Patent Publication Number: US-2020277512-A1

Title: Composition for film deposition and film deposition apparatus

Description:
TECHNICAL FIELD 
     The present invention relates to a composition for film deposition and a film deposition apparatus. 
     BACKGROUND 
     In a film deposition process such as vapor deposition polymerization, a molecule supplied with gas is adsorbed on a substrate and polymerized by thermal energy of the substrate, and a thin film of polymer is formed. Patent Document 1 discloses a film deposition method of forming a polyimide film by supplying a first processing gas that includes a first monomer and a second processing gas that includes a second monomer to a substrate, and performing vapor deposition and polymerization of the first monomer and the second monomer on a surface of a wafer. 
     CITATION LIST 
     Patent Document 
     [Patent Document 1] Japanese Patent No. 5966618 
     SUMMARY 
     Problem to be Solved by the Invention 
     Crystallization in a film may occur in a polymer film formed by a film deposition process. Such crystallization may reduce the uniformity of a film (hereinafter referred to as film roughness) and cause structural defects. 
     It is an object of the present invention to provide a composition for film deposition that can suppress the occurrence of crystallization in a film. 
     Means for Solving Problem 
     In order to achieve the object described above, one aspect of the present invention provides a composition for film deposition that includes a first component that polymerizes with a second component to form a nitrogen-containing carbonyl compound, and wherein the molecular structure of the first component and the molecular structure of the second component are asymmetric with each other. 
     Effect of Invention 
     According to one aspect of the present invention, the occurrence of crystallization in a film can be suppressed. 
    
    
     
       BRIEF DESCRIPTION OF THE DRAWINGS 
         FIG. 1  is a cross-sectional view of a film deposition apparatus according to an embodiment of the present invention; 
         FIG. 2  is a chart illustrating timing of supplying gas in the film deposition apparatus illustrated in  FIG. 1 ; 
         FIG. 3  is a cross-sectional view of a wafer illustrating a process of forming a protective film on the wafer using the film deposition apparatus illustrated in  FIG. 1 ; 
         FIG. 4  is a cross-sectional view of a wafer illustrating a process of etching the wafer illustrated in  FIG. 3 ; 
         FIG. 5  is a cross-sectional view of a wafer illustrating a state in which the protective film is removed from the wafer illustrated in  FIG. 4 ; 
         FIG. 6  is a chart illustrating another timing of supplying gas in the film deposition apparatus illustrated in  FIG. 1 ; 
         FIG. 7  is a schematic view of a film deposition apparatus for evaluating the composition for film deposition according to the subject matter of this application; 
         FIG. 8  is a drawing illustrating a state in which a surface of a substrate deposited by using a composition for film deposition according to the embodiment is imaged by a light microscope dark field method, (a) is a state before heating and (b) is a state after heating; and 
         FIG. 9  is a drawing illustrating a state in which a surface of a substrate deposited by using a composition for film deposition of a comparative example is imaged by a light microscope dark field method, (a) is a state before heating and (b) is a state after heating. 
     
    
    
     DESCRIPTION OF EMBODIMENTS 
     In the following, an embodiment of the present invention will be described in detail. 
     &lt;Composition for Film Deposition&gt; 
     A composition for film deposition according to the embodiment of the present invention includes a first component that polymerizes with a second component to form a nitrogen-containing carbonyl compound, and wherein a molecular structure of the first component and a molecular structure of the second component are asymmetric with each other. 
     &lt;Nitrogen-Containing Carbonyl Compound&gt; 
     In the composition for film deposition according to the embodiment, the nitrogen-containing carbonyl compound formed by polymerization of the first component and the second component is a polymer containing a carbon-oxygen double bond and nitrogen. The nitrogen-containing carbonyl compound constitutes a component of a film deposited by polymerization of the first component and the second component. The nitrogen-containing carbonyl compound can be, for example, a protective film for preventing a specific portion of a wafer from being etched, as a polymer film. 
     The nitrogen-containing carbonyl compound is not particularly limited. With respect to the stability of a formed film, examples of the nitrogen-containing carbonyl compound include polyureas, polyurethanes, polyamides, and polyimides. These nitrogen-containing carbonyl compounds may be used either singly or in combinations of two or more compounds. In the embodiment, among these nitrogen-containing carbonyl compounds, polyureas and polyimides are preferable, and polyureas are more preferable. Here, these nitrogen-containing carbonyl compounds are examples of the nitrogen-containing carbonyl compound in the composition for film deposition according to the subject matter of this application. 
     &lt;First Component&gt; 
     The first component included in the composition for film deposition according to the embodiment is a monomer that can polymerize with the second component to form the nitrogen-containing carbonyl compound. Compounds suitable as a first component are not particularly limited, but includes, for example, isocyanates, amines, acid anhydrides, carboxylic acids, and alcohols. These compounds are examples of suitable first components to be included in the composition for film deposition according to the subject matter of this application. 
     Isocyanates, which are examples of the first component, are a chemical species that can polymerize with amines to form polyureas and can polymerize with alcohols to form polyurethanes. The number of carbon atoms of the isocyanate is not particularly limited, but with respect to obtaining a sufficient film deposition rate, the number of carbon atoms is preferably 2 to 18, 2 to 12 more preferably, and 2 to 8 still more preferably. 
     Additionally, the structure of the isocyanate is not particularly limited, and for example, a basic structure of an aromatic compound, a xylene-based compound, an alicyclic compound, an aliphatic compound, and the like can be employed. Isocyanates including such a basic structure may be used either singly or in combinations of two or more compounds. 
     The functionality of the isocyanate is not particularly limited, but with respect to obtaining a sufficient film deposition rate, the isocyanate is preferably a monofunctional compound or a bifunctional compound. 
     Specific examples of suitable isocyanates include 4,4′-diphenylmethane diisocyanate, 1,3-bis(isocyanatomethyl)cyclohexane (H6XDI), 1,3-bis(isocyanatomethyl)benzene, paraphenylene diisocyanate (PPDI), 4,4′-methylene diisocyanate, benzyl isocyanate, 1,2-diisocyanatoethane, 1,4-diisocyanatobutane, 1,6-diisocyanatohexane, 1,8-diisocyanatooctane, 1,10-diisocyanatodecane, 1,6-diisocyanato-2,4,4-trimethylhexane, 1,2-diisocyanatopropane, 1,1-diisocyanatoethane, 1,3,5-triisocyanatobenzene, 1,3-bis(isocyanato-2-propyl)benzene, isophorone diisocyanate, and 2,5-bis(isocyanatomethyl)bicyclo[2.2.1]heptane. The above-described isocyanate compounds may be used either singly or in combinations of two or more compounds. 
     Amines, which are examples of the first component, are a chemical species that can polymerize with isocyanates to form polyureas, and also can polymerize with acid anhydrides to form polyimides. The number of carbon atoms of the amine is not particularly limited, but with respect to obtaining a sufficient deposition rate, the number of carbon atoms is preferably 2 to 18, more preferably 2 to 12, and still more preferably 4 to 12. 
     Additionally, the structure of the amine is not particularly limited, and, for example, a basic structure of an aromatic compound, a xylene-based compound, an alicyclic compound, an aliphatic compound, and the like can be employed. Amines including such a basic structure may be used either singly or in combinations of two or more compounds. 
     The functionality of the amine is not particularly limited, but with respect to obtaining a sufficient film deposition rate, the amine is preferably a monofunctional or bifunctional compound. 
     Specific examples of suitable amines include 1,3-bis(aminomethyl)cyclohexane (H6XDA), 1,3-bis(aminomethyl)benzene, paraxylylenediamine, 1,3-phenylenediamine (MPDA), paraphenylenediamine (PPDA), 4,4′-methylenedianiline (MDA), 3-(aminomethyl)benzylamine (MXDA), hexamethylenediamine(HMDA), benzylamine, 1,2-diaminoethane, 1,4-diaminobutane, 1,6-diaminohexane, 1,8-diaminooctane, 1,10-diaminodecan, 1,12-diaminododecan (DDA), 2-aminomethyl-1,3-propanediamine, methanetriamine, bicyclo[2.2.1]heptanedimethaneamine, piperazine, 2-methylpiperazine, 1,3-di-4-piperidylpropane, 1,4-diazepane, diethylenetriamine, N-(2-aminoethyl)-N-methyl-1,2-ethanediamine, bis(3-aminopropyl)amine, triethylenetetramine, and spermidine. The above-described amine compounds may be used either singly or in combinations of two or more compounds. 
     Acid anhydrides, which are examples of the first component, are a chemical species that can polymerize with amines to form polyimides. The number of carbon atoms of the acid anhydride is not particularly limited, but with respect to obtaining a sufficient film deposition rate, the number of carbon atoms is preferably 2 to 18, more preferably 2 to 12, and still more preferably 4 to 12. 
     The structure of the acid anhydride is not particularly limited, and for example, a basic structure of an aromatic compound, a xylene-based compound, an alicyclic compound, an aliphatic compound, and the like can be employed. Acid anhydrides including such a basic structure may be used either singly or in combinations of two or more compounds. 
     The functionality of the acid anhydride is not particularly limited, but with respect to obtaining a sufficient film deposition rate, the acid anhydride is preferably a monofunctional or bifunctional compound. 
     Specific examples of suitable acid anhydrides include pyromellitic dianhydride, 3,3′,4,4′-benzophenone tetracarboxylic dianhydride, 2,2′,3,3′-benzophenone tetracarboxylic dianhydride, 2,3,3′,4′-benzophenone tetracarboxylic dianhydride, naphthalene-1,2,5,6-tetracarboxylic dianhydride, naphthalene-1,2,4,5-tetracarboxylic dianhydride, naphthalene-1,4,5,8-tetracarboxylic dianhydride, naphthalene-1,2,6,7-tetracarboxylic dianhydride, 4,8-dimethyl-1,2,3,5,6,7-hexahydronaphthalene-1,2,5,6-tetracarboxylic dianhydride, 4,8-dimethyl-1,2,3,5,6,7-hexahydronaphthalene-2,3,6,7-tetracarboxylic dianhydride, 2,6-dichloronaphthalene-1,4,5,8-tetracarboxylic dianhydride, 2,7-dichloronaphthalene-1,4,5,8-tetracarboxylic dianhydride, 2,3,6,7-tetrachloronaphthalene-1,4,5,8-tetracarboxylic dianhydride, 1,4,5,8-tetrachloronaphthalene-2,3,6,7-tetracarboxylic dianhydride, 3,3′,4,4′-biphenyltetracarboxylic dianhydride, 2,2′,3,3′-biphenyltetracarboxylic dianhydride, 2,3,3′,4′-biphenyltetracarboxylic dianhydride, 3,3″,4,4″-p-terphenyltetracarboxylic dianhydride, 2,2″,3,3″-p-terphenyltetracarboxylic dianhydride, 2,3,3″,4″-p-terphenyltetracarboxylic dianhydride, 2,2-bis(2,3-dicarboxyphenyl)-propane dianhydride, 2,2-bis(3,4-dicarboxyphenyl)-propane dianhydride, bis(2,3-dicarboxyphenyl)ether dianhydride, bis(2,3-dicarboxyphenyl)methane dianhydride, bis(3,4-dicarboxyphenyl)methane dianhydride, bis(2,3-dicarboxyphenyl)sulfone dianhydride, bis(3,4-dicarboxyphenyl)sulfone dianhydride, 1,1-bis(2,3-dicarboxyphenyl)ethane dianhydride, 1,1-bis(3,4-dicarboxyphenyl)ethane dianhydride, perylene-2,3,8,9-tetracarboxylic dianhydride, perylene-3,4,9,10-tetracarboxylic dianhydride, perylene-4,5,10,11-tetracarboxylic dianhydride, perylene-5,6,11,12-tetracarboxylic dianhydride, phenanthrene-1,2,7,8-tetracarboxylic dianhydride, phenanthrene-1,2,6,7-tetracarboxylic dianhydride, phenanthrene-1,2,9,10-tetracarboxylic dianhydride, cyclopentane-1,2,3,4-tetracarboxylic dianhydride, pyrazine-2,3,5,6-tetracarboxylic dianhydride, pyrrolidine-2,3,4,5-tetracarboxylic dianhydride, thiophene-2,3,4,5-tetracarboxylic dianhydride, 4,4′-oxydiphthalic dianhydride, and 2,3,6,7-naphthalenetetracarboxylic dianhydride. The above-described acid anhydride compounds may be used either singly or in combinations of two or more compounds. 
     Carboxylic acids, which are examples of the first component, are a chemical species that can polymerize with amines to form polyamides. The number of carbon atoms of the carboxylic acid is not particularly limited, but with respect to obtaining a sufficient film deposition rate, the number of carbon atoms is preferably 2 to 18, is 2 to 12 more preferably, and is 2 to 8 still more preferably. 
     The structure of the carboxylic acid is not particularly limited, and for example, a basic structure of an aromatic compound, a xylene-based compound, an alicyclic compound, an aliphatic compound, and the like may be employed. Carboxylic acids including such a basic structure may be used either singly or in combinations of two or more compounds. 
     The functionality of the carboxylic acid is not particularly limited, but with respect to obtaining a sufficient film deposition rate, the carboxylic acid is preferably a monofunctional or bifunctional compound. 
     Specific examples of suitable carboxylic acids include butanedioic acid, pentanedioic acid, hexanedioic acid, octanedioic acid, 2,2′-(1,4-cyclohexanediyl)diacetic acid, 1,4-phenylenediacetic acid, 4,4′-methylenedibenzoic acid, phenyleneacetic acid, benzoic acid, salicylic acid, acetylsalicylic acid, succinyl chloride, glutaryl chloride, adipoyl chloride, suberoyl chloride, 2,2′-(1,4-phenylene) diacetyl chloride, terephthaloyl chloride, and phenylacetyl chloride. The above-described carboxylic acid compounds may be used either singly or in combinations of two or more compounds. 
     Alcohols, which are examples of the first component, are a chemical species that can polymerize with isocyanates to form polyurethanes. The number of carbon atoms of the alcohol is not particularly limited, but with respect to obtaining a sufficient film deposition rate, the number of carbon atoms is preferably 2 to 18, is more preferably 2 to 12, and is still more preferably 4 to 12. 
     The structure of the alcohol is not particularly limited, and for example, a basic structure of an aromatic compound, a xylene-based compound, an alicyclic compound, an aliphatic compound, and the like can be employed. Alcohols including such a basic structure may be used either singly or in combinations of two or more compounds. 
     The functionality of the alcohol is not particularly limited, but with respect to obtaining a sufficient film deposition rate, the alcohol is preferably a monofunctional or bifunctional compound. 
     Specific examples of suitable alcohols include 1,3-cyclohexanediyldimethanol, 1,3-phenylenedimethanol, hydroquinone, benzyl alcohol, 1,2-ethanediol, 1,4-butanediol, 1,6-hexanediol, 1,8-octanediol, 1,10-decanediol, 2,5-norbonandiol, methantriol, diethylene glycol, triethylene glycol, and 3,3′-oxydipropane-1-ol. The above-described alcohol compounds may be used either singly or in combinations of two or more compounds. 
     The desorption energy of the first component is the activation energy needed to remove the first component from an interface, and is expressed in the unit of kJ/mol. The range of the desorption energy of the first component is not particularly limited, but with respect to obtaining a sufficient film deposition rate, the range of the desorption energy of the first component is preferably 10 to 130 kJ/mol, is more preferably 30 to 120 kJ/mol, and is still more preferably 50 to 110 kJ/mol. If a minimum value of the range of the desorption energy is too low, the first component that does not contribute to polymerization is also adsorbed, and the purity of a formed polymer may be reduced. If a maximum value of the range of the desorption energy is too high, there is a possibility that a film of the nitrogen-containing carbonyl compound cannot be sufficiently formed or the uniformity of a formed film is reduced. 
     Another physical property of the first component is not particularly limited. To maintain adsorption of the first component, a boiling point of the first component is preferably 100° C. to 500° C. Specifically, the boiling point of the first component is 100° C. to 450° C. for amines, is 100° C. to 450° C. for isocyanates, is 120 to 500° C. for carboxylic acids, is 150° C. to 500° C. for acid anhydrides, and is 150° C. to 400° C. for alcohols. 
     &lt;Second Component&gt; 
     The second component included in the composition for film deposition according to the embodiment is a monomer that can polymerize with the first component to form the nitrogen-containing carbonyl compound. Compounds suitable as a second component are not particularly limited, but includes, for example, isocyanates, amines, acid anhydrides, carboxylic acids, and alcohols. These compounds are examples of suitable second components to be included in the composition for film deposition according to the subject matter of this application. 
     Isocyanates, which are examples of the second component, are a chemical species that can polymerize with amines to form polyureas and can polymerize with alcohols to form polyurethanes. The number of carbon atoms of the isocyanate is not particularly limited, but with respect to obtaining a sufficient film deposition rate, the number of carbon atoms is preferably 2 to 18, 2 to 12 more preferably, and 2 to 8 still more preferably. 
     Additionally, the structure of the isocyanate is not particularly limited, and for example, a basic structure of an aromatic compound, a xylene-based compound, an alicyclic compound, an aliphatic compound, and the like can be employed. Isocyanates including such a basic structure may be used either singly or in combinations of two or more compounds. 
     The functionality of the isocyanate is not particularly limited, but with respect to obtaining a sufficient film deposition rate, the isocyanate is preferably a monofunctional compound or a bifunctional compound. 
     Specific examples of suitable isocyanates include 4,4′-diphenylmethane diisocyanate, 1,3-bis(isocyanatomethyl)cyclohexane (H6XDI), 1,3-bis(isocyanatomethyl)benzene, paraphenylene diisocyanate (PPDI), 4,4′-methylene diisocyanate, benzyl isocyanate, 1,2-diisocyanatoethane, 1,4-diisocyanatobutane, 1,6-diisocyanatohexane, 1,8-diisocyanatooctane, 1,10-diisocyanatodecane, 1,6-diisocyanato-2,4,4-trimethylhexane, 1,2-diisocyanatopropane, 1,1-diisocyanatoethane, 1,3,5-triisocyanatobenzene, 1,3-bis(isocyanato-2-propyl)benzene, isophorone diisocyanate, and 2,5-bis(isocyanatomethyl)bicyclo[2.2.1]heptane. The above-described isocyanate compounds may be used either singly or in combinations of two or more compounds. 
     Amines, which are examples of the second component, are a chemical species that can polymerize with isocyanates to form polyureas, and also can polymerize with acid anhydrides to form polyimides. The number of carbon atoms of the amine is not particularly limited, but with respect to obtaining a sufficient deposition rate, the number of carbon atoms is preferably 2 to 18, more preferably 2 to 12, and still more preferably 4 to 12. 
     Additionally, the structure of the amine is not particularly limited, and, for example, a basic structure of an aromatic compound, a xylene-based compound, an alicyclic compound, an aliphatic compound, and the like can be employed. Amines including such a basic structure may be used either singly or in combinations of two or more compounds. 
     The functionality of the amine is not particularly limited, but with respect to obtaining a sufficient film deposition rate, the amine is preferably a monofunctional or bifunctional compound. 
     Specific examples of suitable amines include 1,3-bis(aminomethyl)cyclohexane (H6XDA), 1,3-bis(aminomethyl)benzene, paraxylylenediamine, 1,3-phenylenediamine (MPDA), paraphenylenediamine (PPDA), 4,4′-methylenedianiline (MDA), 3-(aminomethyl)benzylamine (MXDA), hexamethylenediamine (HMDA), benzylamine, 1,2-diaminoethane, 1,4-diaminobutane, 1,6-diaminohexane, 1,8-diaminooctane, 1,10-diaminodecan, 1,12-diaminododecan (DDA), 2-aminomethyl-1,3-propanediamine, methanetriamine, bicyclo[2.2.1]heptanedimethaneamine, piperazine, 2-methylpiperazine, 1,3-di-4-piperidylpropane, 1,4-diazepane, diethylenetriamine, N-(2-aminoethyl)-N-methyl-1,2-ethanediamine, bis(3-aminopropyl)amine, triethylenetetramine, and spermidine. The above-described amine compounds may be used either singly or in combinations of two or more compounds. 
     Acid anhydrides, which are examples of the second component, are a chemical species that can polymerize with amines to form polyimides. The number of carbon atoms of the acid anhydride is not particularly limited, but with respect to obtaining a sufficient film deposition rate, the number of carbon atoms is preferably 2 to 18, more preferably 2 to 12, and still more preferably 4 to 12. 
     The structure of the acid anhydride is not particularly limited, and for example, a basic structure of an aromatic compound, a xylene-based compound, an alicyclic compound, an aliphatic compound, and the like can be employed. Acid anhydrides including such a basic structure may be used either singly or in combinations of two or more compounds. 
     The functionality of the acid anhydride is not particularly limited, but with respect to obtaining a sufficient film deposition rate, the acid anhydride is preferably a monofunctional or bifunctional compound. 
     Specific examples of suitable acid anhydrides include pyromellitic dianhydride, 3,3′,4,4′-benzophenone tetracarboxylic dianhydride, 2,2′,3,3′-benzophenone tetracarboxylic dianhydride, 2,3,3′,4′-benzophenone tetracarboxylic dianhydride, naphthalene-1,2,5,6-tetracarboxylic dianhydride, naphthalene-1,2,4,5-tetracarboxylic dianhydride, naphthalene-1,4,5,8-tetracarboxylic dianhydride, naphthalene-1,2,6,7-tetracarboxylic dianhydride, 4,8-dimethyl-1,2,3,5,6,7-hexahydronaphthalene-1,2,5,6-tetracarboxylic dianhydride, 4,8-dimethyl-1,2,3,5,6,7-hexahydronaphthalene-2,3,6,7-tetracarboxylic dianhydride, 2,6-dichloronaphthalene-1,4,5,8-tetracarboxylic dianhydride, 2,7-dichloronaphthalene-1,4,5,8-tetracarboxylic dianhydride, 2,3,6,7-tetrachloronaphthalene-1,4,5,8-tetracarboxylic dianhydride, 1,4,5,8-tetrachloronaphthalene-2,3,6,7-tetracarboxylic dianhydride, 3,3′,4,4′-biphenyltetracarboxylic dianhydride, 2,2′,3,3′-biphenyltetracarboxylic dianhydride, 2,3,3′,4′-biphenyltetracarboxylic dianhydride, 3,3″,4,4″-p-terphenyltetracarboxylic dianhydride, 2,2″,3,3″-p-terphenyltetracarboxylic dianhydride, 2,3,3″,4″-p-terphenyltetracarboxylic dianhydride, 2,2-bis(2,3-dicarboxyphenyl)-propane dianhydride, 2,2-bis(3,4-dicarboxyphenyl)-propane dianhydride, bis(2,3-dicarboxyphenyl)ether dianhydride, bis(2,3-dicarboxyphenyl)methane dianhydride, bis(3,4-dicarboxyphenyl)methane dianhydride, bis(2,3-dicarboxyphenyl)sulfone dianhydride, bis(3,4-dicarboxyphenyl)sulfone dianhydride, 1,1-bis(2,3-dicarboxyphenyl)ethane dianhydride, 1,1-bis(3,4-dicarboxyphenyl) ethane dianhydride, perylene-2,3,8,9-tetracarboxylic dianhydride, perylene-3,4,9,10-tetracarboxylic dianhydride, perylene-4,5,10,11-tetracarboxylic dianhydride, perylene-5,6,11,12-tetracarboxylic dianhydride, phenanthrene-1,2,7,8-tetracarboxylic dianhydride, phenanthrene-1,2,6,7-tetracarboxylic dianhydride, phenanthrene-1,2,9,10-tetracarboxylic dianhydride, cyclopentane-1,2,3,4-tetracarboxylic dianhydride, pyrazine-2,3,5,6-tetracarboxylic dianhydride, pyrrolidine-2,3,4,5-tetracarboxylic dianhydride, thiophene-2,3,4,5-tetracarboxylic dianhydride, 4,4′-oxydiphthalic dianhydride, and 2,3,6,7-naphthalenetetracarboxylic dianhydride. The above-described acid anhydride compounds may be used either singly or in combinations of two or more compounds. 
     Carboxylic acids, which are examples of the second component, are a chemical species that can polymerize with amines to form polyamides. The number of carbon atoms of the carboxylic acid is not particularly limited, but with respect to obtaining a sufficient film deposition rate, the number of carbon atoms is preferably 2 to 18, is 2 to 12 more preferably, and is 2 to 8 still more preferably. 
     The structure of the carboxylic acid is not particularly limited, and for example, a basic structure of an aromatic compound, a xylene-based compound, an alicyclic compound, an aliphatic compound, and the like may be employed. Carboxylic acids including such a basic structure may be used either singly or in combinations of two or more compounds. 
     The functionality of the carboxylic acid is not particularly limited, but with respect to obtaining a sufficient film deposition rate, the carboxylic acid is preferably a monofunctional or bifunctional compound. 
     Specific examples of suitable carboxylic acids include butanedioic acid, pentanedioic acid, hexanedioic acid, octanedioic acid, 2,2′-(1,4-cyclohexanediyl)diacetic acid, 1,4-phenylenediacetic acid, 4,4′-methylenedibenzoic acid, phenyleneacetic acid, benzoic acid, salicylic acid, acetylsalicylic acid, succinyl chloride, glutaryl chloride, adipoyl chloride, suberoyl chloride, 2,2′-(1,4-phenylene)diacetyl chloride, terephthaloyl chloride, and phenylacetyl chloride. The above-described carboxylic acid compounds may be used either singly or in combinations of two or more compounds. 
     Alcohols, which are examples of the second component, are a chemical species that can polymerize with isocyanates to form polyurethanes. The number of carbon atoms of the alcohol is not particularly limited, but with respect to obtaining a sufficient film deposition rate, the number of carbon atoms is preferably 2 to 18, is more preferably 2 to 12, and is still more preferably 4 to 12. 
     The structure of the alcohol is not particularly limited, and for example, a basic structure of an aromatic compound, a xylene-based compound, an alicyclic compound, an aliphatic compound, and the like can be employed. Alcohols including such a basic structure may be used either singly or in combinations of two or more compounds. 
     The functionality of the alcohol is not particularly limited, but with respect to obtaining a sufficient film deposition rate, the alcohol is preferably a monofunctional or bifunctional compound. 
     Specific examples of suitable alcohols include 1,3-cyclohexanediyldimethanol, 1,3-phenylenedimethanol, hydroquinone, benzyl alcohol, 1,2-ethanediol, 1,4-butanediol, 1,6-hexanediol, 1,8-octanediol, 1,10-decanediol, 2,5-norbonandiol, methantriol, diethylene glycol, triethylene glycol, and 3,3′-oxydipropane-1-ol. The above-described alcohol compounds may be used either singly or in combinations of two or more compounds. 
     The desorption energy of the second component is the activation energy needed to remove the second component from an interface, and is expressed in the unit of kJ/mol. The range of the desorption energy of the second component is not particularly limited, but with respect to obtaining a sufficient film deposition rate, the range of the desorption energy of the second component is preferably 10 to 130 kJ/mol, is more preferably 30 to 120 kJ/mol, and is still more preferably 50 to 110 kJ/mol. If a minimum value of the range of the desorption energy is too low, the second component that does not contribute to polymerization is also adsorbed, and the purity of a formed polymer may be reduced. If a maximum value of the range of the desorption energy is too high, there is a possibility that a film of the nitrogen-containing carbonyl compound cannot be sufficiently formed or the uniformity of a formed film is reduced. 
     Another physical property of the second component is not particularly limited. To maintain adsorption of the second component, a boiling point of the second component is preferably 100° C. to 500° C. Specifically, the boiling point of the second component is 100° C. to 450° C. for amines, is 100° C. to 450° C. for isocyanate, is 120° C. to 500° C. for carboxylic acids, is 150° C. to 500° C. for acid anhydrides, and is 150° C. to 400° C. for an alcohols. 
     The combination of the first component and the second component is not particularly limited, but either the first component or the second component is preferably isocyanate, and the isocyanate is more preferably a bifunctional alicyclic compound. Still more preferably, the bifunctional alicyclic compound is 1,3-bis(isocyanatomethyl)cyclohexane (H6XDI). 
     Additionally, the other component of the first component or the second component is preferably amine, and the amine is more preferably a bifunctional alicyclic compound. Still more preferably, the bifunctional alicyclic compound is 1,3-bis(aminomethyl)cyclohexane (H6XDA). 
     A method of polymerizing the first component and the second component is not particularly limited as long as a nitrogen-containing carbonyl compound can be formed. However, with respect to obtaining a sufficient film deposition rate, a vapor deposition polymerization method is preferred. The vapor deposition polymerization method is a method of polymerization in which two or more monomers are simultaneously heated and evaporated in a vacuum so that the monomers are polymerized on a substrate. 
     The polymerization temperature is the temperature required for polymerization of the first component and the second component. The polymerization temperature is not particularly limited and may be adjusted based on a type of a nitrogen-containing carbonyl compound to be formed, and the specific first component and second component to be polymerized, for example. The polymerization temperature is indicated by temperature of the substrate for example when the first component and the second component are vapor-deposited and polymerized on the substrate. The specific polymerization temperature, for example, is 20° C. to 200° C. when polyureas are formed as a nitrogen-containing carbonyl compound, is 100° C. to 300° C. when polyimides are formed as a nitrogen-containing carbonyl compound, and is more preferably 38° C. to 150° C. when polyimides are formed as a nitrogen-containing carbonyl compound. 
     In the embodiment, the molecular structure of the first component and the molecular structure of the second component are asymmetric with each other. Here, a description that the molecular structures are asymmetric with each other indicates that basic skeletons of two molecules, excluding a substituent or a functional group, do not have point symmetry, line symmetry, plane symmetry, or rotational symmetry. For example, if the two molecules are a cyclic compound and a stranded compound, aromatic compounds with different orientations, and alicyclic compounds with cis-trans isomers (also called geometric isomers), the molecular structures of the two molecules are asymmetric with each other. 
     In this embodiment, the asymmetry between the molecular structure of the first component and the molecular structure of the second component reduces the occurrence of crystalline aggregation in a polymer as a polymer of the nitrogen-containing carbonyl compound grows by the film deposition process. Additionally, the occurrence of crystallites in a film due to heat treatment after film deposition is also reduced. Therefore, in the embodiment, the occurrence of crystallization in a film can be suppressed, and the occurrence of film roughness and structural defects can be prevented. 
     &lt;Film Deposition Apparatus&gt; 
     Next, a film deposition apparatus  1  according to the embodiment of the present invention will be described with reference to a cross-sectional view illustrated in  FIG. 1 . The film deposition apparatus  1  according to the embodiment includes a treatment vessel  11  in which a vacuum atmosphere is created, a pedestal (i.e., a stage  21 ) on which a substrate (i.e., a wafer W) is placed, provided in the treatment vessel  11 , and a supply (i.e., a gas nozzle  41 ) for supplying the above-described composition for film deposition (i.e., a film deposition gas) into the treatment vessel  11 . Here, the film deposition apparatus  1  is an example of a film deposition apparatus according to the subject matter of this application. 
     The treatment vessel  11  is configured as a circular shape and an airtight vacuum vessel to create a vacuum atmosphere inside. A side wall heater  12  is provided in a side wall of the treatment vessel  11 . A ceiling heater  13  is provided in a ceiling (i.e., a top board) of the treatment vessel  11 . A ceiling surface  14  of the ceiling (i.e., the top board) of the treatment vessel  11  is formed as a horizontal flat surface and the temperature of the ceiling surface  14  is controlled by the ceiling heater  13 . Here, when the film deposition gas that can form a film at a relatively low temperature is used, the heat by the side wall heater  12  or the ceiling heater  13  is not necessary. 
     The stage  21  is provided at a lower side of the treatment vessel  11 . The stage  21  constitutes the pedestal on which the substrate (i.e., the wafer W) is placed. The stage  21  is formed as a circular shape and the wafer W is placed on a horizontally formed surface (i.e., a top surface). Here, the substrate is not limited to the wafer W, and alternatively a glass substrate for manufacturing a flat panel display may be processed. 
     A stage heater  20  is embedded in the stage  21 . The stage heater  20  heats a placed wafer W so that a protective film can be formed on the wafer W placed on the stage  21 . Here, when the film deposition gas that can form a film at a relatively low temperature is used, it is not necessary to heat the placed wafer W by the stage heater  20 . 
     The stage  21  is supported by the treatment vessel  11  through a support column  22  provided on a bottom surface of the treatment vessel  11 . Lift pins  23  that are vertically moved are provided at positions outside of the periphery of the support column  22  in a circumferential direction. The lift pins  23  are inserted into respective through-holes provided at intervals in a circumferential direction of the stage  21 . In  FIG. 1 , two out of three lift pins  23  that are provided, are illustrated. The lift pins  23  are controlled and moved up and down by a lifting mechanism  24 . When the lifting pin  23  protrudes and recedes from a surface of the stage  21 , the wafer W is transferred between a conveying mechanism (which is not illustrated) and the stage  21 . 
     An exhaust port  31 , which is opened, provided in the side wall of the treatment vessel  11 . The exhaust port  31  is connected to an exhaust mechanism  32 . The exhaust mechanism  32  is constituted by a vacuum pump, a valve, and so on with an exhaust pipe to adjust an exhaust flow rate from the exhaust port  31 . Adjusting the exhaust flow rate by the exhaust mechanism  32  controls pressure in the treatment vessel  11 . Here, a transfer port of the wafer W, which is not illustrated, is formed to be able to open and close at a position different from the position where the exhaust port  31  is opened in the side wall of the treatment vessel  11 . 
     The gas nozzle  41  is also provided in the side wall of the treatment vessel  11 . The gas nozzle  41  supplies the film deposition gas that includes the composition for film deposition described above into the treatment vessel  11 . The composition for film deposition contained in the film deposition gas includes a first component M 1  and a second component M 2 . The first component M 1  is included in a first film deposition gas, the second component M 2  is included in a second film deposition gas, and the first component M 1  and the second component M 2  are supplied into the treatment vessel  11 . 
     The first component M 1  included in the first film deposition gas is a monomer that can polymerize with the second component M 2  to form a nitrogen-containing carbonyl compound. In the embodiment, 1,3-bis(isocyanatomethyl)cyclohexane (hereinafter referred to as H6XDI), which is a bifunctional alicyclic isocyanate, is used as the first component M 1 . Here, the first component M 1  is not limited to H6XDI, and may be any compound that is suitable for use as the first component of the above-described composition for film deposition. 
     The second component M 2  included in the second film deposition gas is a monomer that can polymerize with the first component M 1  to form a nitrogen-containing carbonyl compound. In the embodiment, 1,3-bis(aminomethyl)cyclohexane (which will be hereinafter referred to as H6XDA) that is a two-functional alicyclic amine is used as the second component M 2 . Here, the second component M 2  is not limited to H6XDA, and may be any compound that is suitable for use as the second component of the above-described composition for film deposition. 
     The gas nozzle  41  constitutes the supply (i.e., a film deposition gas supply) to supply the film deposition gas (i.e., the first film deposition gas and the second film deposition gas) for forming the protective film described above. The gas nozzle  41  is provided in the side wall of the treatment vessel  11  on a side opposite to the exhaust port  31  as viewed from the center of the stage  21 . 
     The gas nozzle  41  is formed to project from the side wall of the treatment vessel  11  toward the center of the treatment vessel  11 . An end of the gas nozzle  41  horizontally extends from the side wall of the treatment vessel  11 . The film deposition gas is discharged from a discharging port opened at the end of the gas nozzle  41  into the treatment vessel  11 , flows in a direction of an arrow of a dashed line illustrated in  FIG. 1 , and is exhausted from the exhaust port  31 . Here, the end of the gas nozzle  41  is not limited to this shape. To increase the efficiency of film deposition, the end of the gas nozzle  41  may be extending obliquely downward toward the placed wafer W or extending obliquely upward toward the ceiling surface  14  of the treatment vessel  11 . 
     When the end of the gas nozzle  41  is shaped to extend obliquely upward toward the ceiling surface  14  of the treatment vessel  11 , the discharged film deposition gas collides with the ceiling surface  14  of the treatment vessel  11  before being supplied to the wafer W. An area where the gas collides with the ceiling surface  14  is, for example, at a position closer to the discharging port of the gas nozzle  41  than the center of the stage  21  and is near an end of the wafer W in a planar view. 
     As described, the film deposition gas collides with the ceiling surface  14  and is supplied to the wafer W, so that the film deposition gas discharged from the gas nozzle  41  travels a greater distance to reach the wafer W than the film deposition gas travels when the film deposition gas is directly supplied from the gas nozzle  41  toward the wafer W. When a distance in which the film deposition gas travels in the treatment vessel  11  increases, the film deposition gas diffuses laterally and is supplied with high uniformity in a surface of the wafer W. 
     The exhaust port  31  is not limited to a configuration in which the exhaust port  31  is provided in the side wall of the treatment vessel  11  as described above. The exhaust port  31  may be provided in the bottom surface of the treatment vessel  11 . Additionally, the gas nozzle  41  is not limited to a configuration in which the gas nozzle  41  is provided in the side wall of the treatment vessel  11  as described above. The gas nozzle  41  may be provided in the ceiling of the treatment vessel  11 . Here, it is preferable that an exhaust port  31  and a gas nozzle  41  are provided in the side wall of the treatment vessel  11  as described above in order to form an air flow of the film deposition gas so that the film deposition gas flows from one end to the other end of the surface of the wafer W and film deposition is performed on the wafer W with high uniformity. 
     The temperature of the film deposition gas discharged from the gas nozzle  41  is selectable, but the temperature observed until the film deposition gas is supplied to the gas nozzle  41  is preferably higher than the temperature in the treatment vessel  11  in order to prevent the film deposition gas from condensing in a flow path before the film deposition gas is supplied to the gas nozzle  41 . In this case, the film deposition gas cools upon being discharged into the treatment vessel  11  and is supplied to the wafer W. The wafer W then adsorbs the film deposition gas being supplied to the treatment vessel  11  with the decrease in the temperature of the film deposition gas, adsorption of the film deposition gas for the wafer W becomes high, and the film deposition proceeds efficiently. Additionally, with respect to further increasing the adsorption of the film deposition gas for the wafer W, it is preferable that the temperature in the treatment vessel  11  is higher than the temperature of the wafer W (or the temperature of the stage  21  in which the stage heater  20  is embedded). 
     The film deposition apparatus  1  includes a gas supply pipe  52  connected to the gas nozzle  41  from the outside of the treatment vessel  11 . The gas supply pipe  52  includes gas introduction pipes  53  and  54  branched at an upstream side. An upstream side of a gas introduction pipe  53  is connected to a vaporizing part  62  through a flow adjustment part  61  and a valve V 1  in the indicated order. 
     In the vaporizing part  62 , the first component M 1  (H6XDI) is stored in a liquid state. The vaporizing part  62  includes a heater (which is not illustrated) for heating the H6XDI. One end of a gas supply pipe  63 A is connected to the vaporizing part  62 , and the other end of the gas supply pipe  63 A is connected to an N2 (nitrogen) gas supply source  65  through a valve V 2  and a gas heater  64  in the indicated order. With such a configuration, heated N2 gas is supplied to the vaporizing part  62 , H6XDI in the vaporizing part  62  is vaporized, and mixed gas of the N2 gas used for vaporizing and H6XDI gas can be introduced to the gas nozzle  41  as the first film deposition gas. 
     The gas supply pipe  63 A branches to form a gas supply pipe  63 B at a position in a downstream direction from the gas heater  64  and in an upstream direction from the valve V 2 . A downstream end of the gas supply pipe  63 B is connected to the gas introduction pipe  53  at a position in a downstream direction from the valve V 1  and in an upstream direction from the flow adjustment part  61  through a valve V 3 . With such a configuration, when the first film deposition gas described above is not supplied to the gas nozzle  41 , the N2 gas heated by the gas heater  64  is introduced to the gas nozzle  41  without going through the vaporizing part  62 . 
     In  FIG. 1 , a first film deposition gas supply mechanism  5 A includes the flow adjustment part  61 , the vaporizing part  62 , the gas heater  64 , the N2 gas supply source  65 , the valves V 1  to V 3 , the gas supply pipes  63 A and  63 B, and a portion of the gas introduction pipe  53  at an upstream side of the flow adjustment part  61 . 
     An upstream side of a gas introduction pipe  54  is connected to a vaporizing part  72  through a flow adjustment part  71  and a valve V 4  in the indicated order. In the vaporizing part  72 , the second component M 2  (H6XDA) is stored in a liquid state. The vaporizing part  72  includes a heater (which is not illustrated) to heat the H6XDA. One end of a gas supply pipe  73 A is connected to the vaporizing part  72 , and the other end of the gas supply pipe  73 A is connected to an N2 (nitrogen) gas supply source  75  through a valve V 5  and a gas heater  74  in the indicated order. With such a configuration, heated N2 gas is supplied to the vaporizing part  72 , H6XDA in the vaporizing part  72  is vaporized, and mixed gas of the N2 gas used for vaporizing and H6XDA gas can be introduced to the gas nozzle  41  as the second film deposition gas. 
     The gas supply pipe  73 A branches to form a gas supply pipe  73 B at a position in a downstream direction from the gas heater  74  and in an upstream direction from the valve V 5 . A downstream end of the gas supply pipe  73 B is connected to the gas introduction pipe  54  at a position in a downstream direction from the valve V 4  and in an upstream direction from the flow adjustment part  71  through a valve V 6 . With such a configuration, when the second film deposition gas described above is not supplied to the gas nozzle  41 , the N2 gas heated by the gas heater  74  is introduced to the gas nozzle  41  without going through the vaporizing part  72 . 
     In  FIG. 1 , a second film deposition gas supply mechanism  5 B includes the flow adjustment part  71 , the vaporizing part  72 , the gas heater  74 , the N2 gas supply source  75 , the valves V 4  to V 6 , the gas supply pipes  73 A and  73 B, and a portion of the gas introduction pipe  54  at an upstream side of the flow adjustment part  71 , described above. 
     For the gas supply pipe  52  and the gas introduction pipes  53  and  54 , a pipe heater  60 , for example, is provided around each of the pipes to heat the inside of a corresponding pipe to prevent H6XDI and H6XDA in the flowing film deposition gas from condensing. The pipe heater  60  adjusts the temperature of the film deposition gas to be discharged from the gas nozzle  41 . In the embodiment, for convenience of illustration, the pipe heater  60  is illustrated only in a part of the pipe, but the pipe heater  60  is provided over the entire length of the pipe to prevent condensation. 
     When gas supplied from the gas nozzle  41  into the treatment vessel  11  is simply described as N2 gas, the gas indicates N2 gas alone supplied without going through the vaporizing parts  62  and  72  (i.e., bypassed) as described above, and is distinguished from N2 gas contained in the film deposition gas. 
     The gas introduction pipes  53  and  54  are not limited to the configuration in which the gas supply pipe  52  connected to the gas nozzle  41  branches. The gas introduction pipes  53  and  54  may be configured as separate gas nozzles that respectively supply the first film deposition gas and the second film deposition gas into the treatment vessel  11 . This configuration can prevent the first film deposition gas and the second film deposition gas from reacting with each other and forming a film in a flow path before being supplied into the treatment vessel  11 . 
     The film deposition apparatus  1  includes a controller  10  that is a computer, and the controller  10  includes a program, a memory, and a CPU. The program includes an instruction (each step) to proceed processing for the wafer W, which will be described later. The program is stored in a computer storage medium such as a compact disk, a hard disk, a magneto-optical disk, and a DVD, and installed in the controller  10 . The controller  10  outputs a control signal to each part of the film deposition apparatus  1  by the program and the controller  10  controls an operation of each part. Specifically, operations such as control of an exhaust flow rate by the exhaust mechanism  32 , control of a flow rate of each gas supplied into the treatment vessel  11  by the flow adjustment parts  61  and  71 , control of an N2 gas supply from the N2 gas supply sources  65  and  75 , control of power supply to each heater, and control of the lift pins  23  by the lifting mechanism  24  are controlled by the control signal. 
     In the film deposition apparatus  1 , with the configuration described above, the composition for film deposition that includes the first component M 1  and the second component M 2  is supplied into the treatment vessel  11 , and the first component M 1  and the second component M 2  are polymerized to form a nitrogen-containing carbonyl compound. In the embodiment, polymerization of the first component M 1  (H6XDI) and the second component M 2  (H6XDA) forms a polymer (polyurea) containing a urea bond as a nitrogen-containing carbonyl compound. 
     The nitrogen-containing carbonyl compound is deposited as a polymer film on the wafer W by the first film deposition gas and the second film deposition gas being vapor-deposited and polymerized on the surface of the wafer W. The polymer film that is formed of a nitrogen-containing carbonyl compound can be a protective film that prevents a specific portion of the wafer W from being etched for example, as described below. 
     Here, the cis and trans isomers are present in H6XDI constituting the first component M 1  included in the first film deposition gas. Thus, the molecular structure of H6XDI contains cis isomers and trans isomers in a constant ratio. Additionally, the cis and trans isomers are also present in H6XDA that constitutes the second component M 2  included in the second film deposition gas. Thus, the molecular structure of H6XDA contains cis isomers and trans isomers in a constant ratio. 
     Accordingly, in the film deposition apparatus  1 , the molecular structure of the first component M 1  (H6XDI) included in the first film deposition gas supplied into the treatment vessel  11  and the molecular structure of the second component M 2  (H6XDA) included in the second deposition gas are asymmetric with each other. Therefore, in the film deposition process using the film deposition apparatus  1 , the occurrence of crystallization in a film can be suppressed, and the occurrence of film roughness and structural defects can be prevented. 
     In the embodiment, cis isomers and trans isomers are present in both the first component M 1  and the second component M 2 . However, a mixture of cis isomers and trans isomers may be present in only one of either the first component M 1  or the second component M 2  so that the molecular structure of the first component M 1  and the molecular structure of the second component M 2  are asymmetric. 
     Additionally, a case in which the molecular structure of the first component M 1  and the molecular structure of the second component M 2  are asymmetric, is not limited to the case in which either the first component M 1  or the second component M 2  contains cis-trans isomers as described above. For example, the molecular structure of the first component M 1  and the molecular structure of the second component M 2  are asymmetric with each other in a case of a cyclic compound and a chain compound, aromatic compounds with different orientations, and the like. 
     Next, a process performed on the wafer W using the film deposition apparatus  1  described above will be described with reference to  FIG. 2 .  FIG. 2  is a timing chart illustrating duration of time in which each gas is supplied. In the film deposition apparatus  1 , the wafer W is conveyed into the treatment vessel  11  by a conveying mechanism which is not illustrated and is transferred to the stage  21  through the lift pins  23 . The side wall heater  12 , the ceiling heater  13 , the stage heater  20 , and the pipe heater  60  are each heated to a predetermined temperature. Additionally, the inside of the treatment vessel  11  is adjusted to a vacuum atmosphere of a predetermined pressure. 
     The first film deposition gas that includes H6XDI is supplied from the first film deposition gas supply mechanism  5 A to the gas nozzle  41  and the N2 gas is supplied from the second film deposition gas supply mechanism  5 B to the gas nozzle  41 . These are mixed to be at 140° C. and discharged from the gas nozzle  41  into the treatment vessel  11  (see  FIG. 2  and time t 1 ). The mixed gas is cooled down to 100° C. in the treatment vessel  11 , is flowed through the treatment vessel  11  and is supplied to the wafer W. The mixed gas is further cooled on the wafer W to 80° C. and the first film deposition gas in the mixed gas is adsorbed on the wafer W. 
     Subsequently, the N2 gas is supplied from the first film deposition gas supply mechanism  5 A instead of the first film deposition gas, and only N2 gas is discharged from the gas nozzle  41  (time t 2 ). The N2 gas operates as a purge gas and the first film deposition gas that is not adsorbed on the wafer W in the treatment vessel  11  is purged. 
     Subsequently, the second film deposition gas that includes B6XDA is supplied to the gas nozzle  41  from the second film deposition gas supply mechanism  5 B. These are mixed to be at 140° C. and discharged from the gas nozzle  41  (time t 3 ). The mixed gas including the second film deposition gas is cooled down in the treatment vessel  11 , is flowed through the treatment vessel  11 , is supplied to the wafer W, and is further cooled down on the wafer W surface, in a manner similar to the mixed gas that includes the first film deposition gas supplied into the treatment vessel  11  from the time t 1  to the time t 2 . The second film deposition gas included in the mixed gas is adsorbed on the wafer W. 
     The adsorbed second film deposition gas polymerizes with the first film deposition gas already adsorbed on the wafer W, and a polyurea film is formed on the surface of the wafer W. Consequently, the N2 gas is supplied from the second film deposition gas supply mechanism  5 B instead of the second film deposition gas, and only N2 gas is discharged from the gas nozzle  41  (time t 4 ). The N2 gas operates as a purge gas to purge the second film deposition gas that is not adsorbed on the wafer W in the treatment vessel  11 . 
     In a series of the processes described above, the gas nozzle  41  first discharges the mixed gas including the first film deposition gas, then discharges only the N2 gas, and finally discharges the mixed gas including the second film deposition gas. When this series of the processes is defined as one cycle, the cycle is repeated after the time t 4 , and the polyurea film thickness increases. When a predetermined number of cycles are performed, the discharge of gas from the gas nozzle  41  stops. 
     In the embodiment, the molecular structure of the first component M 1  (H6XDI) included in the first film deposition gas and the molecular structure of the second component M 2  (H6XDA) included in the second film deposition gas are asymmetric with each other. In the film deposition apparatus  1 , because the first film deposition gas and the second film deposition gas are supplied to the wafer W in the treatment vessel  11 , it is possible to obtain an effect similar to a case in which the composition for film deposition described above is used. That is, according to the film deposition apparatus  1  of the embodiment, the occurrence of crystallization in a film can be suppressed, and the occurrence of film roughness and structural defects can be prevented in a film deposition process. 
     An example of a process performed using the film deposition apparatus  1  and an etching apparatus will be described.  FIG. 3( a )  illustrates a surface portion of the wafer W that is formed by stacking an underlayer film  81 , an interlayer insulating film  82 , and a hard mask film  83  in the order from the lower side to the upper side, and a pattern  84 , which is an opening, is formed in the hard mask film  83 . In etching the interlayer insulating film  82  through the pattern  84  to form a recess for embedding a wiring, the polyurea film described above is formed as a protective film so that a side wall of the recess is not damaged. 
     First, after a recess  85  is formed in the interlayer insulating film  82  by the etching apparatus ( FIG. 3( b ) ), a polyurea film  86  is formed on the surface of the wafer W by the film deposition apparatus  1  described above. This coats the side wall and bottom of the recess  85  with the polyurea film  86  ( FIG. 3( c ) ). Subsequently, the wafer W is conveyed to the etching apparatus and the depth of the recess  85  is increased by anisotropic etching. At this etching, the bottom of the recess  85  is etched in a state in which the polyurea film  86  is deposited on the side wall of the recess  85  and protects the side wall of the recess  85  ( FIG. 4( a ) ). Next, the wafer W is conveyed to the film deposition apparatus  1  and a polyurea film  86  is newly formed on the surface of the wafer W ( FIG. 4( b ) ). Next, the bottom of the recess  85  is etched again in a state in which the side wall of the recess  85  is protected by the polyurea film  86 , and the etching ends when the underlayer film  81  is exposed ( FIG. 4( c ) ). Subsequently, the hard mask film  83  and the polyurea film  86  are removed by dry etching or wet etching ( FIG. 5 ). 
     As illustrated in  FIG. 3  to  FIG. 5 , even when the etching apparatus is combined with the film deposition apparatus  1 , the molecular structure of the first component M 1  (H6XDI) included in the first film deposition gas and the molecular structure of the second component M 2  (H6XDA) included in the second film deposition gas are asymmetric with each other. This can suppress the occurrence of crystallization in a film, and prevent the occurrence of film roughness and structural defects during a film deposition process. Therefore, this can improve throughput in a manufacturing process of a semiconductor device for example. 
     If the temperature of the first film deposition gas and the temperature of the second film deposition gas are relatively high, adsorption and film deposition on a surface tend to be difficult to occur. Thus, as illustrated in a timing chart of  FIG. 6 , the first film deposition gas and the second film deposition gas may be simultaneously supplied to the gas nozzle  41  and discharged from the gas nozzle  41  into the treatment vessel  11 . 
     As illustrated in  FIG. 6 , even when the first film deposition gas and the second film deposition gas are simultaneously supplied to the gas nozzle  41 , the molecular structure of the first component M 1  (H6XDI) included in the first film deposition gas and the molecular structure of the second component M 2  (H6XDA) included in the second film deposition gas are asymmetric with each other. Therefore, even when the first film deposition gas and the second film deposition gas are simultaneously supplied to the gas nozzle  41 , the occurrence of crystallization in a film can be suppressed, and the occurrence of film roughness and structurals defect can be prevented in a film deposition process. 
     EXAMPLES 
     In the following, the present invention will be described specifically with reference to examples. In the examples and a comparative example, measurement and evaluation were performed as follows. 
     [Film Deposition] 
     A film deposition apparatus  101  illustrated in  FIG. 7  was used to form a polymer film. Here, in  FIG. 7 , the portion common to  FIG. 1  is referred by a reference numeral generated by adding 100 to each reference numeral of  FIG. 1  and a description is omitted. Specifically, the wafer W was placed in a treatment vessel  111 , and a film deposition gas (the composition for film deposition that includes the first component M 1  and the second component M 2 ) was supplied to form a polymer film on the wafer W at room temperature. The film deposition was performed on four wafers W simultaneously. A 300 mm diameter silicon wafer was used for the wafer W. 
     [Heat Treatment] 
     A wafer W on which a polymer film is formed, is placed in a hot plate (which is not illustrated) of a nitrogen atmosphere and heated at 250° C. for 5 minutes. 
     [Dark Field Observation] 
     The surface of the polymer film deposited on the wafer W was observed before and after heat treatment in the dark field using an optical thin film and scatterometry (OCD) measuring device (which is a device named “n&amp;k Analyzer” and manufactured by n&amp;k Technology). When light scattering was observed by the dark field observation, it was evaluated that film roughness (crystallization) occurred. The evaluation was performed using pictures of the surface of the film imaged in the dark field (as illustrated in  FIG. 8  and  FIG. 9 ). In  FIG. 8  and  FIG. 9 , a spotted area indicates light scattering, and a white area indicates no light scattering. 
     In the following, an example and a comparative example will be described. 
     Example 1 
     1,3-bis(isocyanatomethyl)cyclohexane (H6XDI) was supplied as the first component M 1 , 1,3-bis(aminomethyl)cyclohexane (H6XDA) was supplied as the second component M 2 , and a polymer film is formed on the wafer W. Both H6XDI constituting the first component M 1  and H6XDA constituting the second component M 2  are compounds in which cis isomers and trans isomers are present. In Example 1, the surface of the film was evaluated before and after the heat treatment. The results are indicated in Table 1 and  FIG. 8 . 
     Comparative Example 1 
     With the exception that 1,3-bis(isocyanatomethyl)benzene (XDI) was supplied instead of H6XDI as the first component M 1 , and 1,3-bis(aminomethyl)benzene (XDA) was supplied instead of H6XDA as the second component M 2 , the film was formed and evaluated in a manner similar to Example 1. Both XDI and XDA are meta-oriented aromatic compounds. The results are indicated in Table 1 and  FIG. 9 . 
     
       
         
           
               
               
               
               
             
               
                   
                 TABLE 1 
               
               
                   
                   
               
               
                   
                   
                   
                 COMPARATIVE 
               
               
                   
                   
                 EXAMPLE 
                 EXAMPLE 
               
               
                   
                   
                 1 
                 1 
               
               
                   
                   
               
             
            
               
                   
                 FIRST COMPONENT M1 
                 H6XDI 
                 XDI 
               
               
                   
                 SECOND COMPONENT M2 
                 H6XDA 
                 XDA 
               
               
                   
                 LIGHT SCATTERING 
                 NOT  
                 NOT  
               
               
                   
                 (BEFORE HEAT 
                 OBSERVED 
                 OBSERVED 
               
               
                   
                 TREATMENT) 
                   
                   
               
               
                   
                 LIGHT SCATTERING 
                 NOT  
                 OBSERVED 
               
               
                   
                 (AFTER HEAT 
                 OBSERVED 
                   
               
               
                   
                 TREATMENT) 
               
               
                   
                   
               
            
           
         
       
     
     From Table 1, when the cis-trans isomer exists in the first component M 1  (Example 1), light scattering was not observed before and after the heat treatment. 
     With respect to this, when both the first component M 1  and the second component are aromatic compounds and have the same orientation in the basic structure (Comparative example 1), light scattering was observed after the heat treatment. 
     From these results, it has been found that film roughness (crystallization in a film) is suppressed. This can be achieved by performing the film deposition process using a composition for film deposition in which the molecular structures of the first component that polymerizes with the second component to form a nitrogen-containing carbonyl compound is asymmetric with each other. 
     Example embodiments of the present invention have been described in detail above, but the present invention is not limited to a specific embodiment. The various modifications and alterations may be made within the scope of the invention described in the claims. 
     This international application is based upon and claims the benefit of priority of the prior Japanese Patent Application No. 2018-108154, filed Jun. 5, 2018, the entire contents of which are incorporated herein by reference. 
     DESCRIPTION OF REFERENCE SYMBOLS 
     
         
         W wafer 
           1  film deposition apparatus 
           11  treatment vessel 
           21  stage 
           20  stage heater 
           31  exhaust port 
           41  gas nozzle 
           60  pipe heater