JP2006291008A - Fluorine-contained solvent cleaner - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide an alternative solvent technology reducing an environmental load. <P>SOLUTION: This solvent cleaner is represented by general formula (1A)-(1C), in which formula (1A) is Rf-X-Rh, formula (1B) is Rh-X-Rf<SP>1</SP>-X-Rh, and formula (1C) is Rf-X-Rh<SP>1</SP>-X-Rf, wherein Rf represents a monovalent perfluoropolyether group, X is a bonding group, Rh represents a monovalent hydrocarbon group which may have an ethereal oxygen atom, Rf<SP>1</SP>represents a divalent perfluoropolyether group, Rh<SP>1</SP>represents a divalent hydrocarbon group which may have an ethereal oxygen atom, and an alkylene group having a linear chain or a branched chain which may be fluorinated may be contained in Rf, Rf<SP>1</SP>, Rf or Rf<SP>1</SP>and X. <P>COPYRIGHT: (C)2007,JPO&INPIT

Description

  The present invention relates to alternative solvent technology that reduces environmental impact. More specifically, the present invention relates to a fluorine-based cleaning solvent technology that is recyclable and has higher functions than existing organic solvents.

  With the emergence of environmental problems, the reduction of chlorofluorocarbons and alternative chlorofluorocarbons related to ozone destruction or global warming is progressing. On the other hand, the development of new chlorofluorocarbon solvents with low environmental impact is also underway, but the functionality is lower than that of existing chlorofluorocarbons, and the use of additives and the like is being studied to solve this problem. However, as long as a low-boiling point chlorofluorocarbon solvent is used, discharge to the environment is inevitable, and adding a surfactant other than chlorofluorocarbon to the process also causes the possibility of environmental contamination by the surfactant. However, fluorinated solvents have significant advantages in chemical processes that are non-flammable and inert. In order to solve such problems, it is desired to develop a cleaning compound having a high boiling point and a high function.

  However, most high-boiling fluorine compounds are solid and are not suitable for use as a solvent. On the other hand, a perfluoropolyether body has fluidity even at a high molecular weight, and is known as an inert compound for a lubricant (Patent Document 1). However, since these themselves do not have a function of dissolving various compounds, they are not suitable for use as solvents for chemical reaction or washing.

On the other hand, surface treatment technology such as electroplating is widely used as a basic technology in science and technology, but the environmental burden due to waste generated from the process has become a major social problem. In particular, the washing waste liquid occupies a large amount of waste, and the development of efficient washing technology in the pre- and post-processes greatly contributes to reducing the environmental burden in these industrial fields.
JP 08-040964

  An object of this invention is to provide the alternative solvent technique which reduces environmental impact.

As a result of repeated studies in view of the above problems, the present invention has found that a fluorine compound having a specific structure is excellent in cleaning performance and recyclability, and is particularly suitable for use in surface treatment.
The present invention provides the following cleaning agent, cleaning method and surface treatment method.
1. General formula (1A) to (1C)
Rf-X-Rh (1A)
Rf-X-Rh ¹ -X-Rf (1B)
Rh-X-Rf ¹ -X-Rh (1C)
(Wherein Rf represents a perfluoropolyether group of monovalent, X is a linking group, Rh is .Rf ¹ is a divalent perfluoropolyether representing a monovalent hydrocarbon radical which may have an etheric oxygen atom Represents an ether group, and Rh ¹ represents a divalent hydrocarbon group which may have an etheric oxygen atom Rf, Rf ¹ , Rf or Rf ¹ and X may be directly fluorinated. A cleaning agent or a drying agent represented by the formula (may have an alkylene group having a chain or a branch).
2. From the group consisting of each process of semiconductor chip manufacturing including vapor deposition, deposition, electroplating, chemical plating, and resist film formation, lithography, etching and resist stripping in the manufacture of metal thin films, metal oxide films, and composite films Item 2. The cleaning and drying agent according to Item 1, for use in pretreatment and / or posttreatment of at least one selected surface treatment.
3. General formula (1A) to (1C)
Rf-X-Rh (1A)
Rh-X-Rf ¹ -X-Rh (1B)
^{Rf-X-Rh 1 -X-} Rf (1C)
(Wherein Rf represents a perfluoropolyether group of monovalent, X is a linking group, Rh is .Rf ¹ is a divalent perfluoropolyether representing a monovalent hydrocarbon radical which may have an etheric oxygen atom An ether group, and Rh ¹ represents a divalent hydrocarbon group which may have an etheric oxygen atom.) Cleaning and drying methods.
4). Semiconductor chip manufacturing steps including deposition, deposition, electroplating, chemical plating of inorganic compounds, and resist film formation, lithography, etching, and resist stripping when the object is a metal thin film, metal oxide film, and composite film manufacturing Item 4. The cleaning and drying method according to Item 3, wherein the object is at least one kind of surface treatment object selected from the group consisting of, and the object is washed for pretreatment and / or posttreatment of the surface treatment. .
5. At least one solvent selected from the group consisting of the compounds represented by the general formulas (1A) to (1C), an organic solvent, water, organic and inorganic aqueous solutions, ionic liquids, supercritical fluids, and floras solvents; And / or the object is washed and dried by using at least one additive selected from the group consisting of an organic solid, an inorganic solid, or an amphiphilic compound having a surface active function. The cleaning and drying method according to 3 or 4.
6). The compounds represented by the general formulas (1A) to (1C) are continuously used in a pretreatment step, a surface treatment step and a posttreatment step, and the surface treatment is a metal thin film, a metal oxide film, and a composite film In manufacturing, vapor deposition, deposition, electroplating, chemical plating of inorganic compounds, and at least one selected from the group consisting of semiconductor chip manufacturing processes including resist film formation, lithography, etching, and resist stripping. Surface treatment method.

  According to the present invention, it is possible to perform cleaning while greatly reducing the amount of waste.

The inventor has developed fluorine compounds of the following general formulas (1A) to (1C) having the ability to dissolve various compounds while having a recyclable boiling point.

Rf-X-Rh (1A)
Rh-X-Rf ¹ -X-Rh (1B)
^{Rf-X-Rh 1 -X-} Rf (1C)
(Wherein Rf represents a perfluoropolyether group of monovalent, X is a linking group, Rh is .Rf ¹ is a divalent perfluoropolyether representing a monovalent hydrocarbon radical which may have an etheric oxygen atom Represents an ether group, and Rh ¹ represents a divalent hydrocarbon group which may have an etheric oxygen atom Rf, Rf ¹ , Rf or Rf ¹ and X may be directly fluorinated. A cleaning agent or a drying agent represented by the formula (may have an alkylene group having a chain or a branch).

  In the present specification, the term “cleaning agent and desiccant” means that the cleaning agent, the desiccant agent, the cleaning agent and the desiccant agent can be used for any application. For example, the fluorine compound of the present invention is a cleaning agent in these pre-treatments and / or post-treatments in the deposition, deposition, electroplating, and chemical plating of inorganic compounds in the production of metal thin films, metal oxide films, and composite films. Useful as.

  Also, in recent years, in the manufacturing process of semiconductor devices whose structure is becoming finer, in order to prevent pattern collapse after cleaning and drying in each process such as resist film formation, lithography, etching, resist peeling, etc. Cleaning and drying methods using a cleaning liquid to which a surfactant is added are being studied. The compounds of the present invention are also useful as cleaning and drying agents used in such processes. In the manufacture of semiconductor devices, the plating process is a key of the wiring process, and the present invention is effective in both the above-described process of the semiconductor device and the wiring process.

Monovalent Rf groups include the following:
F- (CF ₂ ) _q- (OCF ₃ F ₆ ) _m- (OC ₂ F ₄ ) _n- (OCF ₂ ) _o- (CH ₂ ) _p-
And the divalent Rf group is represented by the following:
-(CH2) _p- (CF ₂ O) _o- (C ₂ F ₄ O) _n- (C ₃ F ₆ O) _m- (CF ₂ ) _q- (OC ₃ F ₆ ) _m- (OC ₂ F ₄ ) _n- (OCF ₂ ) _o- (CH ₂ ) _p-
A group represented by:
(In the monovalent and divalent Rf groups, m, n, o, p, q are the same or different and are integers of 0 or more, and m and n are not 0 but are integers of 0 to 15, n + m ≦ 20, o = 0 to 20, p = 0 to 2, q = 1 to 10. Regardless of the order of each repeating unit,-(OC ₃ F ₆ ) _m- is-(OCF ₂ CF ₂ CF ₂ ) _m- or-(OCF (CF ₃ ) CF ₂ ) _m -,-(OC ₂ F ₄ ) _n- is-(OCF ₂ CF ₂ ) n- or-(OCF (CF ₃ )) n- Represents each.)
X may be the same or different, and may be a single bond or O, S, NH, NR (R ^a : alkyl group), C = O, C (O) O, OC (O), C ( O) S, SC (O), C (O) NH, C (O) NR ^a (R ^a : alkyl group), NH (O) C, NR (O) C, CH ₂ , CHR ^a , CR ^a ₂ (R ^a : alkyl group) represents SO ₂ NH or NHSO ₂ .

Examples of the alkylene group interposed between Rf, Rf ¹ , Rf or Rf ¹ and X include (CH ₂ ) _m , (CF ₂ ) _n , CF (CF ₃ ), (CF ₂ ) _n (CH ₂ ) and the like. Illustrated.

The fluorine compound of the present invention includes the following compounds 1) to 3):
・ F- (CF ₂ ) _q- (OC ₃ F ₆ ) _m- (OC ₂ F ₄ ) _n- (OCF ₂ ) _o- (CH ₂ ) _p X-Rh
・ F- (CF ₂ ) _q- (OC ₃ F ₆ ) _m- (OC ₂ F ₄ ) _n- (OCF ₂ ) _o- (CH ₂ ) _p X-Rh-X- (CH ₂ ) _p- (CF ₂ O) _o- (C ₂ F ₄ O) _n- (C ₃ F ₆ O) _m- (CF ₂ ) _q -F
・ Rh-X (CH ₂ ) _p- (CF ₂ O) _o- (C ₂ F ₄ O) _n- (C ₃ F ₆ O) _m- (CF ₂ ) _q- (OC ₃ F ₆ ) _m- ( OC ₂ F ₄ ) _n- (OCF ₂ ) _o- (CH ₂ ) _p X-Rh
(Where m, n, o, p, q, X and Rh are as defined above)
The Rh group is a group that defines the affinity with the compound to be dissolved or imparts the property of giving the molecule an affinity with a compound other than fluorine, and examples thereof include a hydrocarbon group, a polyoxyalkylene group, and a hydroxyalkyl group. In particular, a polyoxyalkylene group is preferred. Here, as the polyoxyalkylene group,-(CH ₂ CH ₂ O) _n Z,-(CH ₂ (CH ₃ ) CH ₂ ) _n Z,-(CH ₂ (CH ₂ CH ₃ ) CH ₂ O) _n Z ,-(CH ₂ CH ₂ CH ₂ CH ₂ O) _n Z and random or block forms thereof. Here, n is 3 to 20, and Z is hydrogen or a hydrocarbon group such as an alkyl or aralkyl group.

The Rh ¹ group is a group that defines the affinity with the compound to be dissolved or imparts the property of giving the molecule an affinity with a compound other than fluorine, and is a divalent hydrocarbon group, polyoxyalkylene group, hydroxyalkylene group. In particular, a polyoxyalkylene group is preferable. Here, as the polyoxyalkylene group,-(CH ₂ CH ₂ O) _n Z ¹ ,-(CH ₂ (CH ₃ ) CH ₂ ) _n Z ¹ ,-(CH ₂ (CH ₂ CH ₃ ) CH ₂ O) Examples are _n Z ¹ ,-(CH ₂ CH ₂ CH ₂ CH ₂ O) _n Z ¹ and random or block bodies thereof. Here, n is 3 to 20, and Z ¹ is a divalent hydrocarbon group such as an alkylene, arylene, or aralkylene group.

  The compounds (1A) to (1C) shown here can be synthesized and obtained by existing methods, and examples thereof include the following synthetic routes.

Examples of preferable cleaning agents of the present invention include the following fluorine compounds.
F- (CF (CF3) CF2O) nCF (CF3) COO (CH2) mCH3 (n = 1-15, m = 0-30)
F- (CF (CF3) CF2O) nCF (CF3) CH2OOC (CH2) mCH3 (n = 1-15, m = 0-30)
F- (CF (CF3) CF2O) nCF (CF3) CH2O (CH2) mCH3 (n = 1-15, m = 0-30)
F- (CF (CF3) CF2O) nCF (CF3) COO (CH2CH2O) mCH3 (n = 1-15, m = 1-10)
F- (CF (CF3) CF2O) nCF (CF3) COO (CH (CH3) CH2O) mCH3 (n = 1-15, m = 1-10)
F- (CF2CF2O) nCF2COO (CH2) mCH3 (n = 1-15, m = 0-30)
F- (CF2CF2O) nCF2CH2OOC (CH2) mCH3 (n = 1-15, m = 0-30)
F- (CF2CF2O) nCF2CH2O (CH2) mCH3 (n = 1-15, m = 0-30)
F- (CF2CF2O) nCF2COO (CH2CH2O) mCH3 (n = 1-15, m = 1-10)
F- (CF2CF2O) nCF2COO (CH (CH3) CH2O) mCH3 (n = 1-15, m = 1-10)
CF3 (CF2) n- (CF2CF2O) mCF2COO (CH2) pCH3 (n = 1-8, m = 1-15, p = 0-30)
CF3 (CF2) n- (CF2CF2O) mCF2COO (CH2CH2O) pCH3 (n = 1-8, m = 1-15, p = 1-10)
CF3 (CF2) n- (CF2CF2O) mCF2COO (CH (CH3) CH2O) pCH3 (n = 1-8, m = 1-15, p = 1-10)
F- (CF2CF2CF2O) nCF2CF2COO (CH2) mCH3 (n = 1-15, m = 0-30)
F- (CF2CF2CF2O) nCF2CF2CH2OOC (CH2) mCH3 (n = 1-15, m = 0-30)
F- (CF2CF2CF2O) nCF2CF2CH2O (CH2) mCH3 (n = 1-15, m = 0-30)
F- (CF2CF2CF2O) nCF2CF2COO (CH2CH2O) mCH3 (n = 1-15, m = 1-10)
F- (CF2CF2CF2O) nCF2CF2COO (CH (CH3) CH2O) mCH3 (n = 1-15, m = 1-10)
F- (CF2CF2CF2O) nCF2CF2CH2O (CH2CH2O) mCH3 (n = 1-15, m = 1-10)
F- (CF2CF2CF2O) nCF2CF2CH2O (CH (CH3) CH2O) mCH3 (n = 1-15, m = 1-10)
F- (CF (CF3) CF2O) n (CF2CF2O) mCF2COO (CH2) pCH3 (n = 1-10, m = 1-10, p = 0-30)
F- (CF (CF3) CF2O) n (CF2CF2O) mCF2COO (CH2CH2O) pCH3 (n = 1-10, m = 1-10, p = 1-10)
F- (CF (CF3) CF2O) n (CF2CF2O) mCF2COO (CH (CH3) CH2O) pCH3 (n = 1-10, m = 1-10, p = 1-10)
F- (CF (CF3) CF2O) n CF (CF3) COO (CH2CH2O) mOCO (CF3) CF (OCF2 (CF3) CF) p F (n = 1-15, m = 1-20, p = 1-15 )
F- (CF (CF3) CF2O) n CF (CF3) COO (CH2) mOCO (CF3) CF (OCF2 (CF3) CF) p F (n = 1-15, m = 1-30, p = 1-15 )
F- (CF (CF3) CF2O) n CF (CF3) COO (CH (CH3) CH2O) mOCO (CF3) CF (OCF2 (CF3) CF) p F (n = 1-15, m = 1-20, p = 1-15)
CH3 (CH2) nOCOCF (CF3) (CF (CF3) CF2O) mCF (CF3) COO (CH2) pCH3 (n = 0 ~ 20, m = 1 ~ 20, p = 0 ~ 20)
CH3 (CH2) nOCOCF2 (OCF2CF2) mOCF2COO (CH2) pCH3 (n = 0-20, m = 1-20, p = 0-20)
CH3 (OCH2CH2) nOCOCF (CF3) (CF (CF3) CF2O) mCF (CF3) COO (CH2CH2O) pCH3 (n = 1-10, m = 1-20, p = 1-10)
CH3 (OCH2CH2) nOCOCF (CF3) (OCF2CF (CF3)) m (CF2) n (CF (CF3) CF2O) oCF (CF3) COO (CH2CH2O) pCH3 (n = 1-5, m + o = 2-20, p = 1-10)
CH3 (OCH2CH2) nOCOCF2 (OCF2CF2) mOCF2COO (OCH2CH2) pCH3 (n = 0-20, m = 1-20, p = 0-20)
CH3 (OCH2CH (CH3)) nOCOCF (CF3) (CF (CF3) CF2O) mCF (CF3) COO (CH (CH3) CH2O) pCH3 (n = 1-10, m = 1-20, p = 1-10)
F- (CF (CF3) CF2O) nCF (CF3) CH2O (CH2) m (CF2) p CF3 (n = 1-15, m = 1-10, p = 1-20)
XCF2 (CF2) n (CH2) mO (CH2) pCH3 (X = H, F, n = 3 ~ 20, m = 1 ~ 2, p = 1 ~ 20)
XCF2 (CF2) n (CH2) mO (CH2CH2O) pCH3 (X = H, F, n = 3 ~ 20, m = 1 ~ 2, p = 1 ~ 10)
XCF2 (CF2) n (CH2) mO (CH (CH3) CH2O) pCH3 (X = H, F, n = 3 ~ 20, m = 1 ~ 2, p = 1 ~ 10)
XCF2 (CF2) n (CH2) mOOC (CH2) pCH3 (X = H, F, n = 3 ~ 20, m = 1 ~ 2, p = 0 ~ 20)
XCF2 (CF2) n (CH2) mCOO (CH2) pCH3 (X = H, F, n = 3 ~ 20, m = 0 ~ 2, p = 0 ~ 20)
XCF2 (CF2) n (CH2) mCOO (CH2CH2O) pCH3 (X = H, F, n = 3-20, m = 0-2, p = 1-10)
XCF2 (CF2) n (CH2) mCOO (CH (CH3) CH2O) pCH3 (X = H, F, n = 3 ~ 20, m = 0 ~ 2, p = 1 ~ 10)
CH3 (CH2) m OOC (CF2) nCOO (CH2) pCH3 (m = 0 ~ 20, n = 1 ~ 20, p = 0 ~ 20)
CH3 (OCH2CH2) mOOC (CF2) nCOO (CH2CH2O) pCH3 (m = 1 ~ 10, n = 1 ~ 20, p = 1 ~ 10)
CH3 (OCH2CH (CH3)) mOOC (CF2) nCOO (CH (CH3) CH2O) pCH3 (m = 1-10, n = 1-20, p = 1-10)
F- (CF (CF3) CF2O) nCF (CF3) COO (CH2) mCH3 (n = 1-15, m = 0-30);
F- (CF (CF3) CF2O) nCF (CF3) COO (CH2CH2O) mCH3 (n = 1-15, m = 1-10);
XCF2 (CF2) n (CH2) mO (CH2) pCH3 (X = H, F, n = 3-20, m = 1-2, p = 0-20);
And XCF2 (CF2) n (CH2) mCOO (CH2) pCH3 (X = H, F, n = 3-20, m = 0-2, p = 0-20).

  The cleaning agent of the present invention can be used for cleaning an arbitrary object, but is preferably blended in a pretreatment or post-treatment liquid for surface treatment to be used for surface treatment or surface treatment. The cleaned object can be cleaned. You may mix | blend in a surface treatment liquid. Furthermore, the cleaning agent of the present invention can be added to all of the pretreatment liquid, surface treatment liquid and posttreatment liquid for surface treatment, and the process from surface treatment to posttreatment can be performed as a series of operations.

  Surface treatment includes deposition of inorganic compounds, deposition, electroplating, chemical plating, as well as resist film formation, lithography, etching, and resist stripping in the manufacture of metal thin films, metal oxide films, and composite films. The process is preferably exemplified.

Electroplating includes nickel plating, chromium plating, gold, palladium, copper, ruthenium, rhodium, platinum plating and the like. Chemical plating includes electroless plating and chemical conversion treatment. Examples of the electroless plating include metal species such as nickel, copper, gold, silver, palladium, and platinum, and alloy materials containing these.
The cleaning agent of the present invention can be used alone, but other solvents or additives may be used in combination. Other solvents that can be used in combination with the cleaning agent of the present invention include organic solvents (for example, alcohol solvents such as methanol, ethanol and isopropanol, ketone solvents such as acetone and methyl ethyl ketone, ester solvents such as ethyl acetate, diethyl ether). , Ether solvents such as diisopropyl ether and tetrahydrofuran, dioxane, DMF, DMSO, etc.), water, organic and inorganic aqueous solutions, ionic liquids, supercritical fluids, and floras solvents. The above can be used in combination. Additives that can be used in combination with the cleaning agent of the present invention include organic solids, inorganic solids, or amphiphilic compounds having a surface active function. These additives may be used alone or in combination of two or more. You may use together.
As the amphiphilic compound, hydrocarbons, fluorine-containing compounds, silicon surfactants, and anionic surfactants, cationic surfactants, nonionic surfactants, and amphoteric surfactants are all effective. Examples of anionic compounds include alkyl or aryl carboxylic acids, sulfonic acids, sulfonate esters, and phosphates such as ammonium, alkali metals, and alkaline earth metals. Examples of cationic compounds include ammonium salts, sulfonium salts, and phosphonium salts. Onion salts such as salts include nonionic compounds such as polyols such as sugars, esters or ethers of polyols, polyalkylene glycols and the like, and silicon compounds such as these esters, ethers or siloxanes. Examples of the compound include derivatives such as betaine, glycine, alanine, sulfobetaine. Examples of the inorganic solid include alkalis such as carbonic acid, boric acid, phosphoric acid, and silicic acid, alkaline earth metal salts, and alkali and alkaline earth metal hydroxides.
Furthermore, in the cleaning agent of the present invention, at least one of other solvents and at least one additive may be used in combination.

The ionic liquids, tetraalkylphosphonium, trialkylsulfonium, tetraalkylammonium, N- alkylpyridinium, dialkylimidazolium of _{^{BF 4 -, PF 6 -,}} SbF 6 -, NO 3 -, CF 3 SO 3 -, ( CF ₃ SO ₃ ) ₂ N ⁻ , ArSO ₃ ⁻ , CF ₃ CO ₂ ^— salt.

  Examples of the supercritical fluid include carbon dioxide, chlorofluorocarbon, water, and methanol.

  Furthermore, examples of the fluorous solvent include perfluorohexane, perfluoroheptane, perfluoromethylcyclohexane, perfluorotributylamine, and perfluoropolyethers such as demnam, Krytox, Galden, and fomblin.

  In the use of the compounds (1A) to (1C) in the present invention, it can be used in combination with various other solvents besides the use alone. However, if an organic solvent is used, the effect of reducing the environmental load of the present invention is reduced. Therefore, a combination with a low environmental load such as water, a non-volatile solvent such as an ionic liquid, or a supercritical fluid can be used. It is valid. Among these, when a solvent having a high affinity with a fluorine compound, such as supercritical carbon dioxide, is used, it is possible to combine both functions to develop a high function.

  Supercritical carbon dioxide has a low environmental impact, is incombustible, is inexpensive, and is being studied for application to many chemical processes. However, there is a problem in the solubility of inorganic compounds and high molecular weight compounds, and it cannot be said that the technology is sufficiently widespread. In order to solve this problem, various additives have been studied. However, surfactants having high solubility in carbon dioxide are limited, and even prior art techniques are used by adding several percent to carbon dioxide. However, the function is not improved sufficiently.

  The inventor has found that the compounds (1A) to (1C) are very well dissolved in carbon dioxide, and has also demonstrated a cleaning function in which the compounds (1A) to (1C) and supercritical carbon dioxide are mixed. It is known that when a certain amount or more of a surfactant is added to supercritical carbon dioxide, the interfacial tension becomes zero. For this reason, the compound of this invention is very effective in the washing | cleaning technique of the fine structure required by nanotechnology. Carbon dioxide used in the present invention indicates a liquid, subcritical, or supercritical state.

  In the present invention, the mixing ratio of the compounds (1A) to (1C) and supercritical carbon dioxide can be freely changed depending on the compound to be handled. An advantage of the present invention is that compound 1 can be mixed with carbon dioxide in a free ratio. For example, in the drying step after the semiconductor cleaning, the compounds (1A) to (1C) necessary for removing the remaining water are about 1 to 90% with respect to the amount of carbon dioxide. On the other hand, in the surface treatment such as electroplating, although it depends on the substrate adjustment method, it is about 0.001 to 5%, preferably 0.01 to 1%.

  Furthermore, the pressure when used for mixing with carbon dioxide is 10 to 300 atmospheres, but considering the cleaning effect, 50 to 200 atmospheres is desirable.

EXAMPLES The present invention will be specifically described below with reference to examples and reference examples, but the present invention is not limited to these examples.
Reference Example 1 (Measurement of Solubility of Compound 2 in Supercritical Carbon Dioxide)
As shown in FIG. 1, Compound 2 is uniformly dissolved in carbon dioxide at 90 atm at 40 ° C. even at a weight ratio of 20 wt%. When the polyoxyethylene chain is 5 or less, the solubility in carbon dioxide is higher, and it dissolves at 80 ° C. or less at 40 ° C. Moreover, the pressure which makes it melt | dissolve in a carbon dioxide by the quantity ratio of 1-20% from this FIG. 1 is not so high.

From the above, it can be estimated that the compound of the present invention can be mixed with carbon dioxide at a free ratio, and the pressure required for mixing is about 100 atm.

Example 1 Cleaning Function in Electroplating FIG. 2 shows an apparatus used in an example of the present invention.

Nickel plating bath (watt bath: nickel sulfate 280g / L, nickel chloride 60g / L, boric acid 50g / L, appropriate amount of brightener) 20cc, F (CF (CF ₃ ) CF ₂ O) ₃ CF (CF ₃ ) COO (CH ₂ CH ₂ O) ₃ CH ₃ in 0.3 wt% of the plating bath, alkaline degreased brass plate on the cathode, and pure nickel plate (each surface area 4cm ² ) on the anode After mounting and sealing, the temperature was raised to 50 ° C. in the thermostatic chamber 4, and then CO ₂ was sealed up to 10 MPa with the liquid feed pump 3 and the pressure regulator 10. The rotor 6 was rotated at 500 rpm with the stirrer 5 to stir the CO ₂ -plating solution and energized for 6 minutes at 5 A / dm ² to perform nickel plating. After energization, the pressure was reduced, the cathode plate was taken out, and sufficiently washed with water.

  The same plating operation was performed without performing alkaline degreasing of the brass plate. Further, after the plating was stopped, the stirring was stopped and the mixture was left for 5 minutes, and then the pressure was reduced and the sample was taken out. Both specimens were surface observed with a scanning electron microscope (SEM). The obtained scanning electron micrograph is shown in FIG.

From the SEM observation, there was no significant difference between the two plating films. From the above, it was confirmed that this compound exhibited a cleaning effect on the substrate in the pretreatment and posttreatment steps in the electroplating operation.

Example 2. Drying of resist pattern A 70 nm patterned wafer (1 cm square) prepared by EB method on ZEON's resist ZEP520 (thickness 350 nm) was previously wetted with an aqueous solution of ammonium perfluorooctanoate, and further 5 times with water. The resist pattern was rinsed and replaced with water. This sample was placed in a pressure-resistant cell with a window (30 mL), and 1.7 g of F- (CF (CF ₃ ) CF ₂ O) ₃ COO (CH ₂ CH ₂ O) ₅ CH ₃ was added to the apparatus ( (CO2 ratio to 10 wt%). CO2 was introduced at 40 ° C. and 100 atmospheres, and after maintaining this condition for 1 hour, the contents were extracted with 100 atmospheres of CO2 for 10 minutes. SEM observation of the wafer sample taken out from the apparatus confirmed that the pattern was dry without causing pattern collapse. The SEM observation results are shown in FIG.

Example 3. Example of cleaning contaminants adhering to the fiber A sample of cotton fabric with a red wine stain with a radius of 3 cm is placed in the same high-pressure vessel as in Example 2, and F- ( 8.5 g of CF (CF ₃ ) CF ₂ O) ₃ COO (CH ₂ CH ₂ O) ₇ CH ₃ was added. CO2 was introduced to 100 atm, the contents were stirred at 40 ° C. for 10 minutes, and then extracted and removed at 100 ml at 5 ml / min for 10 minutes. After removing the sample, the size of the stain was measured. The radius was reduced to about 2 cm, and the color tone was considerably thinned.

Example 4 Removal of Etching Residue A silicon wafer sample (1 cm × 1 cm square) subjected to dry etching after resist pattern development was placed in a similar high-pressure apparatus. Further, 1.7 g of a surfactant F- (CF (CF ₃ ) CF ₂ O) ₃ COO (CH ₂ CH ₂ O) ₇ CH ₃ was added. CO 2 was introduced to 150 atm and stirred at a temperature of 40 ° C. for 30 minutes with stirring. The surfactant remaining on the wafer was extracted and removed at 5 ml / min for 20 minutes while introducing CO ₂ pressurized to 150 atm. After purging CO2, the wafer sample was observed with SEM, and it was confirmed that the etching residue was removed. The removal rate of the residue was determined by SEM observation, and was determined by the existence ratio of the number of particles existing at 100 nm square before and after the test. The removal rate was 80%.

  All the compounds shown in the examples had a boiling point of 100 ° C. or higher at 1 mmHg, and almost no volatility was observed at normal pressure. These can be regenerated to high purity after use by vacuum distillation or supercritical CO2 extraction.

Compound 2: Solubility curve of F (CF (CF3) CF2O) 3CF (CF3) COO (CH2CH2O) 7CH3. In the region above the line shown in FIG. 1, compound 2 is uniformly dissolved in carbon dioxide. The apparatus used by the Example of this invention is shown. The scanning electron microscope (SEM) photograph obtained about the test piece after the electrolytic plating of Example 1 is shown. The SEM observation result after drying of the resist pattern of Example 2 is shown.

Explanation of symbols

1 Carbon dioxide cylinder 2 Valve 3 Liquid feed pump 4 Constant temperature bath 5 Stirrer 6 Rotor 7a Electrode (anode)
7b Electrode (cathode)
8 High-pressure vessel 9 Power supply for plating 10 Pressure regulator

Claims (6)

General formula (1A) to (1C):
Rf-X-Rh (1A)
Rh-X-Rf ¹ -X-Rh (1B)
^{Rf-X-Rh 1 -X-} Rf (1C)
(Wherein Rf represents a perfluoropolyether group of monovalent, X is a linking group, Rh is .Rf ¹ is a divalent perfluoropolyether representing a monovalent hydrocarbon radical which may have an etheric oxygen atom Represents an ether group, and Rh ¹ represents a divalent hydrocarbon group which may have an etheric oxygen atom Rf, Rf ¹ , Rf or Rf ¹ and X may be directly fluorinated. A cleaning agent or a drying agent represented by the formula (may have an alkylene group having a chain or a branch). From the group consisting of each process of semiconductor chip manufacturing, including vapor deposition, deposition, electroplating, chemical plating, and resist film formation, lithography, etching, and resist stripping in the manufacture of metal thin films, metal oxide films, and composite films The cleaning and drying agent according to claim 1 for use in pre-treatment and / or post-treatment of at least one selected surface treatment. General formula (1A) to (1C)
Rf-X-Rh (1A)
Rf-X-Rh ¹ -X-Rf (1B)
Rh-X-Rf ¹ -X-Rh (1C)
(Wherein Rf represents a perfluoropolyether group of monovalent, X is a linking group, Rh is .Rf ¹ is a divalent perfluoropolyether representing a monovalent hydrocarbon radical which may have an etheric oxygen atom An ether group, and Rh ¹ represents a divalent hydrocarbon group which may have an etheric oxygen atom.) Cleaning and drying methods. Semiconductor chip manufacturing steps including deposition, deposition, electroplating, chemical plating of inorganic compounds, and resist film formation, lithography, etching, resist stripping in the case where the object is a metal thin film, metal oxide film, and composite film manufacturing Washing and drying according to claim 3, wherein the object is at least one kind of surface treatment object selected from the group consisting of, and the object is washed for pretreatment and / or posttreatment of the surface treatment. Method. At least one solvent selected from the group consisting of the compounds represented by the general formulas (1A) to (1C), an organic solvent, water, organic and inorganic aqueous solutions, ionic liquids, supercritical fluids, and floras solvents; And / or washing and drying the object using at least one additive selected from the group consisting of an organic solid, an inorganic solid, or an amphiphilic compound having a surface active function. Item 5. The cleaning and drying method according to Item 3 or 4. The compounds represented by the general formulas (1A) to (1C) are continuously used in a pretreatment step, a surface treatment step and a posttreatment step, and the surface treatment is a metal thin film, a metal oxide film, and a composite film In manufacturing, vapor deposition, deposition, electroplating, chemical plating of inorganic compounds, and at least one selected from the group consisting of semiconductor chip manufacturing steps including resist film formation, lithography, etching, and resist stripping. Surface treatment method.

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