the present invention. By adding such a chelating agent, copper oxide dispersed in the liquid can be solubilized and re-adsorption can be suppressed, and impurities such as Fe and Al, which are slurry-derived impurities in the CMP step, can be removed from the surface. It can also be removed. Examples of such chelating agents having no ability to dissolve copper wiring include ethylenediaminetetraacetic acid (EDTA) and trans-1,2-diaminocyclohexane-N, N, N ', N'-tetraacetic acid (CyDTA). And carboxylic acids such as nitrilotriacetic acid (NTA), and phosphonic acids such as ethylenediaminetetrakis (methylenephosphonic acid) (EDTPO). The amount of these chelating agents used is different depending on the type of chelating agent used, but cannot be specified unconditionally, but when added to the cleaning agent of the present invention, such a cleaning agent can exert the above-described effects. Any amount, for example, usually 0.0001 to 1% of the total amount of the detergent.
(W / v), preferably 0.001 to 0.1% (w / v).

Further, in order to suppress the separation of the nonionic surfactant and the nitrogen-containing alkaline compound as described above, a small amount, for example, usually 0.01 to 5% (w /
v), preferably 0.1 to 1% (w / v) of an organic solvent may be added. Examples of the organic solvent include methanol, ethanol, isopropyl alcohol, acetone, and the like.

In the cleaning agent of the present invention, in addition to the above-mentioned nonionic surfactant, nitrogen-containing alkaline compound, pH adjuster, chelating agent and organic solvent, reagents usually used in this field are used. Can be. Such reagents are used, for example, to protect Cu in wiring and to prevent corrosion of Cu, for example, hydrazine or a derivative thereof,
Ascorbic acid, formic acid, reducing agents such as formalin, for example, benzotriazole or its derivatives, metal corrosion inhibitors such as thioureas, etc., are used for the purpose of improving the wettability of the cleaning agent on the semiconductor surface and improving the cleaning effect. And surfactants other than nonionic surfactants (for example, anionic surfactants such as dodecylbenzenesulfonic acid, cationic surfactants such as alkyltrimethylammonium, and amphoteric surfactants such as carboxybetaine).

These reagents may be used in a concentration range usually used in this field. For example, the amount of reducing agent used is
Any amount that can prevent oxidation of metal Cu may be used, and is usually 0.01 to
It is 5% by weight, preferably 0.05-1% by weight. In addition, the amount of metal corrosion inhibitor used forms a weak bond with metal Cu,
Any amount can be used as long as it can suppress the dissolving power of the detergent with respect to Cu, and is usually 0.01 to 5% by weight, preferably 0.05 to 1% by weight. The amount of the surfactant other than the nonionic surfactant used is Any amount that can lower the surface tension of the agent may be used,
Usually, it is 0.0001 to 1% by weight, preferably 0.001 to 0.1% by weight.

In the cleaning method of the present invention, the semiconductor surface having Cu wiring on the surface may be treated with the cleaning agent of the present invention as described above.

The method of treating the semiconductor surface having Cu wiring on the surface with the cleaning agent of the present invention may be any method known in the art for cleaning a semiconductor surface known per se. Examples of the method include a dip process in which a semiconductor is simply immersed in a cleaning agent, and a single-wafer process in which a cleaning agent is sprinkled on a semiconductor in a shower.

Furthermore, in the present invention, CuO can be more effectively removed by using physical cleaning at the same time as cleaning. As a specific method of combined use, Cu
Subjecting the semiconductor surface on which the wiring has been provided to a physical cleaning step in the presence of the cleaning agent of the present invention.

In the above method, the method of causing the cleaning agent of the present invention to exist is, specifically, a physical condition wherein the cleaning agent of the present invention is present by the above-described dip treatment, single-wafer treatment, or the like. Examples include a method of performing a washing step.
Examples of the physical cleaning (step) include brush scrub cleaning for cleaning the semiconductor surface using a high-speed rotating polyvinyl alcohol brush or the like, megasonic cleaning using high frequency, and the like.

As a more specific method when physical cleaning is used in combination, for example, a condition in which a semiconductor is immersed in the cleaning agent of the present invention, taken out of the cleaning solution, and the cleaning agent is present on the surface of the semiconductor. After the method of performing physical cleaning, the method of performing physical cleaning while immersing the semiconductor in the cleaning agent of the present invention, sprinkling the cleaning agent of the present invention on the semiconductor surface and allowing the cleaning agent to exist on the semiconductor surface Physical cleaning, or a method of performing physical cleaning while sprinkling the cleaning agent of the present invention on the semiconductor surface.

When the cleaning agent of the present invention containing a nonionic surfactant is used, it protects the copper wiring and prevents particles derived from the slurry floating in the cleaning liquid and scum of the slightly etched insulating film. The effect is achieved.
In particular, when the cleaning agent of the present invention containing a quaternary ammonium and a nonionic surfactant is used, the etching of the insulating film by the quaternary ammonium can be reduced, and particles can be removed without corroding the copper wiring. The advantage of quaternary ammonium, which has a high removal effect, can be used, so that the etching of the insulating film is minimized and the surface is not roughened. In addition, the re-adsorption of the peeled copper oxide is effectively prevented.

Further, in the case of cationic, anionic or amphoteric ionic surfactants, a slurry derived from a slurry which electrically binds to the semiconductor surface to prevent washing or which is originally alkaline and electrically repels the semiconductor surface. In some cases, the surface charge of the particles is changed, causing the particles to be re-adsorbed.

As described above, nonionic surfactants, particularly nonionic surfactants having an acetylene group in the molecule, and nitrogen-containing alkaline compounds such as ammonia, primary to tertiary amines or quaternary ammoniums ,
In particular, if the semiconductor surface provided with copper wiring is cleaned with a cleaning liquid containing both quaternary ammonium, the copper wiring is not adsorbed or oxidized, and is adsorbed on the surface without causing surface roughness. The effect that impurities can be removed and the cleanliness of the surface can be improved is particularly prominent.

As described above, the cleaning agent of the present invention is extremely useful for cleaning a semiconductor surface having copper wiring on its surface. However, the cleaning agent is not limited to copper wiring, but may be, for example, aluminum wiring or tungsten wiring. The present invention can also be used for cleaning a semiconductor surface provided with wiring other than copper such as a plug on the surface. Furthermore, the cleaning agent of the present invention can be used for cleaning not only the surface of a semiconductor, but also the surface of a printed circuit board, an LCD substrate and the like.

Examples and comparative examples will be shown below, but the present invention is not limited by these.

Incidentally, the nonionic surfactant used in the following examples can be synthesized by reacting the corresponding glycol compound with an alkylene oxide according to the method described in US Pat. No. 3,291,607.

The thermally oxidized film wafer, the metal-contaminated wafer, the copper-deposited wafer, the particle-contaminated thermal-oxide film wafer and the particle-contaminated copper-deposited wafer used in this example and the comparative example were prepared by the following methods, respectively. The thickness of the oxide film of the thermal oxide film wafer, the film thickness of copper on the surface of the copper deposition wafer, and the amount of copper atoms adsorbed on the surface of the metal-contaminated wafer (residual copper concentration)
And the number of particles were measured by the following methods, respectively.

[Thermal Oxide Film Wafer] A 4-inch silicon wafer is treated with a 1% hydrofluoric acid aqueous solution to remove a natural oxide film on the surface, and then heat-treated at 800 ° C. to form a thermal oxide film (silicon oxide) on the wafer surface. , Insulating film) was used as a thermal oxide film wafer. In addition, it was confirmed by the method described below that the thickness of the oxide film of the thermal oxide film wafer was 500 °.

[Metal Contaminated Wafer] A thermally oxidized film wafer was immersed in a nitric acid aqueous solution to which copper ions were added so as to have a concentration of 1 ppm for 1 minute, washed with ultrapure water for 10 minutes, and then washed with running water.
The spin-dried one was used as a metal-contaminated wafer. In addition, it was confirmed by the method described below that 3 × 10 ¹⁴ atoms / cm ^{2 of} copper atoms remained adsorbed on the metal-contaminated wafer.

[Copper Deposited Wafer] A copper deposited wafer was prepared by depositing metallic copper on the surface of a thermally oxidized film wafer by sputtering. The thickness of copper on the surface of the copper-deposited wafer was confirmed to be 1000 Å by the method described below.

[Particle-Contaminated Thermal Oxide Film Wafer and Particle-Contaminated Copper Deposited Wafer] Each of the thermal oxide film wafer and the copper-deposited wafer is immersed in a 3% alumina slurry aqueous solution having an average particle size of 0.2 μm for 1 minute, and is then immersed in ultrapure water for 10 minutes. After washing with running water for 1 minute, spin-dried wafers were used as particle-contaminated thermal oxide film wafers or particle-contaminated copper deposited wafers, respectively. By the method described below, about 85 particles were present on the particle-contaminated thermal oxide film wafer.
It was confirmed that about 90/4 inch wafers were adsorbed on the 0/4 inch wafer and the particle-contaminated copper deposition wafer, respectively.

[Method of Measuring Film Thickness of Oxide Film] The film thickness was measured with a film thickness meter (ellipsometer).

[Measurement Method of Copper Film Thickness] The wafer was divided in half, the cross section was observed with an electron microscope, and the copper film thickness was measured.

[Method of Measuring Copper Atomic Adsorption (Residual Copper Concentration)] Copper adsorbed on the wafer surface is dissolved and recovered with a hydrofluoric acid-nitric acid aqueous solution, and the copper concentration in the recovered liquid is measured by an atomic absorption method (graphite). Furnace atomic absorption spectrometer). The amount of copper atoms adsorbed (residual copper concentration) was determined based on the obtained measurement values.

[Method of Measuring Number of Particles] Particles remaining adsorbed on the wafer surface were measured by a surface foreign matter inspection device (particle counter).

In Examples and Comparative Examples, all percentages, ppm, and ppb, which represent concentrations, indicate weight ratios, unless otherwise specified. The water used is all ultrapure water, and copper is 0.01%.
It was used after confirming it was less than ppb.

[0128]

Example 1 Example 1 Tetramethylammonium hydroxide (TM
AH) is 1%, and represented by the following general formula [6] which is a nonionic surfactant, and has an average number of moles of oxyethylene groups [p +
p '] is 10, diisobutyldimethylbutynediol polyoxyethylene glycol ether

[0129]

Embedded image

(Hereinafter, abbreviated as surfactant 10)
Was dissolved in a cleaning agent (pH 12 or more) in which 0.03% was dissolved at 60 ° C. for 10 minutes.
Thereafter, the wafer was pulled up, rinsed with ultrapure water for 10 minutes, and spin-dried. Then, the oxide film thickness of the thermal oxide film wafer was measured in order to confirm the presence or absence of corrosion of the oxide film. The results are shown in Table 1.

Comparative Example 1 A thermal oxide film wafer was treated in the same manner as in Example 1, except that a cleaning agent (pH 12 or more) in which only 1% of TMAH was dissolved in ultrapure water was used. The oxide film thickness of the wafer was measured. Table 1 shows the results.

[0132]

[Table 1]

As apparent from Table 1, the cleaning agent of the present invention (Example 1) hardly changes the oxide film thickness of the thermal oxide film wafer, that is, adversely affects the insulating film on the semiconductor surface. It turns out that there is no. On the other hand, it can be seen that the conventional cleaning agent containing only quaternary ammonium (Comparative Example 1) significantly dissolved or etched the oxide film.

Example 2 In ultrapure water, the average number of moles of oxyethylene groups [p +] in the above general formula [6] which is a nonionic surfactant was used.
p ′] was 12 in a detergent (pH 7: neutral solution) in which 0.001% of diisobutyldimethylbutynediol polyoxyethylene glycol ether (hereinafter, abbreviated as surfactant 12) was dissolved. The metal-contaminated wafer was immersed at 60 ° C. for 10 minutes. Thereafter, the wafer was pulled up, rinsed with ultrapure water for 10 minutes, and spin-dried. Then, the amount of copper atoms adsorbed on the surface of the metal-contaminated wafer (residual copper concentration) was measured to evaluate the ability to remove impurities (copper).
Table 2 shows the results.

Comparative Example 2 A cleaning agent (pH 7: neutral solution) in which 0.001% of an anionic surfactant, sodium dodecyl sulfonate, was dissolved in ultrapure water was used. After treating the metal-contaminated wafer, the amount of copper atoms adsorbed (residual copper concentration) on the surface of the metal-contaminated wafer was measured to evaluate the ability to remove impurities (copper). The results are shown in Table 2.

Example 3 0.4% choline in ultrapure water, and diisobutyldimethyl having an average number of oxyethylene groups [p + p '] of 6 in the above general formula [6] which is a nonionic surfactant Example 2 except that a detergent (pH 12 or higher) in which 0.001% of butynediol polyoxyethylene glycol ether (hereinafter, abbreviated as surfactant 6) was dissolved was used.
After treating the metal-contaminated wafer in the same manner as described above, the amount of copper atoms adsorbed (residual copper concentration) on the surface of the metal-contaminated wafer was measured to evaluate the ability to remove impurities (copper). Table 2 shows the results
Are shown together.

Comparative Example 3 0.4% choline in ultrapure water and 0.4% dodecylbenzene sulfonic acid (manufactured by Lion Corporation) as an anionic surfactant.
After treating the metal-contaminated wafer in the same manner as in Example 2 except that a cleaning agent (pH 12 or more) in which 001% was dissolved was used, the amount of copper atoms adsorbed (residual copper concentration) on the surface of the metal-contaminated wafer was measured. The results are shown in Table 2.

Example 4 0.03% of TMAH in ultrapure water and diisobutyl dimethyl having an average number of oxyethylene groups [p + p '] of 8 in the above general formula [6], which is a nonionic surfactant, are 8 A detergent (pH 10.5) in which 0.001% of butynediol polyoxyethylene glycol ether (hereinafter, abbreviated as surfactant 8) was dissolved was sprinkled in a shower shape onto the metal-contaminated wafer produced by the above-described method. Scrub cleaning was performed with a high-speed rotating polyvinyl alcohol brush for minutes. Thereafter, the wafer was rinsed with ultrapure water for 10 minutes and spin-dried, and then the amount of copper atoms adsorbed on the surface of the metal-contaminated wafer (residual copper concentration) was measured in order to evaluate the ability to remove impurities (copper). Table 2 shows the results.

Comparative Example 4 A metal-contaminated wafer was treated in the same manner as in Example 4 except that ultrapure water was used instead of the cleaning agent, and then the amount of copper atoms adsorbed on the surface of the metal-contaminated wafer (residual copper concentration). Was measured.
The results are shown in Table 2.

[0140]

[Table 2]

As is clear from Table 2, the detergent of the present invention containing a nonionic surfactant (Example 2) has a higher metal content than the detergent containing only an anionic surfactant (Comparative Example 2). The residual copper concentration on the contaminated wafer surface can be significantly suppressed,
It can be seen that the concentration of residual copper can be suppressed even when compared with a detergent containing quaternary ammonium and an anionic surfactant (Comparative Example 3). The cleaning agent of the present invention containing a nonionic surfactant and a quaternary ammonium (Example 3) is a cleaning agent containing only an anionic surfactant (Comparative Example 2) and a quaternary ammonium and anionic surfactant. It can be seen that the concentration of residual copper on the surface of the metal-contaminated wafer can be significantly suppressed as compared with the cleaning agent containing the agent (Comparative Example 3). Furthermore, copper can be more effectively removed when chemical cleaning and physical cleaning are used together (Example 4) than when only chemical cleaning is performed (Example 3). I understand.

Example 5 In ultrapure water, 3% of TMAH was added, and diisobutyldimethyl having an average number of moles of oxyethylene groups [p + p '] of 5 in the above general formula [6], which is a nonionic surfactant, was 5. A copper-deposited wafer was treated in the same manner as in Example 5, except that a cleaning agent (pH 12 or more) in which 0.05% of butynediol polyoxyethylene glycol ether (hereinafter abbreviated as surfactant 5) was dissolved was used. After that, the copper film thickness of the copper-deposited wafer was measured. The results are shown in Table 3.

Comparative Example 5 A copper-deposited wafer was treated in the same manner as in Example 5 except that a cleaning agent (pH 10) in which 3% of diethanolamine was dissolved in ultrapure water was used. The thickness was measured. The results are shown in Table 3.

[0144]

[Table 3]

As is clear from Table 3, the cleaning agent of the present invention, which contains a nonionic surfactant and quaternary ammonium (Example 5), has almost no effect on the copper film thickness on the surface of the copper volume wafer. , It is understood that copper is not dissolved or etched. On the other hand, it can be seen that the detergent containing the secondary amine but not containing the nonionic surfactant (Comparative Example 5) significantly dissolved or etched copper.

Example 6 TMAH in ultrapure water was represented by 0003%, and a nonionic surfactant represented by the following general formula [7], wherein the average number of moles of oxyethylene groups [p + p '] was 6, Diisobutyldimethylbutynediol polyoxypropylene-polyoxyethylene glycol ether having an average number of moles [q + q ′] of oxypropylene groups of 2

[0147]

Embedded image

(Hereinafter, abbreviated as surfactant 6-2.) A particle-contaminated thermal oxide film wafer and a particle-contaminated copper-deposited wafer prepared by the above method were washed with a detergent (pH 9) in which 0.03% was dissolved. Immersion at 60 ° C. for 10 minutes. Then, lift the wafer, rinse it with ultrapure water for 10 minutes, spin dry, and evaluate the ability to remove impurities (particles).
The particle numbers of the particle-contaminated thermal oxide film wafer and the particle-contaminated copper deposited wafer were measured. Table 4 shows the results.

Comparative Example 6 The same procedure as in Example 6 was carried out except that a cleaning agent (pH 9) containing 0.003% of TMAH and 0.03% of stearyldimethylammonium chloride as a cationic surfactant was dissolved in ultrapure water. After treating the particle-contaminated thermal oxide film wafer and the particle-contaminated copper deposited wafer by the method, the particle numbers of the particle-contaminated thermal oxide film wafer and the particle-contaminated copper deposited wafer were measured. The results are shown in Table 4.

[0150]

[Table 4]

As is clear from Table 4, the cleaning agent of the present invention containing a nonionic surfactant and a quaternary ammonium (Example 6) has a reduced number of particles adsorbed on the surface of the thermally oxidized film wafer. 30, the number of particles adsorbed on the surface of the copper-deposited wafer was 5, indicating that the particle removal effect was remarkably high in each case. On the other hand, the cleaning agent containing the cationic surfactant and the quaternary ammonium (Comparative Example 6) had 1200 particles adsorbed and remained on the thermally oxidized film wafer surface and 202 particles adsorbed and remained on the copper deposited wafer surface. It can be seen that the particle removal effect is low in each case.

Example 7 A solution of 3% ammonia in ultrapure water and diisobutyldimethyl having an average number of moles of oxyethylene groups [p + p '] of 4 in the above general formula [6] which is a nonionic surfactant The copper-deposited wafer prepared by the above method was immersed in a detergent (pH 11) in which 0.05% of butynediol polyoxyethylene glycol ether was dissolved at room temperature (25 ° C.) for 30 minutes. Thereafter, the wafer was lifted, rinsed with ultrapure water for 10 minutes, and spin-dried.

Example 8 Diethanolamine in ultrapure water at 3% and diisobutyl having a nonionic surfactant represented by the following general formula [8] and having an average number of moles [q + q '] of oxypropylene groups of 4 were 4: Dimethylbutyne diol polyoxypropylene glycol ether

[0154]

Embedded image

A copper-deposited wafer was treated in the same manner as in Example 7, except that a cleaning agent (pH 10) in which 0.05% was dissolved was used.

[0156]

As described above, the present invention can remove impurities adsorbed on the surface of the semiconductor on which the copper wiring has been formed, and can prevent the copper wiring from being corroded and oxidized, and without causing surface roughness.
An object of the present invention is to provide a method capable of cleaning a semiconductor surface. By using the cleaning liquid of the present invention, it is possible to solve various problems in semiconductor production.

──────────────────────────────────────────────────続 き Continued on the front page (51) Int.Cl. ⁷ Identification symbol FI Theme coat ゛ (Reference) H01L 21/304 647 H01L 21/304 647B 21/306 21/306 MF Term (Reference) 4H003 AC07 AC10 AC21 AC23 BA12 DA09 DA15 EB13 EB14 EB19 ED02 FA15 FA21 FA28 5F043 AA26 BB18 DD16 DD19 DD30 GG03

Claims (36)

[Claims] 1. A cleaning agent for a semiconductor surface having a copper wiring on the surface, comprising a nonionic surfactant. 2. A nonionic surfactant having the following formula: The cleaning agent according to claim 1, which has a group represented by the formula: 3. A nonionic surfactant having the following formula: The cleaning agent according to claim 1, which has a group represented by the formula and a polyoxyalkylene group. 4. The cleaning agent according to claim 3, wherein the polyoxyalkylene group is represented by the following general formula [1]. Embedded image (In the formula, X represents an alkylene group, and y represents a positive integer.) 5. The cleaning agent according to claim 3, wherein the polyoxyalkylene group is a polyoxyethylene group and / or a polyoxypropylene group. 6. A nonionic surfactant represented by the following general formula:
The cleaning agent according to claim 1, which is represented by [2]. Embedded image[Where X₁Represents a lower alkylene group, and n is a positive integer
And R₁And R_TwoAre each independently a hydrogen atom, a hydroxyl group,
An alkyl group or a hydroxyalkyl group; _FiveIs water
A hydrogen atom, a hydroxyl group, an alkyl group, a hydroxyalkyl group or
Represents a group represented by the following general formula [3]. Embedded image(Where R_ThreeAnd R_FourAre each independently a hydrogen atom, a hydroxyl group,
X represents an alkyl group or a hydroxyalkyl group;_TwoIs low
And m represents a positive integer. )] 7. In the general formula [2], R ₅ is a group represented by the general formula [3], and n X ₁ and m X ₂ are each independently an ethylene group or a propylene group. The cleaning agent according to claim 6, which is: 8. The cleaning agent according to claim 1, wherein the nonionic surfactant is represented by the following general formula [2 ']. Embedded image Wherein R ₁ and R ₂ are each independently a hydrogen atom, a hydroxyl group,
Represents an alkyl group or a hydroxyalkyl group, and r and s
Each independently represents 0 or a positive integer, and R _{5 ′} represents a hydrogen atom, a hydroxyl group, an alkyl group, a hydroxyalkyl group or a group represented by the following general formula [3 ′]. Embedded image (Wherein R ₃ and R ₄ are each independently a hydrogen atom, a hydroxyl group,
Represents an alkyl group or a hydroxyalkyl group, and r ′ and s ′ each independently represent 0 or a positive integer. )
Except when r, s, r 'and s' are simultaneously 0. ] 9. The cleaning agent according to claim 1, wherein the nonionic surfactant is represented by the following general formula [2 ″]. Embedded image (In the formula, R ₁ , R ₂ , R ₃ , R ₄ , r, r ′, s and s ′ are the same as described above.) 10. The cleaning agent according to claim 1, wherein the nonionic surfactant is selected from compounds represented by the following general formulas [6], [7] or [8]. Embedded image (Where p + p ′ is 1 to 20). (In the formula, p + q + p ′ + q ′ is 1 to 20.) (In the formula, q + q ′ is 1 to 20.) 11. The cleaning agent according to claim 1, which is alkaline. 12. The cleaning agent according to claim 1, further comprising a nitrogen-containing alkaline compound. 13. The nitrogen-containing alkaline compound is ammonia,
The cleaning agent according to claim 12, which is selected from a primary amine, a secondary amine, a tertiary amine, and a quaternary ammonium. 14. A quaternary ammonium represented by the following general formula [5]:
The cleaning agent according to claim 13, which is a quaternary ammonium represented by the formula: Embedded image (In the formula, R _{6 to} R ₉ each independently represent a hydrocarbon residue which may have a hydroxyl group, and M ⁻ represents an anion.) 15. The quaternary ammonium represented by the general formula [5] is a compound represented by the following general formula [5 '].
5. The cleaning agent according to 4. Embedded image (In the formula, R _{6 to} R ₉ each independently represent a lower alkyl group having 1 to 6 carbon atoms or a hydroxy lower alkyl group having 1 to 6 carbon atoms.) 16. The cleaning agent according to claim 15, wherein the quaternary ammonium represented by the general formula [5] is tetramethylammonium hydroxide or trimethyl-2-hydroxyethylammonium hydroxide. 17. The cleaning agent according to claim 13, wherein the ammonia, primary amine, secondary amine or tertiary amine is represented by the following general formula [4]. Embedded image (In the formula, R ₁₁ , R ₁₂ and R ₁₃ each independently represent a hydrogen atom, a lower alkyl group, or a hydroxy lower alkyl group.) 18. A semiconductor device having a surface provided with copper wiring,
A method for cleaning a semiconductor surface having copper wiring on the surface, the method comprising treating with the cleaning agent according to claim 1. 19. A semiconductor surface having copper wiring on the surface,
A method for cleaning a semiconductor surface, comprising performing a physical cleaning step in the presence of the cleaning agent according to claim 1. 20. A semiconductor provided with copper wiring on a surface obtained by cleaning the semiconductor surface provided with copper wiring on the surface by the method according to claim 18. 21. A compound represented by the following general formula [2 ′]: Wherein R ₁ and R ₂ are each independently a hydrogen atom, a hydroxyl group,
Represents an alkyl group or a hydroxyalkyl group, and r and s
Each independently represents 0 or a positive integer, and R _{5 ′} represents a hydrogen atom, a hydroxyl group, an alkyl group, a hydroxyalkyl group or a group represented by the following general formula [3 ′]. Embedded image (Wherein R ₃ and R ₄ are each independently a hydrogen atom, a hydroxyl group,
Represents an alkyl group or a hydroxyalkyl group, and r ′ and s ′ each independently represent 0 or a positive integer. However, this does not apply when r, s, r 'and s' are simultaneously 0. ]
And a nitrogen-containing alkaline compound. 22. The cleaning agent according to claim 21, wherein the compound represented by the general formula [2 ′] is a compound represented by the following general formula [2 ″]. Embedded image (In the formula, R ₁ , R ₂ , R ₃ , R ₄ , r, r ′, s and s ′ are the same as described above.) 23. The cleaning agent according to claim 22, wherein in the general formula [2 ″], R ₁ and R ₃ are a methyl group, and R ₂ and R ₄ are an isobutyl group. 24. In the general formula [2 ″], r, r ′, s
The cleaning agent according to claim 22 or 23, wherein the total number of s 'and s' is 1 to 20. 25. In the general formula [2 ″], r, r ′, s
24. The cleaning agent according to claim 22, wherein the total number of s 'and s' is 1 to 18. 26. The cleaning agent according to claim 22, wherein the compound represented by the general formula [2 ″] is selected from the compounds represented by the following general formulas [6], [7] or [8]. Embedded image (Where p + p ′ is 1 to 20). (In the formula, p + q + p ′ + q ′ is 1 to 20.) (In the formula, q + q ′ is 1 to 20.) 27. The nitrogen-containing alkaline compound is ammonia,
The cleaning agent according to any one of claims 21 to 26, wherein the cleaning agent is selected from a primary amine, a secondary amine, a tertiary amine, and a quaternary ammonium represented by the following general formula [5]. Embedded image (In the formula, R _{6 to} R ₉ each independently represent a hydrocarbon residue which may have a hydroxyl group, and M ⁻ represents an anion.) 28. The nitrogen-containing alkaline compound represented by the general formula [5]:
The cleaning agent according to any one of claims 21 to 26, which is a quaternary ammonium represented by the formula: 29. The quaternary ammonium represented by the general formula [5] is a compound represented by the following general formula [5 '].
9. The cleaning agent according to 8. Embedded image (In the formula, R _{6 to} R ₉ each independently represent a lower alkyl group having 1 to 6 carbon atoms or a hydroxy lower alkyl group having 1 to 6 carbon atoms.) 30. In the general formula [5] or [5 ′], R ₅
The cleaning agent according to claim 28 or 29 hydrocarbon residue is an alkyl group represented by to R _6. 31. The cleaning agent according to claim 30, wherein the alkyl group represented by R _{5 to} R ₆ is a methyl group. 32. The cleaning agent according to claim 29, wherein the quaternary ammonium represented by the general formula [5 '] is tetramethylammonium hydroxide or trimethyl-2-hydroxyethylammonium hydroxide. 33. The cleaning agent according to claim 21, wherein the semiconductor substrate is a semiconductor substrate having a surface provided with copper wiring. 34. A method for cleaning a semiconductor substrate, comprising treating a semiconductor surface with the cleaning agent according to claim 21. 35. The cleaning method according to claim 34, wherein the semiconductor substrate is a semiconductor substrate having a surface provided with copper wiring. 36. A semiconductor substrate obtained by cleaning a semiconductor surface by the method according to claim 34.